JP4615505B2 - Ink set for ink jet recording and ink jet recording method - Google Patents

Description

  The present invention relates to an ink set for ink jet recording and an ink jet recording method using the ink set. More specifically, the present invention relates to an ink set for ink jet recording and an ink jet suitable for forming high-quality images at high speed using multiple liquids. It relates to a recording method.

  An ink jet system that discharges ink in droplets from an ink discharge port such as a nozzle is used in many printers because it is small and inexpensive, and can form an image without contact with a print medium. Among these ink jet methods, the piezo ink jet method that ejects ink using deformation of piezoelectric elements and the thermal ink jet method that ejects ink droplets by utilizing the boiling phenomenon of ink due to thermal energy achieve high resolution and high printability. It has the feature of being excellent.

  2. Description of the Related Art Currently, high speed and high image quality when ink is ejected onto a non-water-absorbing recording medium such as plain paper or plastic by an ink jet printer are important issues.

  Ink-jet recording continuously discharges ink (liquid) droplets as droplet n1, droplet n2, droplet n3,..., Droplet nx, and droplets n1 and n2 on a recording medium. , Droplets n3,..., Lines are formed with droplets nx, or images are formed. However, if it takes time to penetrate the droplets after droplet ejection, bleeding tends to occur in the image. In addition, there are practical problems such as mixing between adjacent ink droplets n1 and ink droplets n2 and hindering sharp image formation. When mixing between droplets, adjacent droplets that have been struck are united to cause movement of the droplets, so that they deviate from the landing position, and when drawing thin lines, the line width is uneven. When a colored surface is drawn, color unevenness or the like occurs.

  One of the methods for suppressing image bleeding and non-uniform line width is a method for promoting ink curing. As one of them, a technique for hardening and fixing by radiation rather than volatilization of the ink solvent has been proposed. Furthermore, in order to give a high-definition drawing property, there is one that uses a two-component ink and causes both to react on a recording medium. For example, after attaching a liquid having a basic polymer, an anionic dye A method of recording an ink containing an anionic compound and a coloring material after applying a liquid composition containing a cationic substance (for example, see Patent Document 1) 2), a recording method using an ink containing a photocurable resin on one side and a photopolymerization initiator on the other (see, for example, Patent Document 3).

  However, these methods have a certain effect in suppressing blurring of the image, but are insufficient for eliminating the non-uniform line width and color unevenness caused by mixing between droplets. Therefore, there is a concern that the drying speed is slow due to the presence of the dye, and the precipitated dye is likely to be unevenly distributed, resulting in a decrease in image quality.

As a technique related to the above, there is a technique in which a pigment is used as a coloring component and cured and fixed by radiation (for example, see Patent Document 4). Here, a pixel is formed using one of an ink containing a solidifying monomer and an ink containing a pigment dispersion, and then the pixel is formed at the same point as the image on the other side. Etc. are described.
In addition, an ink composition containing a reactive monomer, a colorant and the like together with water and an aggregating solution containing an aggregating agent that generates an agglomerate are used, and after the aggregating solution is adhered onto a recording medium, the ink composition Has been described (see, for example, Patent Document 5). Furthermore, there is a description that a monomer-containing ink composition is applied after the reaction liquid containing a photopolymerization initiator is applied over the entire surface, and ultraviolet irradiation is performed (for example, see Patent Document 6).

In addition to the above, there is also a description relating to ink ejection that is divided into two types and overlapped with each other (see, for example, Patent Document 7).
Japanese Unexamined Patent Publication No. 63-60783 JP-A-8-174997 Japanese Patent No. 3478495 Japanese Patent Laid-Open No. 8-21818 JP 2001-348519 A Japanese Patent No. 3642152 JP 2000-135781 A

  However, when a plurality of types of liquids having different compositions are mixed on a recording medium, when the other liquid containing the pigment is ejected onto one liquid, the liquid is in an unstable state. If it is adjacent to a portion that has not been ejected, the pigment-containing liquid tends to spread to the portion that has not been ejected, and in particular, fine lines formed while ink is ejected at high density, such as reversed characters, are crushed. There is a problem that it ends up.

  The present invention has been made in view of the above, and provides an inkjet recording ink set and an inkjet recording method capable of recording an inkjet image having a high droplet ejection density, such as a reversed character, with a high reproducibility of a fine image such as a fine line. It is an object to achieve this purpose.

Specific means for achieving the above object are as follows.
<1> comprising at least a lipophilic recording liquid for forming an image containing a polymerizable material, and a lipophilic processing liquid having a composition different from that of the recording liquid,
The viscosity of the treatment liquid is 100 mPa · s or more at 25 ° C., and the treatment liquid is an ink set for ink jet recording having any one of the following requirements (I) to ( II ).
(I) A polymerizable material having a viscosity of 100 mPa · s or higher at 25 ° C. and higher in viscosity than the polymerizable material contained in the recording liquid is included.
(II) The viscosity is 100 mPa · s or higher at 25 ° C., the boiling point is higher than 100 ° C., and it is lipophilic, and is represented by the formulas [S-1] to [S-9] and (SH-27) described later. including at least one high-boiling organic solvent selected from the compounds
( However, in the formula [S-6] described below, R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms. In [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
<2> The ink set for inkjet recording according to <1>, wherein the high-boiling organic solvent includes at least one selected from compounds represented by (SH-1) to (SH-27) described later. is there.
<3> The polymerizable material shown in the (I) to the total mass of the treatment liquid, wherein the total content of the high-boiling organic Solvent shown in (II) is not less than 50 wt% <1> or <2> The ink set for ink-jet recording described in 1.
<4> The ink set for inkjet recording according to any one of <1> to <3>, wherein the recording liquid includes a colorant.
<5> The ink set for inkjet recording according to any one of <1> to <4>, wherein the content of the colorant in the treatment liquid is 0% by mass or more and less than 1% by mass with respect to the total mass. is there.

< 6 > Using the ink set according to any one of <1> to < 5 >, the processing liquid is recorded in advance in the same or wider range than the image formed with the recording liquid. This is an ink jet recording method in which an image is formed by ejecting the recording liquid after being applied to a medium.
< 7 > A desired image is recorded by ejecting the recording liquid onto the recording medium with at least a droplet a1 and a droplet a2, and the droplet a1 and the droplet a2 are ejected with overlapping portions. The inkjet recording method according to < 6 >.
< 8 > The inkjet recording method according to < 7 >, wherein an overlapping ratio in the overlapping portion is 10% or more and 90% or less.
< 9 > The inkjet recording method according to any one of < 7 > to < 8 >, wherein the droplet size of the droplet a1 and the droplet a2 is 0.1 picoliter or more and 100 picoliter or less. .
< 10 > The inkjet recording method according to any one of < 6 > to < 9 >, wherein active energy is applied to the image after droplet ejection of the recording liquid to polymerize or crosslink the polymerizable material .

  According to the present invention, it is possible to provide an ink set for ink jet recording and an ink jet recording method capable of recording an ink jet image having a high droplet ejection density such as a reversed character with good reproducibility of a fine image such as a fine line.

The ink set for inkjet recording of the present invention is an ink set comprising at least an oleophilic recording liquid for forming an image and an oleophilic processing liquid having a composition different from that of the recording liquid. The recording liquid contains a polymerizable material, the viscosity of the processing liquid is 100 mPa · s or more at 25 ° C., and the processing liquid is any one of the following (I) to ( II ): It is characterized by having requirements.
(I) A polymerizable material having a viscosity of 100 mPa · s or higher at 25 ° C. and higher in viscosity than the polymerizable material contained in the recording liquid is included.
(II) The viscosity is 100 mPa · s or higher at 25 ° C., the boiling point is higher than 100 ° C., and it is lipophilic, and is represented by the formulas [S-1] to [S-9] and (SH-27) described later. including at least one high-boiling organic solvent selected from the compounds
( However, in the formula [S-6] described below, R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms. In [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
Further, the ink jet recording method of the present invention uses the ink set described above, and after applying the treatment liquid to a recording medium in advance in the same range as the image formed by the recording liquid or wider than the image, the recording The liquid is ejected from an ink discharge port (head) in an ink jet printer to form an image.

In a general inkjet image recording method, when a high image density is to be obtained, droplets for forming an image on a recording medium are ejected continuously (or simultaneously) so as to have overlapping portions. That is, after a droplet a1 is ejected as a recording liquid for forming an image, a subsequent droplet a2 is ejected so as to have an overlapping portion with the droplet a1.
In the present invention, before applying the recording liquid for forming the image, a treatment liquid having a composition different from that of the recording liquid is applied in advance to the same area as the image formed by droplets of the recording liquid on the recording medium or the recording liquid. Applies to a wider area than the image.

In a conventional inkjet image recording method, in order to obtain a high image density, adjacent droplets that are applied with overlapping portions (droplets a1 and a2 as recording liquids are ejected so as to have overlapping portions). If the droplets remain on the medium and are in contact with each other before drying, there is a problem that the image blurs and the line width of the fine lines becomes nonuniform and the sharp image formation is impaired. It was.
However, as in the present invention, by applying a high-viscosity treatment liquid on the recording medium in advance before the recording liquid is ejected, the liquid droplets a1 and a2 have overlapping portions. Even if applied, the coalescence between the droplets a1 and a2 is suppressed, and the occurrence of blurring of the image and variations in line width such as fine lines in the image are effectively prevented. It can be formed, and an inkjet image having a high droplet ejection density such as a reversed character can be recorded with good reproducibility of a fine image such as a fine line.
For example, this is particularly effective when an image is recorded on a non-permeable or slowly permeable recording medium having low liquid absorbency as the recording medium.

The recording liquid is usually a single liquid, and a plurality of droplets are ejected from the ink ejection port so as to overlap each other. In more detail, the droplets a1, a2, a3, ... An droplet is ejected so that an overlaps. It may be a mode in which the droplets are ejected at the same time, or may be a preceding droplet and a succeeding droplet that are in a relationship between the preceding droplet and the subsequent droplet, and is preferably a preceding droplet and a subsequent droplet. .
However, the present invention is not limited to these, and can also be used in an embodiment where adjacent droplets do not overlap.

<Ink set for inkjet recording>
First, the ink set of the present invention will be described in detail.
The ink set for ink jet recording of the present invention comprises at least an oleophilic recording liquid for forming an image, and an oleophilic processing liquid having a composition different from that of the recording liquid, It contains a polymerizable material, the treatment liquid has a viscosity of 100 mPa · s or more at 25 ° C., and the treatment liquid further has any one of the following requirements (I) to ( II ).
(I) A polymerizable material having a viscosity of 100 mPa · s or higher at 25 ° C. and higher in viscosity than the polymerizable material contained in the recording liquid is included.
(II) The viscosity is 100 mPa · s or higher at 25 ° C., the boiling point is higher than 100 ° C., and it is lipophilic, and is represented by the formulas [S-1] to [S-9] and (SH-27) described later. including at least one high-boiling organic solvent selected from the compounds
( However, in the formula [S-6] described below, R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms. In [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms.)

(viscosity)
The treatment liquid in the present invention is required to have a viscosity of 100 mPa · s or more at 25 ° C. When the viscosity of the treatment liquid previously applied to the same or wider range than the image formed with the recording liquid is less than 100 mPa · s at 25 ° C., an ink jet image having a high droplet ejection density such as reversed characters is recorded. In this case, a fine image such as a thin line cannot be reproduced well.

In addition, from the viewpoint of better exhibiting the reproducibility of the fine image as described above, the viscosity of the treatment liquid at 25 ° C. is more preferably 200 mPa · s or more, and particularly preferably 300 mPa · s or more. preferable.
Further, the treatment liquid needs to be in a liquid form from the viewpoint of being applied to the recording medium by a method such as ejection or coating with an inkjet head. Here, “liquid” means that the surface of the processing liquid is not completely solid and has fluidity. Specifically, the processing liquid is transferred to the permeation medium by pressing a permeation medium such as plain paper. It can be judged by whether or not. Preferably, the “liquid” viscosity (25 ° C.) is preferably 10,000 mPa or less.

In order to bring the viscosity of the treatment liquid at 25 ° C. into the above range, a method of appropriately selecting and configuring the composition of the liquid can be mentioned. In the present invention, a high-viscosity high-boiling organic solvent, a high-viscosity polymerizable material, and At least one polymer is contained.
More specifically,
(I) A polymerizable material having a viscosity of 100 mPa · s or higher (more preferably 200 mPa · s or higher) at 25 ° C. and having a higher viscosity than the polymerizable material contained in the recording liquid is included.
(II) The viscosity is 100 mPa · s or higher (more preferably 200 mPa · s or higher) at 25 ° C., the boiling point is higher than 100 ° C., and lipophilic, and the following formulas [S-1] to [S-9] and at least one high-boiling organic solvent including selected from compounds represented by (SH-27)
( However, in the formula [S-6] described below, R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms. In [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
Any one of the requirements is provided. The polymerizable material shown in the (I) to the total weight of the developer, the total content of the high boiling organic Solvent shown in the (II) is preferably at least 50 mass%, is 60 wt% or more It is more preferable that the content is 70% by mass or more.
Details of the composition of these treatment liquids (specific examples) will be described later.

  Here, the viscosity at 25 ° C. of the recording liquid and the processing liquid in the present invention is measured with a laboratory-use handheld digital viscometer viscostick (manufactured by Maruyasu Kogyo Co., Ltd.) while maintaining the temperature at 25 ° C.

  Further, the viscosity of the recording liquid ejected onto the recording medium by the ink jet recording method varies depending on the apparatus, but generally the viscosity at 25 ° C. is preferably in the range of 5 to 100 mPa · s, more preferably 10 to 80 mPa · s. preferable.

(Composition of recording liquid and processing liquid)
(1) Composition of recording liquid The composition of the recording liquid used in the ink set for inkjet recording of the present invention will be described. The recording liquid is configured to have at least a composition for forming an image, includes at least a polymerizable material, and includes a polymerization initiator, a lipophilic solvent, a colorant, and other components as necessary. be able to.
It is preferable that the recording liquid contains a colorant and the content of the colorant in the treatment liquid described later is 0% by mass or more and less than 1% by mass. Hereinafter, each component constituting the recording liquid will be described in detail.

~ (Recording liquid) polymerizable material ~
The recording liquid contains at least one polymerizable material for forming an image. The polymerizable material has a function of causing a polymerization reaction by an initiating species such as a radical generated from a polymerization initiator described later, and curing.

As the polymerizable material , a known polymerizable material such as a radical polymerization reaction, a cationic polymerization reaction, or a dimerization reaction can be applied. Addition polymerizable compound having at least one ethylenically unsaturated double bond, epoxy compound, oxetane compound, oxirane compound, polymer compound having maleimide group in side chain, photodimerization adjacent to aromatic nucleus is possible Cinnamyl group having an unsaturated double bond, a polymer compound having a cinnamylidene group or a chalcone group in the side chain, and the like, more preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, It is particularly preferable that the compound is selected from compounds having at least one ethylenically unsaturated bond, more preferably two or more (monofunctional or polyfunctional compound). Specifically, it can be appropriately selected from those widely known in the industrial field according to the present invention, for example, monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and Those having a chemical form such as a copolymer of

  In particular, various known polymerizable monomers known as cationic polymerizable monomers and radical polymerizable monomers are preferable, and specifically, acryloyl group, methacryloyl group, allyl group, vinyl group, internal double bond group in the molecule. (Maleic acid, etc.) and the like, and those having an epoxy group, oxetanyl group, etc. are preferable, and among them, a compound having an acryloyl group, a methacryloyl group, an epoxy group, or an oxetanyl group is preferable in that a curing reaction can be caused with low energy .

  Examples of the cationic polymerizable monomer include various publications such as JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-220526. The epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in the above are suitable.

Examples of the epoxy compound include aromatic epoxides and alicyclic epoxides.
Examples of monofunctional epoxy compounds include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.

Examples of polyfunctional epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl Adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′- Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxy Dioctyl hexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Liglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxy Examples include octane and 1,2,5,6-diepoxycyclooctane.
Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, Trahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like.

Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide. Divinyl ethers such as divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexa Nyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentane And polyfunctional vinyl ethers such as erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound refers to a compound having an oxetane ring, and a known oxetane compound is arbitrarily selected and used as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. it can.
As the compound having an oxetane ring, a compound having 1 to 4 oxetane rings in its structure is preferable. By using such a compound, it becomes easy to maintain the viscosity of the recording liquid in a favorable range of handling properties, and high adhesion to the recording medium after curing can be obtained.

  Examples of monofunctional oxetanes include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [ 1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-Ethylhexyl (3-ethyl-3-oxetanylmethyl) Ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl ( 3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydride Xylethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl- 3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of polyfunctional oxetanes include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene Glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3- Xetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-) Oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) Ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-o Cetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl) -3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl) -3-Oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3- And polyfunctional oxetanes such as oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

The compound having such an oxetane ring is described in detail in paragraphs [0021] to [0084] of JP-A No. 2003-341217, and the compounds described therein can be preferably used.
Among the oxetane compounds, it is preferable to use a compound having 1 to 2 oxetane rings from the viewpoint of the viscosity and tackiness of the recording liquid.

  The cationic polymerizable monomer may be used alone or in combination of two or more. From the viewpoint of effectively suppressing shrinkage during curing, at least one oxetane compound, an epoxy compound, and a vinyl ether compound. It is preferable to use in combination with at least one compound selected from the group consisting of:

In addition, various known radical polymerizable monomers that cause a polymerization reaction with an initiation species generated from a radical initiator are also preferable.
Examples of the radical polymerizable monomer include (meth) acrylates, (meth) acrylamides, aromatic vinyls 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”.

Examples of (meth) acrylates include the following.
Specific examples of monofunctional (meth) acrylates include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth). Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoeth (Meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl ( (Meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H perfluorodecyl (meth) acrylate, 4-butyl Phenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate Glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, Diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (Meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, Reethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxytyl succinic acid, 2- Methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, EO modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified noni Phenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate and the like.

  Specific examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-dimethyl. -1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate Bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di ( Examples include meth) acrylate, 1,9-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecane di (meth) acrylate.

  Specific examples of trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate Rate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

  Specific examples of tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionate dipentaerythritol tetra (meth) acrylate, ethoxylated penta Examples include erythritol tetra (meth) acrylate.

  Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Specific examples of hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa (meth) acrylate Etc.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide, (meth) acryloylmorpholine, etc. are mentioned.

  Specific examples of the aromatic vinyls include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoate. Acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4 -Hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octene Rusuchiren, 4-t-butoxycarbonyl styrene, 4-methoxystyrene, and a 4-t-butoxystyrene.

  In addition to the above, the radical polymerizable monomer in the present invention further includes vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [allyl acetate, etc.], halogen-containing monomers [vinylidene chloride]. Vinyl chloride], vinyl ether [methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, etc.], vinyl cyanide [(meth) acrylonitrile, etc.], olefin And the like [ethylene, propylene, etc.].

  Among the above, as the radical polymerizable monomer, (meth) acrylates and (meth) acrylamides are preferable from the viewpoint of curing speed, and tetrafunctional or higher (meth) acrylate is particularly preferable from the viewpoint of curing speed. Furthermore, from the viewpoint of the viscosity of the recording liquid, it is preferable to use a polyfunctional (meth) acrylate with a monofunctional or bifunctional (meth) acrylate or (meth) acrylamide.

A polymeric material may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the polymerizable material in the recording liquid is preferably in the range of 50 to 99.6% by mass, more preferably in the range of 70 to 99.0% by mass, based on the total solid content (mass). The range of ˜99.0% by mass is more preferable.
In addition, the content in the droplet (that is, the content when a volatile component is included) is preferably in the range of 20 to 98% by mass, and in the range of 40 to 95% by mass with respect to the total mass of the droplet. More preferably, the range of 50 to 90% by mass is particularly preferable.

The polymerizable material can also be contained in the treatment liquid, and the preferable content in that case is the same as described above. Details will be described later.

~ (Recording liquid) polymerization initiator ~
The recording liquid can be suitably configured using at least one kind of polymerization initiator. This polymerization initiator is a compound that generates an initiating species such as a radical by application of actinic light, heat, or both, and initiates, accelerates, and cures the polymerization reaction of the polymerizable material described above. Note that the polymerization initiator is not contained in the recording liquid but is preferably contained in a treatment liquid described later or other liquids, and is also preferred as an aspect in which both are included in the recording liquid and the treatment liquid.

In the polymerizable embodiment, it preferably contains a polymerization initiator that causes radical polymerization or cationic polymerization, and particularly preferably contains a photopolymerization initiator.
A polymerization initiator is a compound that undergoes a chemical change through the action of light or interaction with the electronically excited state of a sensitizing dye to generate at least one of a radical, an acid, and a base. From the viewpoint that polymerization can be initiated by a simple means of exposure, the photo radical generator or the photo acid generator is preferred.

  The photopolymerization initiator is an actinic ray to be irradiated, for example, 400 to 200 nm ultraviolet ray, far ultraviolet ray, g ray, h ray, i ray, KrF excimer laser beam, ArF excimer laser beam, electron beam, X ray, molecular beam. Or what has a sensitivity to an ion beam etc. can be selected suitably, and can be used.

  Specific photopolymerization initiators known to those skilled in the art can be used without limitation, and specifically, for example, Bruce M. et al. Monroe et al., Chemical Review, 93, 435 (1993). R. S. By Davidson, Journal of Photochemistry and biologic A: Chemistry, 73.81 (1993). J. P. Faussier “Photoinitiated Polymerization—Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al. , Prog. Polym. Sci. , 21, 1 (1996). Many are described. In addition, there are many chemical amplification type photoresists and compounds used for photocationic polymerization described in “Organic Materials for Imaging” (see Organic Electronics Materials Research Group, Bunshin Publishing (1993), pages 187-192). ing. Further, F.I. D. Saeva, Topics in Current Chemistry, 156, 59 (1990). G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993). H., et al. B. Shuster et al, JACS, 112, 6329 (1990). , I. D. F. Eaton et al, JACS, 102, 3298 (1980). A group of compounds that undergo bond oxidative or reductive cleavage through interaction with the electronically excited state of the sensitizing dye described in the above.

  Preferred photopolymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaarylbiimidazole compounds, (e) ketoxime ester compounds, f) borate compounds, (g) azinium compounds, (h) metallocene compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and the like.

  Preferable examples of the (a) aromatic ketones include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER J.M. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in RABEK (1993), p77-117. More preferable examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, and JP-B-47-22326. Α-substituted benzoin compounds, benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, Benzoin ethers described in JP-A-60-26403, JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, and α-aminobenzophenones described in European Patent 0284561A1, P-di (dimethyla) described in JP-A-2-211452 Nobenzoyl) benzene, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, acylphosphine described in JP-B-2-9596, JP-B-63- Examples thereof include thioxanthones described in Japanese Patent No. 61950, and coumarins described in Japanese Patent Publication No. 59-42864.

  Examples of the (b) aromatic onium salt compound include elements of groups V, VI and VII of the periodic table, specifically, N, P, As, Sb, Bi, O, S, Se, Te, or I. Of the aromatic onium salt. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. , 294442, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,344, and 2,833,827, sulfonium salts and diazonium salts (Such as benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, JP 63-138345 JP-A-63-142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. And compounds described in JP-B Nos. 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  The (c) “organic peroxide” includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3 ′, 4,4′- Tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxy) Carbonyl) benzophenone, 3,3′4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3′4 Peroxyesters such as 4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate are preferred. There.

  Examples of the (d) hexaarylbiimidazole include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2 , 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 '− Traphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  Examples of the (e) ketoxime ester compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyimino. Pentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of the (f) borate compound include compounds described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773.
Examples of the (g) azinium salt compound include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond as described in each gazette of No. can be mentioned.

  Examples of the (h) metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. And the iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  Examples of the (i) active ester compound include European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531, Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, European Patents 0199672, 84515, 199672, 0441115, and 0101122 , U.S. Pat. Nos. 4,618,564, 4,371,605 and 4,431,774, JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048, respectively. Kosho 62-6223, Shoko 63-143 No. 0, and include compounds described in the JP-A-59-174831.

  Preferred examples of the compound (j) having a carbon halogen bond include those described in Wakabayashi et al., Bull. Chem. Soc. Examples include compounds described in Japan, 42, 2924 (1969), compounds described in British Patent 1388492, compounds described in JP-A-53-133428, compounds described in German Patent 3333724, and the like. .

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like. A compound as described in German Patent No. 2641100, a compound described in German Patent No. 3333450, a group of compounds described in German Patent No. 3021590, or a group of compounds described in German Patent No. 3021599, etc. Can be mentioned.

  Preferable specific examples of the compounds represented by the above (a) to (j) include those shown below.

  It is preferable that the polymerization initiator is excellent in sensitivity. For example, it is not preferable from the viewpoint of storage stability to use one that causes thermal decomposition at a temperature of 80 ° C. or lower, and thermal decomposition occurs at a temperature up to 80 ° C. It is preferred to select a polymerization initiator that is not present.

  A polymerization initiator can be used 1 type or in combination of 2 or more types. Moreover, a well-known sensitizer can also be used together for the purpose of a sensitivity improvement in the range which does not impair the effect of this invention.

  As described above, the polymerization initiator can be contained in either the recording liquid or the processing liquid, or can be contained in another liquid. The content of the polymerization initiator in all of these liquids (that is, the ink set of the present invention) is such that the liquid ejected or applied onto the recording medium is from the viewpoint of temporal stability, curability, and curing speed. The amount is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 3 to 10% by mass with respect to the polymerizable or crosslinkable material applied per unit area.

  When the polymerization initiator is contained in both the recording liquid and the processing liquid, it can be appropriately selected and contained as long as the storage stability of the recording liquid can be maintained at a desired level.

  In addition, when there is too much content of a polymerization initiator, precipitation and isolation | separation with time may arise, or performance, such as the intensity | strength of an ink after hardening and abrasion resistance, may deteriorate.

~ (Recording liquid) sensitizer ~
In the present invention, a sensitizer (sensitizing dye) may be added for the purpose of improving the sensitivity of the polymerization initiator. Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squalium (for example, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (IX) to (XIII).

In formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.
In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (IX).
In the formula (XI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ^4, and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.
In formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferable specific examples of the compounds represented by the general formulas (IX) to (XIII) include the exemplified compounds (A-1) to (A-20) shown below.

~ (Recording liquid) co-sensitizer ~
Furthermore, a known compound having a function of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.
Examples of co-sensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56-75643. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. .
Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in JP-A-8-65779 H, Ge-H compound, etc. are mentioned.

~ (Recording liquid) Colorant ~
The recording liquid can be suitably configured using at least one colorant. The colorant may be contained in the treatment liquid and other liquids in addition to the recording liquid. However, the ink set of the present invention contains the recording liquid in the recording liquid and the treatment liquid content is 0 mass% or more and 1 mass. Less than% (more preferably not contained) is preferred.

  The colorant is not particularly limited, and can be appropriately selected from known water-soluble dyes, oil-soluble dyes, pigments, and the like. Among them, the recording liquid and the processing liquid according to the present invention are preferably composed of a water-insoluble organic solvent system from the viewpoint of the effect of the present invention, and an oil-soluble dye that is easily dispersed and dissolved in a water-insoluble medium, Preference is given to using pigments.

  The content of the colorant in the recording liquid is preferably 1 to 30% by mass, more preferably 1.5 to 25% by mass, and particularly preferably 2 to 15% by mass.

Hereinafter, the oil-soluble dye and pigment suitable for the present invention will be mainly described.
-Oil-soluble dye There is no restriction | limiting in particular as an oil-soluble dye, It can select and use arbitrary things. Hereinafter, oil-soluble dyes are exemplified for each hue.
Examples of yellow dyes include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; open-chain active methylene compounds as coupling components. Azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and the like. Examples include acridine dyes and acridinone dyes.

  Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; arylidene dyes, styryl dyes, and merocyanine dyes Methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, condensed polycyclic dyes such as dioxazine dyes Etc.

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

  Each of the dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore group is dissociated. In this case, the counter cation is an alkali metal or an inorganic substance such as ammonium. Or an organic cation such as pyridinium or quaternary ammonium salt, or a polymer cation having such a cation in a partial structure.

-Pigment A mode in which a pigment is used as the colorant is also preferable in that aggregation is likely to occur when a plurality of liquids are mixed. As the pigment, either an organic pigment or an inorganic pigment can be used, and as the black pigment, a carbon black pigment or the like is preferable. In general, pigments of three primary colors of black and cyan, magenta, and yellow are used, but other hues such as pigments having hues such as red, green, blue, brown, white, gold, silver, etc. Metal luster pigments, colorless or light extender pigments, and the like can also be used depending on the purpose.

  The organic pigment is not limited in terms of hue.For example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbox Examples thereof include nium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone, and isoviolanthrone pigments, or a mixture thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene pigments such as CI Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105) or C.I. I. Perinone pigments such as CI Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment red 207 (C.I. No. 73900, 73906), or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone pigment, C.I. I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridone quinone pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20003), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensation pigments such as CI Pigment Brown 23 (C.I. No. 20060),

C. I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo pigments such as C.I. Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone pigments such as CI Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment Green 36 (C.I. No. 74265), Pigment Green 37 (C.I. No. 74255), Pigment Blue 16 (C.I. No. 74100), C.I. I. Phthalocyanine pigments such as CI Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800) or C.I. I. Triarylcarbonium pigments such as C.I. Pigment Blue 61 (C.I. No. 42765: 1); I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Dioxazine pigments such as CI Pigment Violet 37 (C.I. No. 51345); I. Aminoanthraquinone pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 73; I. Thioindigo pigments such as CI Pigment Red 88 (C.I. No. 7313), CI Pigment Yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210) and the like, isoindoline pigments such as C.I. I. Pigment yellow 109 (C.I. No. 56284), or C.I. Pigment Orange 61 (C.I. No. 11295) and the like, isoindolinone pigments such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone pigments such as CI Pigment Red 216 (C.I. No. 59710), or C.I. I. And isoviolanthrone pigments such as CI Pigment Violet 31 (60010).
In the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.

  In addition, particles having silica, alumina, resin, or the like as a core material and having a dye or pigment fixed on the surface, an insoluble raked product of a dye, a colored emulsion, a colored latex, or the like can also be used as a pigment. Furthermore, resin-coated pigments can also be used. This is called a microcapsule pigment, and commercially available products such as those manufactured by Dainippon Ink and Chemicals and Toyo Ink are available.

  The volume average particle diameter of the pigment particles contained in the liquid is preferably in the range of 10 to 250 nm, more preferably 50 to 200 nm, from the viewpoint of balance between optical density and storage stability. Here, the volume average particle diameter of the pigment particles can be measured by a measuring device such as LB-500 (manufactured by HORIBA).

  The colorant may be used alone or in combination of two or more. Further, a different colorant may be used for each droplet of the recording liquid ejected, or the same colorant may be used.

~ (Recording liquid) Lipophilic solvent ~
The oleophilic solvent is effective for preventing the occurrence of blurring of the image and line width variations such as fine lines in the image. “Lipophilic” means a compound having a solubility of 1 g or less with respect to 100 cc of water.

  The oleophilic solvent may be contained in the treatment liquid instead of being contained in the recording liquid, or in an embodiment in which it is contained in both the recording liquid and the treatment liquid.

Examples of the oleophilic solvent include high-boiling organic solvents and the polymerizable materials described above. From the viewpoint of avoiding solidification of the nozzle, it is preferable to use a high-boiling organic solvent, and the film (image) to be formed From the viewpoint of increasing the strength, it is preferable to use a polymerizable compound selected from the polymerizable materials described above.
Hereinafter, the high boiling point organic solvent suitable for the recording liquid will be described.

  The high boiling point organic solvent used for the recording liquid is (1) a viscosity at 25 ° C. of 100 mPa · s or less or a viscosity at 60 ° C. of 30 mPa · s or less and (2) a boiling point higher than 100 ° C. Is preferred.

  In the high boiling point organic solvent that does not satisfy any of the viscosity conditions of (1), the viscosity is increased, which may hinder droplet ejection onto a recording medium by an ejection device such as an inkjet head, In the case of a high-boiling organic solvent that does not satisfy the boiling point condition (2), the boiling point becomes too low and it evaporates during image recording, which may reduce the effect of the present invention.

  Among the conditions (1), the viscosity at 25 ° C. is further preferably in the range of 70 mPa · s or less, more preferably in the range of 40 mPa · s or less, and particularly preferably in the range of 20 mPa · s or less. The viscosity at 60 ° C. is more preferably in the range of 20 mPa · s or less, and particularly preferably in the range of 10 mPa · s or less. Moreover, about the conditions of said (2), the boiling point has the more preferable range of 150 degreeC or more, and the range which is 170 degreeC or more is especially preferable. Moreover, as a lower limit of melting | fusing point, the range of 80 degrees C or less is preferable. Furthermore, the solubility (25 ° C.) of water is preferably 4 g or less, more preferably 3 g or less, further preferably 2 g or less, and particularly preferably 1 g or less.

  The viscosity of the high boiling point organic solvent is a viscosity determined using a RE80 viscometer manufactured by Toki Sangyo Co., Ltd. The RE80 type viscometer is a conical rotor / flat plate type viscometer corresponding to the E type, and the rotor code No. 1 rotor was used and the measurement was performed at a rotation speed of 10 rpm. However, for those having a viscosity higher than 60 mPa · s, the rotational speed is 5 r.p.m., 2.5 r.p.m., 1 r.p.m., 0.5 r.p.m. The measurement was performed by changing to.

  The “water solubility” is the saturation concentration of water in a high boiling point organic solvent at 25 ° C., and means the mass (g) of water that can be dissolved in 100 g of the high boiling point organic solvent at 25 ° C.

  As the high boiling point organic solvent used for the recording liquid, compounds represented by the following formulas [S-1] to [S-9] are preferable.

In the formula [S-1], R ₁ , R ₂ and R ₃ each independently represents an aliphatic group or an aryl group. A, b and c each independently represent 0 or 1;

In the formula [S-2], R ₄ and R ₅ each independently represent an aliphatic group or an aryl group, and R ₆ represents a halogen atom (F, Cl, Br, I and so on), an alkyl group, an alkoxy group, Represents an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and d represents an integer of 0 to 3. When d is plural, plural R ₆ may be the same or different.

In the formula [S-3], Ar represents an aryl group, e represents an integer of 1 to 6, and R ₇ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-4], R ₈ represents an aliphatic group, f represents an integer of 1 to 6, and R ₉ represents a f-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-5], g represents an integer of 2 to 6, R ₁₀ represents a g-valent hydrocarbon group (excluding an aryl group), and R ₁₁ represents an aliphatic group or an aryl group.

In the formula [S-6], R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an aliphatic group or an aryl group. X represents —CO— or —SO ₂ —. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may be bonded to each other to form a ring.

In the formula [S-7], R ₁₅ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group, and R ₁₆ represents a halogen atom, an aliphatic group, an aryl group. Represents a group, an alkoxy group or an aryloxy group, and h represents an integer of 0 to 3. When h is plural, plural R ₁₆ may be the same or different.

In the formula [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group or an aryl group, R ₁₉ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group, and i Represents an integer of 0 to 5. When i is plural, plural R ₁₉ may be the same or different.

In the formula [S-9], R ₂₀ and R ₂₁ each independently represents an aliphatic group or an aryl group. j represents 1 or 2; R ₂₀ and R ₂₁ may be bonded to each other to form a ring.

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are an aliphatic group or a group containing an aliphatic group, the aliphatic group is linear. It may be branched or cyclic, and may contain an unsaturated bond or may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the formulas [S-1] to [S-9], R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are cyclic aliphatic groups, that is, cycloalkyl groups, or groups containing cycloalkyl groups. Sometimes, the cycloalkyl group may contain an unsaturated bond in the 3- to 8-membered ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, and an epoxy group, and examples of the crosslinking group include methylene, ethylene, isopropylidene, and the like.

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ , R _{11 to} R ₂₁ , Ar is an aryl group or a group containing an aryl group, the aryl group is a halogen atom or an aliphatic group It may be substituted with a substituent such as a group, an aryl group, an alkoxy group, an aryloxy group, or an alkoxycarbonyl group.

In the formulas [S-3], [S-4], and [S-5], when R ₇ , R _9, or R ₁₀ is a hydrocarbon group, the hydrocarbon group has a cyclic structure (for example, a benzene ring, a cyclopentane ring, A cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Hereinafter, among the high boiling point organic solvents represented by the formulas [S-1] to [S-9], a high boiling point organic solvent that is particularly preferably used for the recording liquid will be described.
In the formula [S-1], R ₁ , R ₂ and R ₃ are each independently an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms (for example, n-butyl, n-hexyl, n -Octyl, EH-octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, 3,5,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2,3-dichloro Propyl, 2-butoxyethyl, 2-phenoxyethyl, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, phenyl, Cresyl, p-nonylphenyl, xylyl, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl). Good. Among these, R ₁ , R ₂ and R ₃ are particularly n-hexyl, n-octyl, EH-octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, n-dodecyl, 2-chloroethyl, 2-chloro Butoxyethyl, cyclohexyl, phenyl, cresyl, p-nonylphenyl and cumenyl are preferred.
a, b, and c are each independently 0 or 1, and more preferably, all of a, b, and c are 1.

In the formula [S-2], R ₄ and R ₅ are each independently an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms (for example, the same group as the aliphatic group mentioned for R ₁ above). , Heptyl, ethoxycarbonylmethyl, 1,1-diethylpropyl, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl, 3,5,5-trimethylcyclohexyl, menthyl, bornyl, 1-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, the aryl group mentioned for R ₁ , 4-t-butylphenyl, 4-t-octylphenyl, 1, 3,5-trimethylphenyl, 2,4, -di-t-butylphenyl, 2,4, -di-t-pentylphenyl) are preferred. Among these, R ₄ and R ₅ are more preferably aliphatic groups, and particularly preferably n-butyl, heptyl, 2-ethylhexyl, n-dodecyl, 2-butoxyethyl, and ethoxycarbonylmethyl.
R ₆ is a halogen atom (preferably a chlorine atom), an alkyl group having 1 to 18 carbon atoms (for example, methyl, isopropyl, t-butyl, n-dodecyl), an alkoxy group having 1 to 18 carbon atoms (for example, methoxy, n -Butoxy, n-octyloxy, methoxyethoxy, benzyloxy), an aryloxy group having 6 to 18 carbon atoms (for example, phenoxy, p-tolyloxy, 4-methoxyphenoxy, 4-t-butylphenoxy) or 2 carbon atoms A C-19 alkoxycarbonyl group (for example, methoxycarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl) or an aryloxycarbonyl group having 6 to 25 carbon atoms is preferred. Among these, R ₆ is further preferably an alkoxycarbonyl group, and particularly preferably n-butoxycarbonyl.
d is preferably 0 or 1.

In the formula [S-3], Ar is an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, phenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, 1-naphthyl, 4- n-butoxyphenyl, 1,3,5-trimethylphenyl, 2- (2-n-butoxycarbonylphenyl) phenyl) are preferable, and among these, Ar is phenyl, 2,4-dichlorophenyl, 2- (2 -N-Butoxycarbonylphenyl) phenyl is preferred.
e is preferably an integer of 1 to 4 (more preferably 1 to 3).
R ₇ is an e-valent hydrocarbon group having 2 to 24 (preferably 2 to 18) carbon atoms [for example, the aliphatic group mentioned above for R ₄ , n-octyl, the aryl group mentioned for R ₄ ,-( CH _{2) 2} -,

] Or e-valent hydrocarbon groups linked together by an ether bond of carbon atoms from 4 to 24 (preferably 4 to 18) [for _{example, -CH 2 CH 2 OCH 2 CH} 2 -, - CH 2 CH 2 (OCH 2 _{CH 2) 3 -, - CH} 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -,

] Is preferable. Among these, R ₇ is more preferably an alkyl group, and particularly preferably n-butyl, n-octyl, or 2-ethylhexyl.

In the formula [S-4], R ₈ is an aliphatic group having 1 to 24 (preferably 1 to 17) carbon atoms (for example, methyl, n-propyl, 1-hydroxyethyl, 1-ethylpentyl, n-heptyl, n - undecyl, n- tridecyl, pentadecyl, 8,9-epoxy heptadecyl, cyclopropyl, cyclohexyl, 4-methylcyclohexyl). among them, _{R 8} in particular, n- heptyl, n- tridecyl, 1-hydroxy Ethyl, 1-ethylpentyl, and 8,9-epoxyheptadecyl are preferred.
f is preferably an integer of 1 to 4 (more preferably 1 to 3).
R ₉ is a hydrocarbon group having 2 to 24 (preferably 2 to 18) f-valent carbon atoms or a hydrocarbon group linked to each other by an ether bond having 4 to 24 (preferably 4 to 18) f-valent carbon atoms. (For example, the groups mentioned for R ₇ , 1-methyl-2-methoxyethyl, 2-hexyldecyl), among which R ₉ is particularly 2-ethylhexyl, 2-hexyldecyl, 1-methyl-2 -Methoxyethyl,

Is preferred.

In the formula [S-5], g is preferably 2 to 4 (more preferably 2 or 3).
R ₁₀ represents a g-valent hydrocarbon group [for example, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₇ —, — (CH ₂ ) ₈ —,

Among these, R ₁₀ is particularly — (CH ₂ ) ₄ —, — (CH ₂ ) ₈ —,

Is preferred.
R ₁₁ is an aliphatic group having 1 to 24 carbon atoms (preferably 4 to 18 carbon atoms) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18 carbon atoms) (for example, the aliphatic groups mentioned for R ₄ above, Aryl group), and among these, R ₁₁ is more preferably an alkyl group, and particularly preferably n-butyl, n-octyl, and 2-ethylhexyl.

In the formula [S-6], R ₁₂ is a hydrogen atom, an aliphatic group having 1 to 24 carbon atoms (preferably 3 to 20) [for example, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2,4-di-t-pentylphenoxymethyl, 4-t-octylphenoxymethyl, 3- (2,4-di-t-butylphenoxy) propyl, 1- (2,4-di-t-butylphenoxy) propyl Cyclohexyl, 4-methylcyclohexyl, 8-N, N-diethylcarbamoyloctyl], or an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (for example, the aryl group mentioned for Ar, 3-methylphenyl) , 2-(N, N-di -n- octylcarbamoyl) phenyl). among _{them, R 12} is especially, n- undecyl, 8-N, - diethylcarbamoyl-octyl, 3-methylphenyl, 2-(N, N-di -n- octylcarbamoyl) phenyl are preferred.
R ₁₃ and R ₁₄ are each a hydrogen atom, an aliphatic group having 1 to 24 carbon atoms (preferably 1 to 18 carbon atoms) (for example, methyl, ethyl, isopropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl). , N-dodecyl, n-tetradecyl, cyclopentyl, cyclopropyl) or an aryl group having 6 to 18 carbon atoms (preferably 6 to 15) (for example, phenyl, 1-naphthyl, p-tolyl), among these, R ₁₃ and R ₁₄ are particularly preferably methyl, ethyl, n-butyl, n-octyl, n-tetradecyl and phenyl.
R ₁₃ and R ₁₄ may be bonded to each other to form a pyrrolidine ring, piperidine ring or morpholine ring together with N, and R ₁₂ and R ₁₃ may be bonded to each other to form a pyrrolidone ring or piperidine ring together with N. Also good.
X is —CO— or —SO ₂ —, and preferably X is —CO—.

In the formula [S-7], R ₁₅ represents an aliphatic group having 1 to 24 (preferably 3 to 18) carbon atoms (for example, methyl, isopropyl, t-butyl, t-pentyl, t-hexyl, t-octyl, 2 -Butyl, 2-hexyl, 2-octyl, 2-dodecyl, 2-hexadecyl, t-pentadecyl, cyclopentyl, cyclohexyl), an alkoxycarbonyl group having 2 to 24 (preferably 5 to 17) carbon atoms (for example, n-butoxy) Carbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl), aryloxycarbonyl group having 7 to 24 carbon atoms (preferably 7 to 18) (for example, phenoxycarbonyl group, naphthoxycarbonyl group, cresyloxycarbonyl group) An alkylsulfonyl group having 1 to 24 (preferably 1 to 18) carbon atoms (Eg, methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), arylsulfonyl groups having 6 to 30 carbon atoms (preferably 6 to 24) (eg, p-tolylsulfonyl, p-dodecylphenylsulfonyl, p-hexadecyl) Oxyphenylsulfonyl), an aryl group having 6 to 32 carbon atoms (preferably 6 to 24 carbon atoms) (for example, phenyl, p-tolyl) or a cyano group is preferable, and among these, R ₁₅ is further having 1 to 24 carbon atoms. Are more preferable, and an alkoxycarbonyl group having 2 to 24 carbon atoms is more preferable, and an aliphatic group having 1 to 24 carbon atoms is particularly preferable.
R ₁₆ is a halogen atom (preferably Cl), an aliphatic group having 1 to 24 carbon atoms (preferably 1 to 18 carbon atoms) {more preferably an alkyl group (for example, the alkyl groups mentioned for R ₁₅ above), or the number of carbon atoms 3-18 (more preferably 5-17) cycloalkyl group (for example, cyclopentyl, cyclohexyl)}, aryl group having 6-32 (preferably 6-24) carbon atoms (for example, phenyl, p-tolyl), carbon atom An alkoxy group of 1 to 24 (preferably 1 to 18) (for example, methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n-hexadecyloxy) or 6 to 32 carbon atoms (preferably 6-24) aryloxy groups (for example, phenoxy, pt-butylphenoxy, pt-octylphenoxy, m Pentadecylphenoxy, p- dodecyloxy-phenoxy). Among them, R ₁₆ is further more preferably an aliphatic group having 1 to 24 carbon atoms, particularly preferably an aliphatic group having 1 to 12 carbon atoms.
h is preferably an integer of 1 to 2.

In the formula [S-8], preferred examples of R ₁₇ and R ₁₈ are the same as the examples other than the hydrogen atom in R ₁₃ and R ₁₄ , and among these, R ₁₇ and R ₁₈ further have an aliphatic group. More preferred are n-butyl, n-octyl and n-dodecyl. However, R ₁₇ and R ₁₈ are not bonded to each other to form a ring.
Preferred examples of R ₁₉ are the same as R ₁₆ described above, and among these, R ₁₉ is more preferably an alkyl group and an alkoxy group, and particularly preferably n-octyl, methoxy, n-butoxy, and n-octyloxy. .
i is preferably an integer of 1 to 5.

In the formula [S-9], preferred examples of R ₂₀ and R ₂₁ are the same as those of R ₁ , R ₂ and R ₃ when they are not bonded to form a ring, and among these, R ₂₀ and R ₂₁ Is particularly preferably a substituted or unsubstituted aliphatic group having 1 to 24 carbon atoms.
R ₂₀ and R ₂₁ may be bonded to each other to form a ring, and the formed ring is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring.
j represents 1 or 2, and preferably j is 1.

Hereinafter, specific examples (Exemplary Compounds S-1 to S-53) of high boiling point organic solvents suitably used for the recording liquid and the viscosity of each high boiling point organic solvent (measured by the above means in an environment of 25 ° C. and 60 ° C.) Value; mPa · s) and boiling point (° C.).
Here, the boiling point of the following high-boiling organic solvent is a value converted from the boiling point during vacuum distillation to normal pressure. In the following specific examples, those having no boiling point are confirmed not to boil at 170 ° C., and those having no viscosity at 25 ° C. are solid at 25 ° C.

  Even if one kind of high boiling point organic solvent used for the recording liquid is used alone, two or more kinds [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (Nt-butylacrylamide)] may be mixed and used.

  Examples of other high boiling point organic solvents used in the recording liquid and / or methods for synthesizing these high boiling point organic solvents include, for example, U.S. Pat. Nos. 2,322,027 and 2,533,514. 2,772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3, 700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393, 4,220 711, 4,239,851, 4,278,757, 4,353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483 No. 918, No. 4,540,657, No. 4,684,606, No. 4,728,599, No. 4,745,049, No. 4,935,321, No. 5,013,639, European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, No. 509,311A, No. 510,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091, Each specification such as 124A, Japanese Patent Laid-Open No. 48-4 No. 335, No. 50-26530, No. 51-25133, No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149028, No. 52-46816, No. 53-1520. 53-1521, 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84641, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 64-64 No. 9452, No. 64-9454, No. 64-68745, JP-A-1-101543, No. 1-102454, No. 2-792, No. 2-4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338, and the like.

  In the recording liquid, a high boiling point organic solvent having a boiling point higher than 100 ° C. is preferable, and a high boiling point organic solvent having a boiling point higher than 170 ° C. is more preferable.

  The addition amount of the oleophilic solvent in the recording liquid is preferably in the range of 0% by mass to 50% by mass, more preferably 0% by mass to 30% by mass, and more preferably 0% by mass with respect to the total mass of the recording liquid. % To 10% by mass is particularly preferable.

~ (Recording fluid) Other ingredients ~
In addition to the above-described components, known additives and the like can be used in the recording liquid depending on the purpose.

Surfactant The composition of the recording liquid may be selected so that a desired surface tension can be obtained, but it is preferable to add a surfactant to these recording liquids.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. Specifically, for example, anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene -Nonionic surfactants such as polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the known surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
The addition amount of these surfactants is preferably 0.2 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass with respect to the entire recording liquid.

・ Storage stabilizer
A storage stabilizer can be added to the recording liquid which must contain a polymerizable material for the purpose of suppressing undesired polymerization during storage. It is preferable to use a storage stabilizer that is soluble in other components in the recording liquid.

  Storage stabilizers include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinones, hydroquinone monoethers, organic phosphines, copper compounds, and the like. Specific examples include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monomethyl ether, hydroquinone monobutyl ether, and copper naphthenate. It is done.

The amount of storage stabilizer added is preferably adjusted as appropriate based on the activity of the polymerization initiator, the polymerizability of the polymerizable material , the type of storage stabilizer, etc., but the balance between storage stability and curability In terms of solid content in the liquid, 0.005 to 1% by mass is preferable, 0.01 to 0.5% by mass is more preferable, and 0.01 to 0.2% by mass is more preferable.

Conductive salts Conductive salts are solid compounds that improve conductivity. In the present invention, it is preferable not to use it substantially because there is a great concern of precipitation during storage, but it is possible to increase the solubility of conductive salts or use a highly soluble liquid component. If it is good, an appropriate amount may be added.
Examples of the conductive salts include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like.

-Solvent In this invention, a well-known solvent can be used as needed. The solvent can be used for the purpose of improving the polarity and viscosity of the liquid, the surface tension, the solubility / dispersibility of the colorant, adjusting the conductivity, and adjusting the printing performance.
Note that the solvent is a water-insoluble liquid and does not contain an aqueous solvent because it is preferable from the viewpoint of recording a high-quality image with quick drying and uniform line width. The configuration used is desirable.

  A low-boiling organic solvent that is an organic solvent having a boiling point of 100 ° C. or lower can also be used, but there is a concern of affecting the curability, and it is desirable not to use the low-boiling organic solvent in consideration of environmental pollution. When used, it is preferable to use a highly safe solvent, and a highly safe solvent is a solvent having a high management concentration (an index indicated by the work environment evaluation criteria), preferably 100 ppm or more, More preferably, it is 200 ppm or more. Specific examples include alcohols, ketones, esters, ethers, hydrocarbons, and the like, and specific examples include methanol, 2-butanol, acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran.

  Solvents can be used in combination other than one kind alone, but when water and / or a low boiling point organic solvent is used, the amount of both used is preferably 0 to 20% by mass in the recording liquid. 10 mass% is still more preferable, and it is preferable not to contain substantially. When the recording liquid according to the present invention contains water, the recording liquid is non-permeable or slowly penetrable in terms of stability over time such as non-uniformity over time, turbidity of the recording liquid due to dye precipitation, etc. It is not preferable in terms of drying property when using. Note that “substantially free” means accepting the presence of inevitable impurities.

-Other additives Furthermore, well-known additives, such as a polymer, a surface tension regulator, a ultraviolet absorber, antioxidant, a fading inhibitor, and a pH adjuster, can be used together.
Regarding the surface tension adjusting agent, the ultraviolet absorber, the antioxidant, the anti-fading agent, and the pH adjusting agent, a known compound may be appropriately selected and used. Specifically, for example, described in JP-A No. 2001-181549. Additives that have been used can be used.

(2) Composition of treatment liquid The treatment liquid is configured to have at least a composition different from that of the recording liquid, and uses a polymerizable material , a polymerization initiator, a lipophilic solvent, a colorant, and other components as necessary. Can be configured . Also, recording liquid described above contains a colorant, constructed and treatment liquid content of the colorant is less than 1 mass% or more 0% by mass.

As described above, the treatment liquid needs to have a high viscosity of 100 mPa · s or higher at 25 ° C., and from the viewpoint of controlling the viscosity within the above range,
(I) A polymerizable material having a viscosity of 100 mPa · s or higher (more preferably 200 mPa · s or higher) at 25 ° C. and having a higher viscosity than the polymerizable material contained in the recording liquid is included.
(II) The viscosity is 100 mPa · s or higher (more preferably 200 mPa · s or higher) at 25 ° C., the boiling point is higher than 100 ° C., and lipophilic, and the following formulas [S-1] to [S-9] and at least one high-boiling organic solvent including selected from compounds represented by (SH-27)
( However, in the formula [S-6] described below, R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms. In [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms.)
Any one of the requirements is provided. In addition, from the viewpoint of adjusting the viscosity of the treatment liquid, the high-viscosity component can be appropriately selected and used, the polymerizable material shown in (I) above with respect to the total mass of the treatment liquid, and the high boiling point shown in (II) the total content of the organic solvent medium is preferably at least 50 mass%, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.
Of the high-viscosity compositions shown in the above (I) to ( II ), a polymerizable compound is particularly preferably used from the viewpoint of adjusting the viscosity of the treatment liquid. By using the polymerizable compound, advantages are obtained preferably with the effects of the present invention can be exhibited without lowering the film strength after the formation of post-curing.

~ (Processing liquid) Polymerizable material ~
From the viewpoint of controlling the viscosity of the treatment liquid within the above range, the polymerizable material has a high viscosity of 100 mPa · s or higher (more preferably 200 mPa · s or higher) at 25 ° C. as shown in (I) above. It is preferable to use a polymerizable material .
In addition, although the specific example of the said high viscosity polymeric material is shown below, it is not limited to this.

In addition to the above, the treatment liquids similar to those listed as the polymerizable materials suitably used for the recording liquid can be used as long as the viscosity of the treatment liquid is not deviated.

In the treatment liquid, the polymerizable material may be used alone or in combination of two or more.
The content of the polymerizable material in the treatment liquid is preferably in the range of 50 to 99.6% by mass, more preferably in the range of 60 to 99.0% by mass, based on the total solid content (mass). The range of ˜99.0% by mass is more preferable.

~ (Treatment solution) Polymerization initiator and sensitizer / co-sensitizer ~
The treatment liquid can be constituted using at least one kind of polymerization initiator. As specific examples, those listed as polymerization initiators preferably used for the recording liquid described above can be used.

  As already described, the polymerization initiator can be contained in any of the recording liquid and the processing liquid described above, or can be contained in other liquids. The content of the polymerization initiator in all of these liquids (that is, the ink set of the present invention) is a polymerizable or crosslinkable material coated per unit area of the liquid deposited or applied on the recording medium. The content is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 3 to 10% by mass.

  In the treatment liquid, sensitizers and co-sensitizers listed as suitable for use in the above-described recording liquid can be used in the same manner.

~ (Processing liquid) Colorant ~
The treatment liquid may contain a colorant, but as described, the ink set of the present invention includes the recording liquid and the content of the treatment liquid is 0% by mass or more and less than 1% by mass. Is preferred. The content of the colorant in the treatment liquid is preferably less than 1% by mass, more preferably 0.5% by mass or less, and particularly preferably not contained.
In the case where a colorant is contained in the treatment liquid, the same ones listed as the colorants that are preferably used in the recording liquid can be used.

~ (Processing liquid) Lipophilic solvent ~
Examples of the oleophilic solvent include high boiling point organic solvents and the polymerizable materials described above.
From the viewpoint of controlling the viscosity of the treatment liquid within the above range, the high-viscosity organic solvent having a viscosity of 100 mPa · s or higher (more preferably 100 mPa · s or higher) at 25 ° C. as shown in (II) above. It is preferable to use a high boiling point organic solvent.
In addition, although the specific example of the said high-viscosity high boiling point organic solvent is shown below, it is not limited to this. The specific examples of (SH-1) to (SH-27) shown below all have a boiling point of 100 ° C. or higher.

In addition to the above, the processing liquids similar to those listed as the high-boiling organic solvents preferably used for the recording liquid can be used as long as the viscosity of the processing liquid is not deviated. In particular, the compounds represented by the above-mentioned formulas [S-1] to [S-9] (provided that, in the above-mentioned formula [S-6], R ₁₃ and R ₁₄ each independently has 1 to 24 carbon atoms. Represents an aliphatic group or an aryl group having 6 to 18 carbon atoms, and R ₁₇ and R ₁₈ in the above formula [S-8] are each independently an aliphatic group or carbon having 1 to 24 carbon atoms. Represents an aryl group having 6 to 18 atoms).

  The high boiling point organic solvent used in the treatment liquid may be used alone or in combination of two or more.

  The addition amount of the lipophilic solvent in the treatment liquid is preferably in the range of 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, and 70% by mass with respect to the total mass of the treatment liquid. % To 100% by mass is particularly preferable.

~ (Processing liquid) Polymer ~
From the viewpoint of controlling the viscosity of the treatment liquid to the range, it is preferable to use a port Rimmer. Many polymers are solid, and those which are added and dissolved to fall within the physical properties of the treatment liquid of the present invention are preferably used.
Although the specific example of the said high viscosity polymer is shown below, it is not limited to this.
The copolymerization ratio of the copolymer in the specific examples shown below is a molar ratio.

P-1) Polymethacrylate P-2) Polyethylmethacrylate P-3) Polyisopropylmethacrylate P-4) Polymethylchloroacrylate P-5) Poly (2-tert-butylphenylacrylate)
P-6) Poly (4-tert-butylphenyl acrylate)
P-7) Ethyl methacrylate-n-butyl acrylate copolymer (70:30)
P-8) Methyl methacrylate-acrylonitrile copolymer (65:35)
P-9) Methyl methacrylate-styrene copolymer (90:10)
P-10) N-tert-butylmethacrylamide-methylmethacrylate-acrylic acid copolymer (60:30:10)
P-11) Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10)
P-12) Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50)
P-13) Methyl methacrylate-acrylic acid copolymer (95: 5)

P-14) Methyl methacrylate-n-butyl methacrylate copolymer (65:35)
P-15) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10)
P-16) Poly (N-sec-butylacrylamide)
P-17) Poly (N-tert-butylacrylamide)
P-18) Polycyclohexylmethacrylate-methylmethacrylate copolymer (60:40)
P-19) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (20:70:10)
P-20) Diacetone acrylamide-methyl methacrylate copolymer (20:80)
P-21) N-tert-butylacrylamide-methyl methacrylate copolymer (40:60)
P-22) Poly (Nn-butylacrylamide)
P-23) tert-butyl methacrylate-N-tert-butylacrylamide copolymer (50:50)
P-24) tert-butyl methacrylate-methyl methacrylate copolymer (70:30)
P-25) Poly (N-tert-butylmethacrylamide)
P-26) N-tert-butylacrylamide-methyl methacrylate copolymer (60:40)
P-27) Methyl methacrylate-acrylonitrile copolymer (70:30)
P-28) Methyl methacrylate-styrene copolymer (75:25)
P-29) Methyl methacrylate-hexyl methacrylate copolymer (70:30)

P-30) Poly (4-biphenyl acrylate)
P-31) Poly (2-chlorophenyl acrylate)
P-32) Poly (4-chlorophenyl acrylate)
P-33) Poly (pentachlorophenyl acrylate)
P-34) Poly (4-ethoxycarbonylphenyl acrylate)
P-35) Poly (4-methoxycarbonylphenyl acrylate)
P-36) Poly (4-cyanophenyl acrylate)
P-37) Poly (4-methoxyphenyl acrylate)
P-38) Poly (3,5-dimethyladamantyl acrylate)
P-39) Poly (3-dimethylaminophenyl acrylate)
P-40) Poly (2-naphthyl acrylate)
P-41) Poly (phenyl acrylate)
P-42) Poly (N, N-dibutylacrylamide)
P-43) Poly (isohexylacrylamide)
P-44) Poly (isooctylacrylamide)
P-45) Poly (N-methyl-N-phenylacrylamide)
P-46) Poly (adamantyl methacrylate)
P-47) Poly (sec-butyl methacrylate)
P-48) N-tert-butylacrylamide-acrylic acid copolymer (97: 3)
P-49) Poly (2-chloroethyl methacrylate)

P-50) Poly (2-cyanoethyl methacrylate)
P-51) Poly (2-cyanomethylphenyl methacrylate)
P-52) Poly (4-cyanophenyl methacrylate)
P-53) Poly (cyclohexyl methacrylate)
P-54) Poly (2-hydroxypropyl methacrylate)
P-55) Poly (4-methoxycarbonylphenyl methacrylate)
P-56) Poly (3,5-dimethyladamantyl methacrylate)
P-57) Poly (phenyl methacrylate)
P-58) Poly (4-butoxycarbonylphenylmethacrylamide)
P-59) Poly (4-carboxyphenylmethacrylamide)
P-60) Poly (4-ethoxycarbonylphenylmethacrylamide)
P-61) Poly (4-methoxycarbonylphenylmethacrylamide)
P-62) Poly (cyclohexyl chloroacrylate)
P-63) Poly (ethyl chloroacrylate)
P-64) Poly (isobutylchloroacrylate)
P-65) Poly (isopropylchloroacrylate)
P-66) Poly (phenylacrylamide)
P-67) Poly (cyclohexylacrylamide)
P-68) Poly (phenylmethacrylamide)
P-69) Poly (cyclohexylmethacrylamide)
P-70) Poly (butylene adipate)
P-71) Polystyrene P-72) Poly (α-methylstyrene)
P-73) Poly (β-methylstyrene)
P-74) Poly (4-chlorostyrene)
P-75) Poly (4-methoxystyrene)
P-76) Poly (4-methylstyrene)
P-77) Poly (2,4-dimethylstyrene)
P-78) Poly (4-isopropylstyrene)
P-79) Poly (4-t-butylstyrene)
P-80) Poly (3,4-dichlorostyrene)
P-81) Poly (N-ethylacrylamide)
P-82) Poly (Nn-octylacrylamide)
P-83) Poly (Nt-octylacrylamide)
P-84) Poly (N-laurylacrylamide)
P-85) Poly (N-methoxyethylacrylamide)
P-86) Poly (N-lauryl methacrylamide)
P-87) Poly (t-butyl acrylate)
P-88) Poly (t-butyl methacrylate)

As the polymer used in the treatment liquid, one kind may be used alone, or two or more kinds may be mixed and used.
The addition amount of the polymer in the treatment liquid is preferably in the range of 1 to 30% by mass, more preferably 2 to 20% by mass, and particularly preferably 5 to 15% by mass with respect to the total mass of the treatment liquid.

~ (Processing liquid) Other ingredients ~
In addition to the above-described components, known additives and the like can be used in combination with the treatment liquid depending on the purpose.

-Surfactant What is necessary is just to select a composition so that a desired surface tension may be obtained for a processing liquid, However It is preferable to add surfactant to these processing liquids. As the surfactant, those similar to those listed as the surfactants suitably used for the above-mentioned recording liquid can be used, and the preferable addition amount range is the same as that of the recording liquid. However, the amount added to the treatment liquid is preferably larger than the amount added to the recording liquid.

-Other additives A storage stabilizer, a conductive salt, a solvent, and the like can be used for the treatment liquid in the same manner as the recording liquid described above. Moreover, well-known additives, such as a surface tension regulator, a ultraviolet absorber, antioxidant, a fading inhibitor, and a pH adjuster, can be used together.

In the ink set for inkjet recording of the present invention, as a preferred form,
(I) Form in which recording liquid and processing liquid contain polymerizable material , and processing liquid further contains polymerization initiator (ii) Recording liquid contains polymerizable material and colorant, and processing liquid contains polymerizable material and polymerization initiator And (iii) the recording liquid contains a polymerizable material and a colorant, and the processing liquid contains a polymerizable material , a polymerization initiator, and an oleophilic solvent. And the content of the colorant is 0% by mass or more and less than 1%.
In the above, the polymerization initiator may be contained in the recording liquid as long as it is contained in the processing liquid according to the present invention and does not impair the effects of the present invention.

(Physical properties of recording liquid and processing liquid (surface tension))
The recording liquid and the processing liquid used in the ink set for inkjet recording of the present invention preferably contain a surfactant from the viewpoint of forming recording liquid dots of a desired size on the recording medium. It is preferable to satisfy all of the following conditions (A), (B) and (C).
(A) The surface tension of the treatment liquid is smaller than the surface tension of any recording liquid included in the ink set for inkjet recording.
(B) At least one of the surfactants contained in the treatment liquid is
γs (0) −γs (saturated)> 1 mN / m
Satisfy the relationship.
(C) The surface tension of the treatment liquid is
γs <(γs (0) + γs (saturation) ^maximum ) / 2
Satisfy the relationship.

Here, γs is the value of the surface tension of the treatment liquid. γs (0) is the value of the surface tension of the processing liquid excluding all surfactants. γs (saturation) is obtained when one surfactant among the surfactants contained in the treatment liquid is added to the “liquid excluding all surfactants” and the concentration of the surfactant is increased. It is the value of the surface tension of the liquid that saturates. The γs (saturation) ^maximum is the maximum value of γs (saturation) obtained for all surfactants satisfying the condition (B) among the surfactants contained in the treatment liquid.

<Condition (A)>
In the present invention, as described above, in order to form a recording liquid dot of a desired size on a recording medium, the surface tension γs of the processing liquid is set to any of the recording liquids included in the ink set for ink jet recording. The surface tension is preferably smaller than γk.
Further, from the viewpoint of more effectively preventing the expansion of the recording liquid dots from the landing to the exposure, γs <γk-3 (mN / m) is more preferable, and γs <γk-5 (mN / m) is particularly preferable. preferable.
In the case of printing a full-color image, from the viewpoint of improving the sharpness of the image, the surface tension γs of the treatment liquid may be made at least smaller than the surface tension of the recording liquid containing a colorant having high visibility. More preferably, it is less than the surface tension of all the recording liquids contained in the ink set for inkjet recording. Here, the colorant having high visibility includes a magenta, black, or cyan colorant.

Even if the values of the surface tension γk of the recording liquid and the surface tension γs of the processing liquid satisfy the above relationship, it may be difficult to form droplets during ink jetting and cause non-ejection.
For this reason, the surface tension γk of the recording liquid is preferably 15 mN / m or more from the viewpoint of obtaining ejection stability. On the other hand, since the wettability with the ink jet head may deteriorate and the problem of non-ejection may occur, the surface tension γk of the recording liquid is preferably 50 mN / m or less from the viewpoint of obtaining good ejection suitability. In addition, 18 mN / m or more and 40 mN / m or less are more preferable, and 20 mN / m or more and 38 mN / m or less are particularly preferable.
Also, in the case of applying the treatment liquid to the recording medium by discharging with an ink jet head, the surface tension γs is preferably in the above range.

  Here, the surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter CBVP-Z, etc.) at a liquid temperature of 20 ° C. and 60% RH. It is the value measured by.

<Condition (B) and Condition (C)>
In the present invention, in order to form a recording liquid dot having a target size on a recording medium, the treatment liquid preferably contains at least one kind of surfactant. In this case, it is preferable that at least one of the surfactants contained in the treatment liquid satisfies the following condition (B).
γs (0) −γs (saturation)> 1 mN / m Condition (B)

Furthermore, the surface tension of the treatment liquid preferably satisfies the relationship of the following condition (C).
γs <(γs (0) + γs (saturation) ^maximum ) / 2 ... condition (C)

As described above, γs is the value of the surface tension of the treatment liquid. γs (0) is the value of the surface tension of the processing liquid excluding all surfactants. γs (saturation) is obtained when one surfactant among the surfactants contained in the treatment liquid is added to the “liquid excluding all surfactants” and the concentration of the surfactant is increased. It is the value of the surface tension of the liquid that saturates. The γs (saturation) ^maximum is the maximum value of γs (saturation) obtained for all surfactants satisfying the condition (B) among the surfactants contained in the treatment liquid.

  The γs (0) can be obtained by measuring the surface tension value of the liquid obtained by removing all the surfactants from the processing liquid. The γs (saturation) is obtained by adding one surfactant among the surfactants contained in the treatment liquid to the “liquid excluding all surfactants” and setting the concentration of the surfactant to 0. It is obtained by measuring the surface tension of the liquid when the amount of change in surface tension becomes 0.01 mN / m or less when it is increased by 01% by mass.

As for the condition (C), from the viewpoint of more effectively preventing expansion of ink droplets from landing to exposure, the surface tension of the treatment liquid is as follows:
γs <γs (0) −3 × {γs (0) −γs (saturated)} / 4
It is more preferable to satisfy the relationship
γs ≦ γs (saturated)
It is particularly preferable to satisfy this relationship.

  Here, the surface tension was measured at a liquid temperature of 20 ° C. by the Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter CBVP-Z, etc.). Value.

  The composition of the recording liquid and the processing liquid may be selected so as to obtain a desired surface tension, but it is preferable to add a surfactant to these liquids. As described above, in order to form a recording liquid dot having a target size on a recording medium, the treatment liquid preferably contains at least one surfactant. The surfactant is shown below.

~ Surfactant ~
The surfactant here is hexane, cyclohexane, p-xylene, toluene, ethyl acetate, methyl ethyl ketone, butyl carbitol, cyclohexanone, triethylene glycol monobutyl ether, 1,2-hexanediol, propylene glycol monomethyl ether, isopropanol, methanol. , Water, isobornyl acrylate, 1,6-hexane diacrylate, polyethylene glycol diacrylate is a substance having a strong surface activity against at least one solvent, preferably hexane, toluene, propylene glycol monomethyl ether, Strong surface activity against at least one solvent among isobonyl acrylate, 1,6-hexane diacrylate and polyethylene glycol diacrylate More preferably, a substance having strong surface activity against at least one solvent among propylene glycol monomethyl ether, isobornyl acrylate, 1,6-hexane diacrylate, and polyethylene glycol diacrylate is particularly preferable. Is a substance having a strong surface activity against at least one solvent among isobornyl acrylate, 1,6-hexane diacrylate, and polyethylene glycol diacrylate.

Whether or not a certain compound has a strong surface activity with respect to the solvents listed above can be determined by the following procedure.
(procedure)
One solvent is selected from the solvents listed above, and the surface tension γ (0) solvent of the solvent is measured. When the compound is added to the same solution as the solvent for which the γ (0) solvent was obtained, the concentration of the compound is increased by 0.01% by mass, and the change in the surface tension becomes 0.01 mN / m or less The surface tension γ (saturated) solvent of the solution is measured. The relationship between the γ (0) solvent and the γ (saturated) solvent is
γ (0) solvent-γ (saturated) solvent> 1 mN / m
If so, the compound is judged to be a substance having a strong surface activity with respect to the solvent.

  Specific examples of the surfactant contained in the treatment liquid include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, Nonionic surfactants such as acetylene glycols and polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and fluorosurfactants. In addition, examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457.

(Physical properties of recording liquid and processing liquid (sp value))
Further, in the present invention, the sp value of the treatment liquid to be applied in advance before droplet ejection of the recording liquid is set to 35 or less, and the difference in sp value between the recording liquid and the processing liquid is set to 10 or less. It is preferable to do.
When the sp value is 35 or less, for example, when the recording liquid is ejected so that the recording liquid has overlapping portions with “droplet a1, droplet a2,. The affinity between a2... is increased, the coalescence of the droplets can be suppressed, and the occurrence of line width variations such as image blurring and fine lines in the image can be more effectively prevented.

Adjustment of sp value can be suitably performed using a lipophilic solvent (high boiling point organic solvent, polymerizable compound) or the like. As one of the preferable adjustment modes, the lipophilic solvent may be contained in the range of 50% by mass to 100% by mass with respect to the total mass of the treatment liquid. When the content of the lipophilic solvent is within the above range, the sp value can be reduced and adjusted to a range of 35 or less.
In the treatment liquid, the sp value is more preferably 30 or less, and particularly preferably 25 or less.

  Further, when the difference in sp value between the recording liquid and the processing liquid is within the above range, they are easily dissolved, and the droplet a1 is in contact with the processing liquid rather than between the droplet a2. Therefore, the affinity with the processing solution is good. Therefore, for example, when the droplets a1, droplets a2,... Applied with overlapping portions of each other contain a colorant, color bleeding or color mixing occurs between the droplets a1 and droplets a2. This is effective in avoiding line width variations in the line image.

The sp value can be suitably adjusted using the above-described lipophilic solvent, polymerizable material, etc. For example, the sp value can be further lowered by increasing the ratio of the lipophilic solvent in the droplets.
The difference in sp value between the recording liquid and the processing liquid is more preferably 5 or less.

The sp value is defined for various solvents and solutes, and is a value indicating the easiness of dissolution between solvent / solvent and between solvent / solute. This value is calculated from a change in energy when the solvent and the solvent are mixed, and when the solute is dissolved in the solvent. Specifically, the sp value used in the present invention is the R.I. L. It is obtained by calculating with a sp value calculation program by Smith. In the calculation, with reference to 25 ° C., except for compounds not containing carbon atoms, the structural units such as polymers and polyethylene chains are saturated repeating units having a bond (for example, —CH ₂ —CH (C in the case of styrene). ₆ H ₅₎ -) and then, water _(H 2 O) is calculated as 47.8.

<Inkjet recording method>
(Recording liquid ejection and treatment liquid application)
In the ink jet recording method of the present invention, the recording liquid described above is ejected using an ink jet nozzle or the like, and the treatment liquid is applied by other means such as application or application using an ink jet nozzle. Can be granted. In addition, since the treatment liquid of the present invention has a high viscosity of 100 mPa · s or more at 25 ° C., droplet ejection using an inkjet nozzle or the like may be subject to ejection stability. It is preferable to apply by other means.
Hereinafter, an applying unit used when applying the processing liquid onto the recording medium will be described.

(I) Coating using a coating apparatus A mode in which an image is recorded by coating a processing liquid on a recording medium using a coating apparatus and then ejecting the recording liquid by an inkjet nozzle is preferable.

The coating device is not particularly limited and can be appropriately selected from known coating devices according to the purpose, for example, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, an impregnation coater, Examples include reverse roll coaters, transfer roll coaters, gravure coaters, kiss roll coaters, cast coaters, spray coaters, curtain coaters, and extrusion coaters. For details, see Yuji Harasaki's “Coating Engineering”.
The ink jet nozzle is not particularly limited and can be appropriately selected from known nozzles according to the purpose. The ink jet recording method will be described later.

  Note that other liquids other than the recording liquid and the treatment liquid may be used, and the other liquid may be applied to the recording medium by any method such as coating by the coating apparatus or jetting by an inkjet nozzle. Also, the timing of application is not particularly limited. However, in the case of containing a colorant, it is preferable to spray by an ink jet nozzle, and it is preferable to spray onto a recording medium after applying the treatment liquid.

(Ii) Injection by inkjet nozzle A processing liquid is ejected continuously (or simultaneously) into droplets b1, droplets b2, droplets b3,. A mode in which an image is recorded by ejecting the ink droplets by an ink jet nozzle so as to become droplets a1, a2, a3,. The ink jet nozzle is the same as described above.

  In this case as well, liquids other than the recording liquid and the treatment liquid may be applied to the recording medium by any method such as application by a coating apparatus or ejection by an inkjet nozzle, and the timing of application is also particularly limited. Is not to be done. In the case of containing a colorant, it is preferable that the colorant is injected by an inkjet nozzle, and it is preferable that the treatment liquid is further injected after being applied from the nozzle.

Next, an ejection method (inkjet recording method) using an inkjet nozzle will be described.
In the present invention, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electric signal is converted into an acoustic beam into ink. Known systems such as an acoustic ink jet system that irradiates and discharges ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating ink and generate pressure Is preferred.
The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method using is included.

  In the case of the applying means (i), at least the recording liquid is ejected onto the processing liquid previously applied on the recording medium by an ink jet recording method to form an image. In the case of using the applying means (ii), at least the recording liquid is further ejected by the ink jet recording system on the processing liquid previously applied to the recording medium by the ink jet recording system, and an image is formed.

  In the present invention, when the droplet a1 and the droplet a2 as the recording liquid are ejected so as to have an overlapping portion, the number of droplets deposited per unit length is increased and higher-resolution image recording is performed. Can be realized.

The overlapping rate when droplets are ejected with an overlapping portion is an overlapping rate at least one second after the droplets a1 and a2 are overlapped and ejected, and in particular after the droplet a1 is ejected. It is preferable that the droplets be ejected so that the overlapping rate at the overlapping portion after 1 second from the droplet a2 is 10% or more and 90% or less. It is effective for higher resolution image recording.
Among these, the overlapping rate is preferably 20% or more and 80% or less, and more preferably 30% or more and 70% or less.

  The overlapping rate is an index indicating at what rate the adjacent droplets (droplet a1, droplet a2,...) In the recording liquid overlap. Assuming that the diameter of the droplet after landing on the recording medium is a, the overlap ratio is 50% when (1/2) a overlaps. In the case of the present invention, adjacent droplets that are ejected adjacently can maintain the droplet ejection shape without being united with each other, but the overlapping rate is defined as b being the radius of the droplet one second after droplet ejection. When the interval between adjacent droplet ejection center points is c, 100 × (2b−c) / (2b) [%].

  The application of the treatment liquid is not particularly limited as long as it can be applied to the same region as the image formed by droplet ejection with the recording liquid or a region wider than the image.

  At the time of image recording, the balance of the applied amount of the treatment liquid per one shot of the recording liquid (droplet a1, droplet a2,...) Is set to 1 for the amount of droplet a1, droplet a2, etc. The application amount (mass ratio) of the treatment liquid in this case is preferably in the range of 0.05 to 5, more preferably in the range of 0.07 to 1, and particularly preferably in the range of 0.1 to 1.

  The droplet size of the recording liquid (size of the droplets a1 and the like) is preferably ejected at 0.1 pL (picoliter; the same applies hereinafter) to 100 pL (preferably by an inkjet nozzle). When the droplet size is within the above range, it is effective in that an image having a high sharpness can be drawn with a density. More preferably, it is 0.5 pL or more and 50 pL or less.

(Recording medium)
In the inkjet recording method of the present invention, any of a permeable recording medium, a non-permeable recording medium, and a slowly permeable recording medium can be used as a recording medium. Among these, a non-permeable or slowly permeable recording medium is preferable from the viewpoint of more remarkable effects of the present invention.

  In particular, when image recording is performed on a recording medium having low liquid absorbency, conventionally, adjacent liquid droplets that have been provided with overlapping portions (in order to obtain a high image density) If the droplets are deposited on the medium before being dried, they will merge with each other and the blurring of the image and the line width of the fine lines will become non-uniform, resulting in a loss of sharp image formation. There was a problem. However, as in the present invention, by applying a high-viscosity treatment liquid on the recording medium in advance before the recording liquid is ejected, the liquid droplets a1 and a2 have overlapping portions. Even if applied, the coalescence between the droplets a1 and a2 is suppressed, and the occurrence of blurring of the image and variations in line width such as fine lines in the image are effectively prevented. It can be formed, and an inkjet image having a high droplet ejection density such as a reversed character can be recorded with good reproducibility of a fine image such as a fine line.

  Here, the permeable recording medium is a medium that has a time of 100 milliseconds or less until the total liquid amount permeates when a 10 pL (picoliter) droplet is dropped on the recording medium. Examples of the paper include plain paper and porous paper. The non-permeable recording medium refers to a medium in which droplets do not substantially permeate, and examples thereof include a medium using synthetic resin or glass. “Substantially does not penetrate” means that the penetration rate of a droplet after 1 minute is 5% or less. Further, the slow-penetrating recording medium refers to a medium in which when a 10 pL droplet is dropped onto a recording medium, the time until the total liquid permeates is 100 ms or more. For example, paper. Details of the non-permeable or slowly permeable recording medium will be described later.

Examples of the permeable recording medium include plain paper, porous paper, and other media that can absorb liquid.
Examples of the non-permeable or slowly permeable recording medium include art paper, synthetic resin, rubber, resin-coated paper, glass, metal, earthenware, and wood. In addition, for the purpose of adding a function, a base material obtained by combining a plurality of these materials can be used.

  As the synthetic resin, any synthetic resin can be used. For example, polyesters such as polyethylene terephthalate and polybutadiene terephthalate, polyolefins such as polyvinyl chloride, polystyrene, polyethylene, polyurethane, and polypropylene, acrylic resins, polycarbonates, and acrylonitrile-butadiene. -Styrene copolymer etc., Diacetate, Triacetate, Polyimide, Cellophane, Celluloid etc. are mentioned. When the synthetic resin is used, the thickness and shape may be any of a film shape, a card shape, and a block shape, and are not particularly limited, and may be either transparent or opaque.

  The synthetic resin is preferably used in the form of a film used for so-called soft packaging, and various non-absorbable plastics and films thereof can be used. Examples of the plastic film include a PET film, an OPS film, an OPP film, a PNy film, a PVC film, a PE film, and a TAC film. Other plastics that can be used include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers.

  Examples of the resin-coated paper include a transparent polyester film, an opaque polyester film, an opaque polyolefin resin film, and a paper support in which both sides of paper are laminated with a polyolefin resin. Particularly preferred is a paper support in which both sides of the paper are laminated with a polyolefin resin.

  There is no restriction | limiting in particular as said metal, For example, aluminum, iron, gold | metal | money, silver, copper, nickel, titanium, chromium, molybdenum, silicon | silicone, lead, zinc etc., or stainless steel etc., and these composite materials are suitable. .

  Further, a read-only optical disk such as a CD-ROM or DVD-ROM, a write-once optical disk such as a CD-R or DVD-R, a rewritable optical disk, or the like can also be used. And a gloss-imparting layer.

(Give active energy)
In the present invention, the treatment liquid is applied in advance as described above, and then at least after the recording liquid is deposited, from the viewpoint of obtaining excellent fixability, the recording image is fixed by applying active energy. A step can be provided. By the application of actinic energy, to promote polymerization by curing reaction of the polymerizable material contained, it is possible to more efficiently form a stronger image. For example, in a system including a polymerization initiator, generation of active species due to decomposition of the polymerization initiator is promoted by application of active energy such as actinic light and heating, and due to the increase of active species and temperature rise, the result is due to the active species. The curing reaction by polymerization of the polymerizable material is accelerated.
The application of energy can be suitably performed by irradiation with active light or heating.

In addition, when the activation energy is applied by heating, it is preferable to heat for 0.1 to 1 second under the condition that the surface temperature of the recording medium is in a temperature range of 40 to 80 ° C.
Heating can be performed using a non-contact type heating means, such as a heating means for passing through a heating furnace such as an oven, a heating means by full exposure of ultraviolet light to visible light to infrared light, etc. are suitable. It is. Examples of light sources suitable for exposure as the heating means include metal halide lamps, xenon lamps, tungsten lamps, carbon arc lamps, mercury lamps and the like.

(Image recording principle and recording device)
Next, an example of the principle of the present invention for forming an image on a recording medium will be described with reference to FIG. In the following description, an example in which the recording liquid contains a colorant and the processing liquid does not contain a colorant will be described.
First, as shown in FIG. 1A, a treatment liquid is applied to the recording medium 16, and a liquid film 81 made of the treatment liquid is formed on the surface of the recording medium 16. Such a treatment liquid may be applied in any manner such as droplet ejection (also referred to as “ejection”) and coating.

  The thickness of the liquid film of the applied treatment liquid is an average thickness obtained by dividing the volume of the applied treatment liquid by the area of the portion to which the treatment liquid is applied. When the treatment liquid is applied by droplet ejection, it can be determined from the volume of droplet ejection and the area of the portion where the treatment liquid is deposited. The thickness of the liquid film of the treatment liquid is desirably uniform and does not have a local difference in thickness. From this point of view, it is desirable that the physical properties that easily spread on the recording medium, that is, the static surface tension is small.

Next, as shown in FIG. 1B, the gas-liquid interface is limited only to the boundary surface 81a between the processing liquid and the atmosphere, that is, the surface area of the gas-liquid interface 81a is not changed, or the surface area is changed. In a state where the liquid film 81 made of the processing liquid is present on the recording medium 16, the recording liquid droplet 82a (droplet a1) is ejected. By this droplet ejection, as shown in FIG. 1C, the droplet 82 a is buried in the liquid film 81.
Further, as shown in FIG. 1 (d), in the region where the liquid film 81 made of the processing liquid on the recording medium 16 is present, the recording liquid is located in the vicinity of the landing position of the previously ejected droplet 82a. A droplet 82b (droplet a2) is ejected. As shown in FIG. 1 (e), the droplet 82 b is also buried in the liquid film 81.

In this way, even if the plurality of droplets 82a and 82b are landed at positions close to each other by burying the plurality of droplets 82a and 82b in the liquid film 81 of the processing liquid, a new gas-liquid interface is obtained. Will not occur. Specifically, the boundary surface between the gas and the liquid is limited to the boundary surface 81a between the liquid film 81 made of the processing liquid and the atmosphere, and the area of the gas-liquid interface 81a does not change or the change in the area is small.
If a plurality of droplets 82a and 82b of the recording liquid are ejected in a state where the liquid film 81 made of the processing liquid is not on the recording medium 16, the surface energy of the gas-liquid interface is reduced, that is, the surface energy is minimized. However, in the present invention, such droplet ejection interference is avoided, although a plurality of droplets 82a and 82b of the recording liquid are coalesced.

  In FIG. 1, in order to simplify the drawing, the recording liquid droplets 82a and 82b are shown so as not to overlap each other. However, from the viewpoint of obtaining a high image density, the droplets 82a and 82b are mutually separated. Drops are deposited so as to have an overlapping portion. Conventionally, when the droplets 82a and 82b are in contact with the recording medium 16 before being dried in this way, the images are merged with each other and the image blur and the line width of the thin line become non-uniform. Image formation was impaired. However, as in the present invention, by applying a high-viscosity treatment liquid on the recording medium in advance before the recording liquid is ejected, the droplets 82a and 82b have overlapping portions. Even if it is applied, unification is suppressed, and the occurrence of blurring of the image and line width variations such as fine lines in the image is effectively prevented, so that a sharp line can be formed with a uniform width. Inkjet images with high droplet density can be recorded with good reproducibility of fine images such as fine lines.

Further, as shown in FIG. 1E, while the droplet ejection interference is avoided and the shape of the recording liquid droplets 82a and 82b is maintained inside the liquid film 81 (in the case of the present invention, it is several hundred millimeters). 5 seconds to 5 seconds), that is, before the dot shape is destroyed, the recording liquid droplets 82 a and 82 b are cured, and the colorant in the recording liquid droplets 82 a and 82 b is fixed to the recording medium 16. At least the recording liquid in the present invention contains a polymerizable material, and is cured by a so-called polymerization reaction when activated energy is applied by ultraviolet rays or the like. The treatment liquid can also contain a polymerizable compound, and the entire liquid on the recording medium 16 is cured, which is preferable for improving the adhesion.

Next, the overall configuration of the image recording apparatus will be described with reference to the drawings.
FIG. 2 is an overall configuration diagram illustrating an example of the image recording apparatus 10. The image recording apparatus 10 forms a desired image on the recording medium 16 by applying a treatment liquid for forming a liquid film on the recording medium 16 and a recording liquid to a predetermined recording medium 16. .
Recording media that are not particularly permeable (for example, OPP (Oriented Polypropylene Film), CPP (Casted Polyproptlene Film), PE (polyethylene), PET (Polyethylene terephthalate), soft wrapping materials with low permeability, laminated paper , Coated paper, art paper, etc.) can be used to form a good image.

In FIG. 2, the image recording apparatus 10 includes a liquid applying unit 12 that applies a treatment liquid to the recording medium 16 by coating and applies ink (recording liquid) to the recording medium 16 by droplet ejection.
The image recording apparatus 10 also includes a liquid storage / loading unit 14 that stores processing liquid and ink to be supplied to the liquid applying unit 12, a paper feeding unit 18 that supplies the recording medium 16, and curling of the recording medium 16. The decurling unit 20 to be removed, the belt conveying unit 22 that is disposed to face the ejection surface of the liquid application unit 12 and conveys the recording medium 16 while maintaining the flatness of the recording medium 16, and the ink by the liquid application unit 12 An image detection unit 24 that reads an image as a result of droplet ejection of (recording liquid) (in an ink droplet landing state) and a paper discharge unit 26 that ejects a recorded recording medium to the outside.

  In FIG. 2, as an example of the paper supply unit 18, one that feeds roll paper (continuous paper) is shown, but one that feeds cut paper that has been cut in advance may be used. In the case of an apparatus configuration that uses roll paper, a cutter 28 is provided. Incidentally, the recording medium 16 delivered from the paper supply unit 18 generally retains curl and curls. In order to remove the curl, heat is applied to the recording medium 16 by the heating drum 30 in the direction opposite to the curl direction in the decurling unit 20. After the decurling process, the cut recording medium 16 is sent to the belt conveyance unit 22.

  The belt conveyance unit 22 has a structure in which an endless belt 33 is wound between rollers 31 and 32, and a portion facing the ejection surface of the liquid application unit 12 and the sensor surface of the image detection unit 24 is flat (flat). Surface). The belt 33 has a width that is wider than the width of the recording medium 16, and a plurality of suction holes (not shown) are formed on the belt surface. An adsorption chamber 34 is provided at a position facing the ejection surface of the liquid application unit 12 and the sensor surface of the image detection unit 24 inside the belt 33 spanned between the rollers 31 and 32. The recording medium 16 on the belt is sucked and held by sucking with the fan 35 to be a negative pressure. The power of a motor (not shown) is transmitted to at least one of the rollers 31 and 32 around which the belt 33 is wound, whereby the belt 33 is driven in the counterclockwise direction in FIG. The recording medium 16 is conveyed from right to left in FIG. Note that, when a borderless print or the like is formed, the ink also adheres to the belt 33. Therefore, the belt cleaning unit 36 is provided at a predetermined position outside the belt 33 (an appropriate position other than the recording area). In this embodiment, the recording medium is held and transported by the negative pressure as an example of holding the recording medium. However, other holding and transporting means (electrostatic suction transport, roller transport, etc.) are selectively used. You can also

FIG. 3 is a plan view showing the liquid application unit 12 and its peripheral portion of the image recording apparatus 10.
In FIG. 3, the liquid application unit 12 includes a treatment liquid coating device 12 </ b> P that applies the treatment liquid to the recording medium 16, and ink droplet ejection heads 12 </ b> Y and 12 </ b> M that eject ink onto the recording medium 16 in a single pass. , 12C, 12K.

In the present embodiment, a rod coater is used as the coating apparatus 12P for the treatment liquid. However, the coating apparatus is not particularly limited thereto, and a known coating apparatus can be appropriately selected according to the purpose. Examples thereof include an air doctor coater, a blade coater, a knife coater, a squeeze coater, an impregnation coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a cast coater, a spray coater, a curtain coater, and an extrusion coater.
In the present invention, as means for applying the treatment liquid onto the recording medium, droplet ejection by an ink jet head or other means may be used.

  Further, the droplet ejection heads 12Y, 12M, 12C, and 12K have a line type head having a length corresponding to the entire recordable width of the recording medium 16 in detail in the medium transport direction (the sub-line indicated by the arrow S in FIG. 3). This is a so-called full-line head arranged in a direction (main scanning direction) orthogonal to the scanning direction.

In each of the droplet ejection heads 12Y, 12C, 12M, and 12K, a plurality of nozzles (liquid ejection ports) are arranged over a length that exceeds at least one side of the recording medium 16 of the maximum size targeted by the image recording apparatus 10.
Further, from the upstream side (the right side in FIG. 3) along the medium transport direction S, the processing liquid (P), the yellow ink (Y), the cyan ink (C), the magenta ink (M), A coating device (rod coater) 12P corresponding to each liquid and droplet ejection heads 12Y, 12C, 12M, and 12K are arranged in the order of black ink (K), and a color image is formed on the recording medium 16. obtain.

  Specifically, first, the treatment liquid is applied onto the recording medium 16 by applying the treatment liquid from the coating apparatus 12P for treatment liquid to the recording medium 16, and the treatment liquid is present in a region where the treatment liquid exists as a liquid film. Next, ink is ejected from the ink droplet ejection heads 12Y, 12M, 12C, and 12K toward the recording medium 16. Here, by embedding the ink droplets in the liquid film of the processing liquid on the recording medium 16, landing interference is avoided without causing a significant increase in the gas-liquid interface.

  Further, according to the liquid application unit 12 including the coating device (rod coater) and the full-line type droplet ejection head, the operation of relatively moving the recording medium 16 and the liquid application unit 12 in the medium conveyance direction (sub-scanning direction). It is possible to record an image on the entire surface of the recording medium 16 by performing only once. Thereby, high-speed printing is possible and productivity can be improved as compared with a shuttle type head in which the droplet ejection head reciprocates in a direction (main scanning direction) orthogonal to the medium conveyance direction.

  The main scanning direction and the sub-scanning direction are used in the following meaning. That is, when driving a nozzle with a full line head having a nozzle row corresponding to the full width of the recording medium, (1) whether all the nozzles are driven simultaneously, or (2) whether the nozzles are driven sequentially from one side to the other (3) The nozzles are divided into blocks, and one of the nozzles is driven sequentially from one side to the other for each block, and the width direction of the recording medium (the recording medium conveyance direction and Driving a nozzle that prints one line (a line made up of one row of dots or a line made up of a plurality of rows of dots) in an orthogonal direction is defined as main scanning. A direction indicated by one line (longitudinal direction of the belt-like region) recorded by the main scanning is called a main scanning direction.

  On the other hand, by relatively moving the above-described full line head and the recording medium, printing of one line (a line composed of one line of dots or a line composed of a plurality of lines) formed by the above-described main scanning is repeatedly performed. Is defined as sub-scanning. A direction in which sub-scanning is performed is referred to as a sub-scanning direction. Accordingly, the conveyance direction of the recording medium is the sub-scanning direction, and the direction perpendicular to the recording medium is the main scanning direction.

  In this embodiment, the configuration of the standard colors (4 colors) of YMCK is exemplified. However, the number of ink colors and color combinations are not limited to the examples shown in this embodiment, and the light colors may be used as necessary. Ink, dark ink, white or other special color ink, transparent ink, or the like may be added. For example, a configuration in which a droplet ejection head that discharges light-colored ink such as light cyan or light magenta is added, a configuration in which a background is drawn with white ink, or a glossiness adjustment with transparent ink is possible.

The UV light source 27 irradiates the recording medium 16 with ultraviolet rays in order to cure the ink containing the polymerizable compound. A known light source such as a high pressure mercury lamp, a medium pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a fluorescent lamp for ultraviolet light, an ultraviolet LED, an ultraviolet LD, etc. can be used as the ultraviolet light source. From the viewpoint of properties, it is preferable to use a high-pressure mercury lamp or a metal halide lamp. The UV light source preferably has a light amount peak in the wavelength range of 200 nm to 400 nm, and preferably has an irradiation light amount in the range of 1 to 500 mJ / cm ^{2 at} the light amount peak wavelength. The UV light source preferably uses a cold mirror for the reflector and an infrared cut glass for the cover glass, thereby preventing a temperature rise of the recording medium due to heat ray irradiation. Although omitted in FIG. 2, in the case of ink containing a radical polymerizable compound, the ink is cured and fixed better by replacing the curing atmosphere of the UV irradiation part with an inert gas (such as nitrogen). be able to.

  Although not shown, an electron beam irradiation apparatus and a curing atmosphere inert gas replacement means for preventing polymerization inhibition by oxygen may be used as means for curing ink containing a polymerizable compound.

  In the above, examples of the UV light source and the electron beam irradiation apparatus are exemplified as means for curing the polymerizable compound, but these means are not limited to the examples shown here, and other radiation rays such as α Lines, γ-rays, X-rays, etc. may be used.

  The liquid storage / loading unit 14 illustrated in FIG. 2 includes a processing liquid tank that stores the processing liquid, and a liquid tank that stores ink for each color of YMCK. The droplet ejection heads 12Y, 12C, 12M, and 12K are communicated with each other.

  The image detection unit 24 includes an image sensor (line sensor or the like) for imaging the droplet ejection result of the liquid application unit 12, and as means for checking nozzle clogging or other application abnormality from an image read by the image sensor. Function.

  The recording medium 16 as a printed matter on which an image is formed is discharged from the paper discharge unit 26. The image recording apparatus 10 is provided with sorting means (not shown) for switching the paper discharge path in order to select the printed material of the main image and the printed material of the test print and send them to the respective discharge units 26A and 26B. ing. When the main image and the test print are simultaneously formed in parallel on a large sheet, the test print portion is separated by a cutter (second cutter) 48. The cutter 48 is provided immediately before the paper discharge unit 26, and cuts the main image and the test print unit when a test print is performed on an image margin. Although not shown, the paper output unit 26A for the target prints is provided with a sorter for collecting prints according to print orders.

* Structure of the droplet ejection head FIG. 4A shows a basic configuration of the droplet ejection head 50 by attaching a reference numeral 50 to the droplet ejection head representing the droplet ejection heads 12Y, 12C, 12M and 12K shown in FIG. It is a plane perspective view which shows an example of a whole whole structure.
The droplet ejection head 50 shown as an example in FIG. 4A is a so-called full-line head, and is in a direction (in the drawing) orthogonal to the conveyance direction of the recording medium 16 (in the sub-scanning direction indicated by arrow S in the drawing). A number of nozzles 51 (liquid ejection ports) that eject liquid toward the recording medium 16 are two-dimensionally arranged over a length corresponding to the width Wm of the recording medium 16 in the main scanning direction indicated by the arrow M). It has a structure.

  The droplet ejection head 50 includes a nozzle 51, a pressure chamber 52 communicating with the nozzle 51, and a plurality of pressure chamber units 54 including a liquid supply port 53 with respect to the main scanning direction M and the main scanning direction M. They are arranged along two oblique directions forming an acute angle θ (0 degree <θ <90 degrees). In FIG. 4A, only a part of the pressure chamber units 54 is shown for convenience of illustration.

  Specifically, the nozzles 51 are arranged at a constant pitch d in an oblique direction that forms a predetermined acute angle θ with respect to the main scanning direction M, and thus, “on a straight line along the main scanning direction M” d × cos θ ”can be handled equivalently.

FIG. 4B shows a cross-sectional view taken along the line bb in FIG. 4A with respect to the pressure chamber unit 54 described above as one ejection element constituting the droplet ejection head 50.
As shown in FIG. 4B, each pressure chamber 52 communicates with a common liquid chamber 55 via a liquid supply port 53. The common liquid chamber 55 communicates with a tank which is a liquid supply source (not shown), and the liquid supplied from the tank is distributed and supplied to each pressure chamber 52 via the common liquid chamber 55.

A piezoelectric body 58a is disposed on the diaphragm 56 constituting the top surface of the pressure chamber 52, and an individual electrode 57 is disposed on the piezoelectric body 58a. The diaphragm 56 is grounded and functions as a common electrode. These diaphragm 56, individual electrode 57 and piezoelectric body 58a constitute a piezoelectric actuator 58 as means for generating a liquid ejection force.
When a predetermined drive voltage is applied to the individual electrode 57 of the piezoelectric actuator 58, the piezoelectric body 58a is deformed to change the volume of the pressure chamber 52, and the pressure in the pressure chamber 52 is changed accordingly. Liquid is discharged. After the liquid is discharged, when the volume of the pressure chamber 52 is restored, a new liquid is supplied from the common liquid chamber 55 through the liquid supply port 53 to the pressure chamber 52.

  FIG. 4A shows an example in which a plurality of nozzles 51 are two-dimensionally arranged as a structure capable of forming a high-resolution image on the recording medium 16 at a high speed. The droplet head is not particularly limited to a structure in which a plurality of nozzles 51 are two-dimensionally arranged, and may have a structure in which a plurality of nozzles 51 are one-dimensionally arranged. The pressure chamber unit 54 shown in FIG. 4B as an ejection element constituting the droplet ejection head is an example, and is not particularly limited to such a case. For example, instead of disposing the common liquid chamber 55 below the pressure chamber 52 (that is, the discharge surface 50a side than the pressure chamber 52), the common liquid is disposed above the pressure chamber 52 (that is, opposite to the discharge surface 50a). The chamber 55 may be disposed. Further, for example, instead of using the piezoelectric body 58a, a liquid discharge force may be generated using a heating element.

* Liquid Supply System FIG. 5 is a schematic diagram showing the configuration of the liquid supply system in the image recording apparatus 10.
The liquid tank 60 is a base tank for supplying liquid to the droplet ejection head 50. A liquid supply pump 62 that feeds liquid from the liquid tank 60 to the droplet ejection head 50 is provided in the middle of a pipe line that connects the liquid tank 60 and the droplet ejection head 50. It is preferable that the temperature of the liquid tank 60, the droplet ejection head 50, and the pipe line connecting the two are adjusted together with the liquid inside by the temperature detecting means and the heater. The liquid temperature at this time is preferably adjusted to 40 ° C to 80 ° C.

  Also, the image recording apparatus 10 includes a cap 64 as a means for preventing the meniscus from drying out of the nozzle 51 or preventing an increase in viscosity in the vicinity of the meniscus during a long discharge suspension period, and a cleaning as a means for cleaning the discharge surface 50a. A blade 66 is provided. The maintenance unit including the cap 64 and the cleaning blade 66 can be moved relative to the droplet ejection head 50 by a moving mechanism (not shown), and if necessary, a maintenance position below the droplet ejection head 50 from a predetermined retraction position. To be moved to.

The cap 64 is moved up and down relatively with respect to the droplet ejection head 50 by a lifting mechanism (not shown). The elevating mechanism raises the cap 64 to a predetermined ascending position and contacts the droplet ejection head 50 to cover at least the nozzle region of the ejection surface 50a with the cap 64.
Preferably, the inside of the cap 64 is divided into a plurality of areas corresponding to the nozzle rows by a partition wall, and each of the partitioned areas can be selectively sucked by a selector or the like.

The cleaning blade 66 is made of an elastic member such as rubber, and can slide on the ejection surface 50a of the droplet ejection head 50 by a cleaning blade moving mechanism (not shown). When droplets or foreign matter adhere to the discharge surface 50a, the discharge surface 50a is wiped by sliding the cleaning blade 66 on the discharge surface 50a, and the discharge surface 50a is cleaned.
The suction pump 67 sucks the liquid from the nozzle 51 of the droplet ejection head 50 in a state where the discharge surface 50 a of the droplet ejection head 50 is covered with the cap 64, and sends the sucked liquid to the recovery tank 68.

Such a suction operation is stopped for a long time in addition to the case where the liquid tank 60 is loaded in the image recording apparatus 10 and liquid is filled from the liquid tank 60 to the droplet ejection head 50 (at the time of initial filling), and the viscosity is increased by stopping for a long time. It is also performed when removing the liquid (when starting to use for a long time).
Here, if the discharge from the nozzle 51 is arranged, first, there is normal discharge that is directed toward the recording medium in order to form an image on a recording medium such as paper, and second, the cap 64 is liquid. There is a purge (also referred to as idle discharge) performed toward the cap 64 as a receiver.

Further, if bubbles are mixed in the nozzle 51 or the pressure chamber 52 of the droplet ejection head 50 or if the viscosity increase in the nozzle 51 exceeds a certain level, the liquid cannot be discharged from the nozzle 51 by the above-described empty discharge. An operation in which the cap 64 is applied to the ejection surface 50 a of the droplet ejection head 50 and the liquid in which the bubbles in the pressure chamber 52 of the droplet ejection head 50 are mixed or the thickened liquid is sucked by the suction pump 67 is performed.
Here, the droplet ejection head 50, the liquid tank 60, the liquid supply pump 62, the cap 64, the cleaning blade 66, the suction pump 67, the recovery tank 68, the liquid flow path connecting them, and other members and devices that are in direct contact with liquid are: It preferably has dissolution resistance and swelling resistance. Moreover, it is preferable that these members and devices have light shielding properties.

* Control System FIG. 6 is a principal block diagram showing the system configuration of the image recording apparatus 10.
In FIG. 6, the image recording apparatus 10 mainly includes a liquid application unit 12, an image detection unit 24, a UV light source 27, a communication interface 110, a system controller 112, memories 114 and 152, a transport motor 116, a motor driver 118, and a heater. 122, heater driver 124, medium type detection unit 132, ink type detection unit 134, illuminance detection unit 135, environmental temperature detection unit 136, environmental humidity detection unit 137, medium temperature detection unit 138, liquid supply unit 142, liquid supply driver 144 , A print controller 150, a head driver 154, and a light source driver 156.
The liquid application unit 12, the image detection unit 24, and the UV light source 27 are the same as those described in FIG. 2 and have already been described.

  The communication interface 110 is an image data input unit that receives image data transmitted from the host computer 300. As the communication interface 110, a wired or wireless interface such as USB (Universal Serial Bus) or IEEE1394 can be applied. The image data input to the image recording apparatus 10 via the communication interface 110 is temporarily stored in the first memory 114 for storing image data.

  The system controller 112 includes a central processing unit (CPU) and its peripheral circuits, and is a main control unit that controls the entire image recording apparatus 10 according to a predetermined program stored in the first memory 114 in advance. That is, the system controller 112 controls each unit such as the communication interface 110, the motor driver 118, the heater driver 124, the medium type detection unit 132, the ink type detection unit 134, and the print control unit 150.

  A conveyance motor 116 applies power to a roller, a belt, or the like for conveying a recording medium such as paper. The liquid application unit 12 and the recording medium are relatively moved by the transport motor 116. The motor driver 118 is a circuit that drives the conveyance motor 116 in accordance with an instruction from the system controller 112.

  The heater 122 is a circuit that drives the heating drum 30 and other heaters 122 in FIG. The heater driver 124 is a circuit that drives the heater 122 in accordance with an instruction from the system controller 112.

  The medium type detection unit 132 detects the type of the recording medium. There are various detection modes for the type of recording medium. For example, an aspect in which a sensor is provided in the paper feeding unit 18 in FIG. 2, an aspect in which the sensor is input by a user operation, an aspect in which the image is input from the host computer 300, and an image input from the host computer 300 There is a mode in which data (for example, resolution and color) or additional data of the image data is automatically detected by analyzing the data.

  The ink type detection unit 134 detects the type of ink. There are various types of ink type detection modes. For example, a mode in which a sensor is provided in the liquid storage / loading unit 14 in FIG. 2, a mode in which the liquid is input by a user operation, a mode in which the liquid is input from the host computer 300, and a mode in which the data is input from the host computer 300 There is a mode in which image data (for example, resolution and color) or additional data of the image data is automatically detected by analysis.

The illuminance detection unit 135 detects the illuminance of ultraviolet rays emitted from the UV light source 27. As an illuminance detection mode, for example, an illuminance sensor is provided in the vicinity of the UV light source 27 in FIG.
The environmental temperature detection unit 136 detects the temperature of the outside air or the image recording apparatus. As an environmental temperature detection mode, for example, there is a mode of detection by providing a temperature sensor outside or inside the device.
The environmental humidity detector 137 detects the outside air or the humidity inside the image recording apparatus. As an environmental humidity detection mode, for example, there is a mode of detection by providing a humidity sensor outside or inside the device.
The medium temperature detection unit 138 detects the temperature at the time of image formation on the recording medium. There are various medium temperature detection modes. For example, there is a mode in which a contact-type temperature sensor is provided in the belt conveyance unit 22 of FIG.

The liquid supply unit 142 includes a conduit for flowing ink from the liquid tank 60 to the liquid applying unit 12 in FIG.
The liquid supply driver 144 is a circuit that drives the liquid supply pump 62 and the like constituting the liquid supply unit 142 so that the liquid is supplied to the liquid application unit 12.

The print control unit 150 applies or discharges (droplets) the coating device and the droplet ejection heads constituting the liquid application unit 12 toward the recording medium based on the image data input to the image recording device 10. Data required for the operation (hereinafter referred to as droplet ejection data) is generated. That is, the print control unit 150 functions as an image processing unit that performs image processing such as various processes and corrections for generating droplet ejection data from image data in the first memory 114 under the control of the system controller 112. The generated droplet ejection data is supplied to the head driver 154.
The print controller 150 also determines the thickness of the liquid film formed on the recording medium by the processing liquid based on the medium type detected by the medium type detector 132 and the ink type detected by the ink type detector 134. And the thickness of the liquid film is switched by controlling the coating amount of the processing liquid using the head driver 154.
The print controller 150 is accompanied by a second memory 152, and droplet ejection data and the like are temporarily stored in the second memory 152 during image processing in the print controller 150.

  In FIG. 6, the second memory 152 is shown in a form associated with the print control unit 150, but it can also be used as the first memory 114. Also possible is an aspect in which the print controller 150 and the system controller 112 are integrated and configured with one processor.

  The head driver 154 is based on droplet ejection data (actually, droplet ejection data stored in the second memory 152) given from the print control unit 150. An application or ejection drive signal is output to the head. The coating drive signal output from the head driver 154 is applied to the coating device, and the ejection drive signal is applied to each droplet ejection head (specifically, the actuator 58 shown in FIG. 4B), whereby the coating device. A treatment liquid is applied to the recording medium from 12P, and a liquid (droplet) is ejected from the droplet ejection head 50 toward the recording medium.

  The light source driver 156 detects an instruction from the print control unit 150, the illuminance detected by the illuminance detection unit 135, the environmental temperature detected by the environmental temperature detection unit 136, the environmental humidity detected by the environmental humidity detection unit 137, and the medium temperature detection. This is a circuit that controls the voltage, time, and timing input to the UV light source 27 based on the medium temperature detected by the unit 138 and drives the UV light source 27.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

<Preparation of pigment dispersion>
16 g of PB15: 3 (IRGALITE BLUE GLO; manufactured by Ciba Specialty Chemicals), 48 g of 1,6-hexanediol diacrylate (HDDA; manufactured by Daicel Cytec Co., Ltd.), and 16 g of BYK-168 (manufactured by BYK Chemie) Mix and stir with a stirrer for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain pigment dispersion P-1.
The dispersion conditions were such that zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 1 hour.

<Preparation of Inkjet Recording Liquid I-1 Containing Pigment>
The following composition was mixed with stirring and dissolved to prepare inkjet recording liquid I-1. In addition, sp value of the obtained liquid I-1 was 20, and the surface tension was 32 N / m.
-Pigment dispersion P-1 ... 3.75 g
・ 1,6 hexanediol diacrylate (polymerizable compound) ... 11.25g
(HDDA; manufactured by Daicel Cytec Co., Ltd.)

  Here, the sp value is R.D. L. It was calculated by a sp value calculation program by Smith (Tohoku University) (25 ° C.). However, the compound containing no carbon atom was excluded from the calculation, and the structural unit such as a polymer or polyethylene chain was a saturated repeating unit having a bond, and water was calculated as 47.8.

<Preparation of Inkjet Recording Liquids II-1 to II-8 not Containing Pigment>
The following composition was mixed with stirring and dissolved to prepare inkjet recording liquid II-1. The sp value of liquid II-1 was 20, and the surface tension was 23 N / m.
・ 1,6-hexanediol diacrylate (polymerizable compound) ... 11.7 g
(HDDA; manufactured by Daicel Cytec Co., Ltd.)
-The following polymerization initiator-1 ... 1.5g
(Irg907 Ciba Specialty Chemicals)
-The following sensitizer-1 ... 0.75g
(Darocur ITX Ciba Specialty Chemicals)
-The following sensitizer-1 ... 0.75g
(Darocur EDB Ciba Specialty Chemicals)
・ Megafuck F781F ... 0.3g
(Dainippon Ink Chemical Co., Ltd.)

Further, in the preparation of liquid II-1, in the same manner as the preparation of liquid II-1, except that 1,6-hexanediol diacrylate, which is a polymerizable compound, was replaced with an equivalent amount of the compounds shown in Table 1 below, Liquids II-2 to II-8 were prepared. The sp values and surface tensions of liquids II-2 to II-8 were the same as those of II-1. The viscosities at 25 ° C. of liquids II-2 to II-8 are shown in Table 1 below.
As described, the viscosity of the liquid at 25 ° C. was measured with a laboratory-use handheld digital viscometer viscostick (manufactured by Maruyasu Kogyo Co., Ltd.) while maintaining the temperature at 25 ° C.

<Preparation of Inkjet Recording Liquids II-11 to II-18 not Containing Pigment>
In the preparation of the liquid II-1, the same procedure as in the preparation of the liquid II-1 was performed except that 1,6 hexanediol diacrylate, which is a polymerizable compound, was replaced with an equal weight organic solvent as shown in Table 2 below. Liquid II-11 to II-18 were prepared. The sp values and surface tension of liquids II-11 to II-18 were the same as those of II-1. The viscosities at 25 ° C. of liquids II-11 to II-18 are shown in Table 2 below.

<Preparation of Inkjet Recording Liquids II-21 to II-26 not Containing Pigment>
A liquid was used except that the polymer shown in Table 3 below was replaced by 15% by mass of 1,6 hexanediol diacrylate (11.7 g), which is a polymerizable compound, used in the preparation of the liquid II-1. Liquids II-21 to II-26 were prepared in the same manner as II-1. The sp values and surface tension of liquids II-21 to II-26 were the same as those of II-1. The viscosities at 25 ° C. of liquids II-21 to II-26 are shown in Table 3 below.

<Preparation of Liquid I-0 for Inkjet Recording for Comparison Containing Pigment>
The following composition was mixed by stirring and dissolved to prepare an inkjet recording liquid I-0. The sp value of liquid I-0 was 20, and the surface tension was 32 N / m.
-The above-mentioned pigment dispersion P-1 ... 3.75 g
・ 1,6 hexanediol diacrylate (polymerizable compound) ... 8.25g
(HDDA; manufactured by Daicel Cytec Co., Ltd.)
・ Polymerization initiator-1 1.5g
(Irg907 Ciba Specialty Chemicals)
・ Sensitizer-1 0.75g
(Darocur ITX Ciba Specialty Chemicals)
・ Sensitizer-1 0.75g
(Darocur EDB Ciba Specialty Chemicals)

[Comparative Example 1]
-Image recording-
Prepared inkjet recording liquid I-1 and liquid II-1 with an inkjet printer (Toshiba tech head (CA3) mounted = droplet frequency: 4.8 KHz, number of nozzles: 318, nozzle density 150 npi (nozzle / inch), drop size : 4 sets of headsets each having 300 npi by arranging two variable heads in 6 stages from 6 pL to 42 pL. The head is fixed to the airframe, and the recording medium is configured to be movable immediately below the head, and is separated from the head loaded with the ink jet recording liquid I-1 by 15 cm in the traveling direction of the recording medium. An experimental machine with a metal halide lamp installed at the position was prepared. The recording medium was transported on a roll.

First, using the above experimental machine, the liquid II-1 was uniformly applied to the entire surface of the recording medium by the head loaded with the liquid II-1 (drop size: 42 pL). After the liquid II-1 was applied, the head loaded with the liquid I-1 was overprinted with the liquid I-1 on the screen to which the liquid II-1 was applied, and drawn in a line shape (drop size: 42 pL). ). Subsequently, “Aiueo” was drawn with a reverse character of 5 pt. Thereafter, an ultraviolet ray (wavelength 365 nm) was irradiated with a metal halide lamp at an ultraviolet ray amount of 500 mJ / cm ² to fix the image.

  Here, a polyethylene terephthalate (PET: Lumirror: manufactured by Toray Industries, Inc.) sheet having a thickness of 100 μm was used as a recording medium (hereinafter referred to as a PET sheet).

Further, the interval from application of liquid II-1 to droplet ejection of liquid I-1 was 30 seconds. At this time, the transport speed of the PET sheet is adjusted to supply the liquid II-1 at 300 dpi × 300 dpi, and the liquid I-1 between adjacent droplets (for example, the droplets a1 and a2) The overlap ratio between the two was adjusted to 50%.
In addition, as described above, the overlap rate is 100 × (2b−c) / 2b [, where b is the radius of the droplet after 1 second is dropped and c is the interval between adjacent droplet center points. %].

[Comparative Example 2]
In the ink jet printer used in Comparative Example 1, an image was formed on the recording medium in the same manner as in Comparative Example 1, except that the method for applying the liquid II-1 to the recording medium was changed to coating with a rod coater. .
Specifically, the ink jet head for liquid II-1 of TOSHIBA TEC head (CA3) is changed to a rod coater (Matsubo), the diameter of the coil is changed, and the coating thickness of liquid II-1 is set to 6 μm. did. Further, the interval from the application of the liquid II-1 to the droplet ejection of the liquid I-1 was set to 30 seconds as in the comparative example 1.

[Comparative Examples 3 to 5]
An image was formed on a recording medium in the same manner as in Comparative Example 2 except that Liquids II-2, II-11, and II-12 were used instead of Liquid II-1 used in Comparative Example 2.

[Examples 1 to 18]
A comparison was made except that (Liquid II-3 to II-8), (II-13 to II-18), and (II-21 to II-26) were used instead of Liquid II-1 used in Comparative Example 2. An image was formed on the recording medium in the same manner as in Example 2.

[Comparative Example 6]
The liquid I-0 was used in place of the liquid I-1 used in Comparative Example 2 and the liquid II-1 was not used (that is, the liquid I-0 was directly ejected onto the recording medium). An image was formed on the recording medium in the same manner as in Comparative Example 2.

≪Evaluation≫
The following evaluation was performed about each obtained liquid and image. The evaluation results are shown in the following table. Of the liquids prepared above, the liquid “II-” is the liquid II (treatment liquid).

-1. Character quality of reversed characters
Based on the character quality of the reversed characters when ejected on photo paper (Fuji Photo Film), the character portion with the narrowest white space in “Aiueo” is the original character. In comparison, the evaluation was made according to the following evaluation criteria.
<Evaluation criteria>
A: The shape of the letters was in order and the white areas were not narrowed.
B: The white spots are narrowed by 10% or more and less than 30%.
C: The blank portion was narrowed by 30% or more.

-2. Evaluation of stickiness −
Immediately after UV irradiation, the image surface (recording surface) was touched with a finger and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: There was no stickiness.
B: Some stickiness was recognized.
C: Significant stickiness was recognized.

-3. Evaluation of scratch resistance
The PET sheet on which the line-shaped image was recorded was observed for changes when the image after 30 minutes had passed after UV irradiation was rubbed 10 times with an eraser and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: There was no decrease in density due to abrasion.
B: A slight decrease in density due to rubbing was observed.
C: The concentration was remarkably reduced by rubbing.

-4. Evaluation of light resistance
A PET sheet on which a line-shaped image is recorded is irradiated with xenon light (85,000 Lux) using a weather meter (Atlas C.I65) for one week, and the density before and after irradiation is measured with a microdensitometer (model name). : MICRO-PHOTOMETER MPM-No. 172, manufacturer name: manufactured by Union Optical Co., Ltd.) to obtain a dye residual ratio [%], and evaluated in five stages according to the following evaluation criteria. The light resistance was evaluated only for the image on the PET sheet.
<Evaluation criteria>
A: The pigment residual ratio was 90% or more.
B: Dye remaining rate was 89-80%.
C: The pigment residual ratio was 79 to 70%.
D: Dye residual ratio was 69 to 50%.
E: Dye remaining rate was less than 49%.

-5. Evaluation of ozone resistance
A PET sheet on which a line-shaped image was recorded was stored for 1 week under an ozone concentration of 5.0 ppm, and the concentration of the image before and after storage was measured using a microdensitometer (model name: MICRO-PHOTOMETER MPM-No. 172, manufacturer). Name: Union Optical Co., Ltd.) to obtain a dye residual ratio (%), and evaluated in 5 stages according to the following evaluation criteria. The ozone resistance was evaluated only for the image on the PET sheet.
<Evaluation criteria>
A: The pigment residual ratio was 90% or more.
B: Dye remaining rate was 89-80%.
C: The pigment residual ratio was 79 to 70%.
D: Dye residual ratio was 69 to 50%.
E: Dye remaining rate was less than 49%.

As shown in Table 4, it can be seen that the embodiment according to the present invention can obtain better character quality of inverted characters than the comparative example. Specifically, in the image in which the non-image portion is in the wide image portion such as the reversed character, the image obtained in the comparative example has a problem that the area of the non-image portion is reduced and the character quality is deteriorated. However, in the embodiment according to the present invention using a high-viscosity processing liquid, such deterioration of character quality could be avoided.
Examples 13 to 18 using liquids (II-21 to II-26) are shown as reference examples of the present invention.

It is process drawing for demonstrating the image formation principle. 1 is a schematic cross-sectional view showing an overall configuration of an image recording apparatus that records an image by an inkjet recording method of the present invention. It is a top view which expands and shows the liquid provision part and its peripheral part of the image recording apparatus of FIG. (A) is a top view which shows the example of the fundamental whole structure of the droplet ejection head of FIG. 3, (b) is the bb sectional view taken on the line of (a). It is the schematic which shows the structural example of the liquid supply system which comprises an image recording device. It is a block diagram which shows the structural example of the control system which comprises an image recording device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Image recording device 12 Liquid application part 12Y Drop ejection head 12P Coating apparatus 14 Loading part 16 Recording medium 18 Paper supply part 20 Decal process part 22 Belt conveyance part 24 Image detection part 26 Paper discharge part 26A, 26B Paper discharge part 27 Light source 28 Cutter 30 Heating drum 31, 32 Roller 33 Belt 34 Adsorption chamber 35 Fan 36 Belt cleaning unit 48 Cutter 50 Droplet ejection head 50a Discharge surface 51 Nozzle 52 Pressure chamber 53 Liquid supply port 54 Pressure chamber unit 55 Common liquid chamber 56 Diaphragm 57 Individual electrode 58 Piezoelectric actuator 58a Piezoelectric body 60 Liquid tank 62 Liquid supply pump 64 Cap 66 Cleaning blade 67 Suction pump 68 Collection tank 81 Liquid film 81a Gas-liquid interface 82a Liquid droplet 82b Liquid droplet 110 Communication interface 112 System controller 114 Memory 1 6 Motor 116 Conveying motor 118 Motor driver 122 Heater 124 Heater driver 132 Medium type detection unit 134 Ink type detection unit 135 Illuminance detection unit 136 Environmental temperature detection unit 137 Environmental humidity detection unit 138 Medium temperature detection unit 142 Medium temperature detection unit 142 Liquid supply unit 144 Liquid supply Driver 150 Print controller 152 Memory 154 Head driver 156 Light source driver 300 Host computer

Claims (10)

Comprising at least an oleophilic recording liquid for forming an image containing a polymerizable material, and an oleophilic processing liquid having a composition different from that of the recording liquid,
An ink set for ink jet recording, wherein the viscosity of the treatment liquid is 100 mPa · s or more at 25 ° C., and the treatment liquid has any one of the following requirements (I) to ( II ):
(I) A polymerizable material having a viscosity of 100 mPa · s or higher at 25 ° C. and higher in viscosity than the polymerizable material contained in the recording liquid is included.
(II) A compound represented by the following formulas [S-1] to [S-9] and (SH-27) having a viscosity of 100 mPa · s or higher at 25 ° C. and a boiling point higher than 100 ° C. including at least one high-boiling organic solvent selected from

In the formula [S-1], R ₁ , R ₂ and R ₃ each independently represents an aliphatic group or an aryl group. A, b and c each independently represent 0 or 1;
In the formula [S-2], R ₄ and R ₅ each independently represents an aliphatic group or an aryl group, and R ₆ represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl. Represents a group, and d represents an integer of 0 to 3. When d is plural, plural R ₆ may be the same or different.
In the formula [S-3], Ar represents an aryl group, e represents an integer of 1 to 6, and R ₇ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.
In the formula [S-4], R ₈ represents an aliphatic group, f represents an integer of 1 to 6, and R ₉ represents a f-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.
In the formula [S-5], g represents an integer of 2 to 6, R ₁₀ represents a g-valent hydrocarbon group (excluding an aryl group), and R ₁₁ represents an aliphatic group or an aryl group.
In the formula [S-6], R ₁₂ represents a hydrogen atom, an aliphatic group or an aryl group, and R ₁₃ and R ₁₄ each independently represents an aliphatic group having 1 to 24 carbon atoms or an aryl having 6 to 18 carbon atoms. Represents a group. X represents —CO— or —SO ₂ —. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may be bonded to each other to form a ring.
In the formula [S-7], R ₁₅ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group, and R ₁₆ represents a halogen atom, an aliphatic group, an aryl group. Represents a group, an alkoxy group or an aryloxy group, and h represents an integer of 0 to 3. When h is plural, plural R ₁₆ may be the same or different.
In the formula [S-8], R ₁₇ and R ₁₈ each independently represent an aliphatic group having 1 to 24 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ₁₉ represents a halogen atom or an aliphatic group. Represents an aryl group, an alkoxy group or an aryloxy group, and i represents an integer of 0 to 5. When i is plural, plural R ₁₉ may be the same or different.
In the formula [S-9], R ₂₀ and R ₂₁ each independently represents an aliphatic group or an aryl group. j represents 1 or 2; R ₂₀ and R ₂₁ may be bonded to each other to form a ring.
The ink set for ink-jet recording according to claim 1, wherein the high-boiling organic solvent contains at least one selected from compounds represented by the following (SH-1) to (SH-27).


Polymerizable material shown in the (I) to the total mass of the treatment liquid, the to claim 1 or 2 the total content of the high-boiling organic Solvent shown in (II) is equal to or less than 50 wt% The ink set for inkjet recording as described.   The ink set for inkjet recording according to any one of claims 1 to 3, wherein the recording liquid contains a colorant.   5. The ink set for ink jet recording according to claim 1, wherein the content of the colorant in the treatment liquid is 0% by mass or more and less than 1% by mass with respect to the total mass. Using the ink set according to any one of claims 1 to 5,
An ink jet comprising: applying the treatment liquid to a recording medium in advance in a range equal to or wider than the image formed with the recording liquid, and then ejecting the recording liquid to form an image. Recording method.   A desired image is recorded by ejecting the recording liquid onto a recording medium with at least a droplet a1 and a droplet a2, and the droplet a1 and the droplet a2 are ejected with overlapping portions. The inkjet recording method according to claim 6.   The ink jet recording method according to claim 7, wherein an overlapping ratio in the overlapping portion is 10% or more and 90% or less.   9. The ink jet recording method according to claim 7, wherein a droplet size of the droplet a <b> 1 and the droplet a <b> 2 is 0.1 picoliter or more and 100 picoliter or less.   10. The ink jet recording method according to claim 6, wherein the polymerizable material is polymerized or cross-linked by applying active energy to the image after the recording liquid is ejected.