JP2007098683A - Inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording method, with which a high image quality image favorable in storage stability and excellent in line quality with no color mixture is formed. <P>SOLUTION: In the inkjet recording method, in which at least a first liquid X and a second liquid A, the composition of which is different from that of the first liquid X are employed and a desired image is recorded by striking liquid droplets a1 and liquid droplets a2 of the second liquid A against a medium to be recorded, the medium to be recorded is non-permeable or slow-permeable one, the second liquid A includes polymerizable or crosslinkable material and the first liquid X includes an oleophilic solvent and an oil-soluble polymer compound so as to strike the liquid droplets a1 and the liquid droplets a2 over some part or the whole range, to which liquid droplets X are applied before in such a manner that the liquid droplets overlap partially with one another after the application of the first liquid X to the medium to be recorded. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an inkjet image recording method, and more particularly, to an inkjet image recording method capable of forming a high-quality image.

  An ink jet system that ejects ink as droplets from an ink ejection port such as a nozzle is small and inexpensive, and is used in many printers because it can form an image without contact with a print medium. Among these ink jet systems, the piezoelectric ink jet system that ejects ink using deformation of piezoelectric elements and the thermal ink jet system that ejects ink using the boiling phenomenon of ink due to thermal energy are excellent in high resolution and high speed printability. Has characteristics.

Currently, high speed and high image quality are important issues when printing on non-water-absorbing recording media such as plain paper or plastic with an inkjet printer. In particular, if it takes a long time to dry the droplets after printing, image bleeding tends to occur, and droplet ejection interference occurs due to mixing between adjacent ink droplets, which not only prevents sharp image formation. In the case of using a non-water-absorbing recording medium, there is a practical problem such that it is necessary to dry without overlapping the recorded matter immediately after printing because the drying of the solvent is extremely slow. Ink jet recording continuously discharges ink (liquid) droplets as droplet n1, droplet n2, droplet n3,..., Droplet nx, and droplets n1 and n2 on the recording medium. , Droplets n3,... Form a line or form an image, and droplet ejection interference refers to droplets that are ejected adjacent to each other (for example, droplet n1). And the droplet n2) are combined to reduce the surface energy (to reduce the surface area). Since the movement of the droplets occurs when adjacent droplets coalesce, they deviate from the landing position, especially when drawing thin lines with ink containing colorant, the line width is non-uniform and the surface is drawn If it does, it will appear uneven.
As one of the methods for accelerating ink curing in order to suppress image bleeding and droplet ejection interference, an inkjet ink that is cured and fixed by radiation rather than volatilization of the ink solvent has been proposed (for example, Patent Document 1). reference). However, since the pigment dispersion is used as the coloring component, the nozzles are clogged due to the aggregation of the pigment, and it is difficult to discharge the ink stably.
For this reason, in order to perform image formation excellent in transparency and color tone without using a pigment, an ultraviolet curable ink using a dye as a colorant is also disclosed (for example, see Patent Document 2). This ink has a problem that an undesirable polymerization reaction easily occurs during storage and storage stability is not sufficient. Furthermore, since conductive salts are contained and the solubility in these inks may be poor, there is a concern of poor printing due to precipitation in a long-term storage state.

For the purpose of achieving both storage stability and high-speed drying properties, a technique has been proposed in which a two-component ink is used to react both on a recording medium. For example, after a liquid having a basic polymer is adhered, A method of recording an ink containing a dye (for example, see Patent Document 3), a method of applying an ink containing an anionic compound and a coloring material after applying a liquid composition containing a cationic substance (for example, Patent Document) 4), and a recording method using an ink containing a photocurable resin on one side and a photopolymerization initiator on the other side (for example, see Patent Document 5). However, these methods are intended to suppress blurring of the image by precipitation of the dye itself, and cannot suppress droplet ejection interference, and since the aqueous solvent is included, the drying speed is low. Further, the precipitated dye tends to be unevenly distributed on the recording medium, and there is a concern that the image quality is deteriorated.
Further, as a method for providing a good image for light-proof and heat-resistant printing quality, a method for forming an image at the same point of an ink containing a monomer that solidifies upon application of energy and an ink having a plurality of colorants is disclosed. (For example, see Patent Document 6). Also disclosed is an ink jet recording method in which a reaction liquid containing a photopolymerization initiator and an ink composition containing an acrylate monomer are attached to a recording medium (see, for example, Patent Document 7).
However, these methods are intended to suppress blurring of the image by precipitation of the dye itself, and cannot sufficiently prevent deterioration in image quality due to droplet ejection interference. In addition, when the time until curing with actinic rays is long, there is a problem that the dot diameter becomes larger than the intended one. Further, when a multicolor image is to be formed with multicolor ink, there is a problem that inks having different hues are mixed on the image forming support, and improvement has been demanded.
Japanese Patent Laid-Open No. 5-214279 U.S. Pat. No. 4,303,924 Japanese Unexamined Patent Publication No. 63-60783 JP-A-8-174997 Japanese Patent No. 3478495 Japanese Patent Laid-Open No. 8-21818 Japanese Patent No. 3642152

An object of the present invention is to provide an ink jet recording method that forms a high-quality image with excellent line quality even when storage time is good and time until irradiation after droplet ejection is available.
In particular, an object of the present invention is to provide an inkjet recording method for forming a high-quality image without color mixing even when performing multi-color inkjet recording.

In view of the above circumstances, the present inventors conducted extensive research and found that the use of the liquid X containing an oleophilic solvent and an oil-soluble polymer compound can solve the above-mentioned problems, thereby completing the present invention. did.
That is, the present invention is achieved by the following means.

<1> At least the first liquid X and the second liquid A having a different composition are used, and the second liquid A is ejected onto the recording medium with at least the droplets a1 and a2. In the ink jet recording method for recording an image, the recording medium is a non-permeable or slow-permeable recording medium, the second liquid A contains a polymerizable or crosslinkable material, and the first liquid X is a parent material. An oily solvent and an oil-soluble polymer compound are contained, and after the first liquid X is applied onto the recording medium, the droplet a1 and the droplet a2 are overlapped on a part or the entire area on the application of the droplet X An ink jet recording method comprising ejecting droplets so as to have

<2> After application of the first liquid X, before application of the second liquid A, simultaneously or after application, the hue of the second liquid A is different and contains a polymerizable or crosslinkable material. The inkjet recording method according to <1>, wherein at least the droplet b1 and the droplet b2 of the third liquid B are ejected onto a recording medium so as to have an overlapping portion.

<3> The inkjet recording method according to <1> or <2>, wherein the oil-soluble polymer compound has a mass average molecular weight of 80000 or less.
<4> The inkjet recording method according to <3>, wherein the oil-soluble polymer compound has a mass average molecular weight of 1,000 to 20,000.
<5> The inkjet recording method according to any one of <1> to <4>, wherein the oil-soluble polymer compound has a group polarized in the molecule.

<6> The content of the oil-soluble polymer compound is 0.1 to 50% by mass with respect to the total mass of the liquid X, according to any one of the above <1> to <5> The inkjet recording method as described.
<7> The inkjet according to any one of <1> to <6>, wherein the content of the lipophilic solvent is 50 to 99.5% by mass with respect to the total mass of the liquid X. Recording method.

<8> The inkjet recording method according to any one of <1> to <7>, wherein the lipophilic solvent is a high-boiling organic solvent having a boiling point higher than 100 ° C.
<9> The inkjet recording method according to any one of <1> to <8>, wherein an overlapping ratio of the droplets a1 and a2 is 10 to 90%.

<10> The inkjet recording method according to any one of the above <1> to <9>, wherein an interval between the droplets a1 and a2 is 5 to 400 milliseconds.
<11> The inkjet recording method according to any one of <1> to <10>, wherein the second droplet A contains a colorant.

<12> The inkjet according to any one of <1> to <11>, wherein the droplet size of at least one of the droplet a1 and the droplet a2 is 0.1 μL to 10 μL. Recording method.
<13> At least the droplets a1 and a2 are ejected to form a desired image, and then active energy is applied to the image to polymerize or crosslink the polymerizable or crosslinkable material. The inkjet recording method according to any one of <1> to <12> above.

<14> The active energy is applied within 5 minutes and 60 seconds after the droplets a1 and a2 or the droplets b1 and b2 are deposited. Inkjet recording method.

  According to the present invention, the storability is good, the line quality is excellent even when there is time until irradiation after droplet ejection, and even when performing multi-color ink jet recording, the image quality is not mixed. An ink jet recording method for forming an image can be provided.

  The inkjet recording method of the present invention uses at least a first liquid X and a second liquid A having a composition different from that of the first liquid X, and deposits the second liquid A on a recording medium with at least a droplet a1 and a droplet a2. An ink jet recording method for recording a desired image, wherein the recording medium is a non-permeable or slowly permeable recording medium, and the second liquid A contains a polymerizable or crosslinkable material, The first liquid X contains an oleophilic solvent and an oil-soluble polymer compound. After the first liquid X is applied onto the recording medium, the droplet a1 and the droplet a1 are applied to a part or the entire area of the application of the droplet X. The droplet a2 is ejected so as to have an overlapping portion.

  First, the main components constituting the first liquid X, the second liquid A, and the third liquid B used in the ink jet recording method of the present invention will be described in detail below.

(Oil-soluble polymer compound)
The droplet ejection shape of the droplet a1 after the first liquid X is applied on the recording medium contains the oil-soluble polymer compound in the first liquid X, whereby the physical properties of the oil-soluble polymer compound itself. In particular, due to the mobility in the liquid, the droplet ejection shape is maintained, and after the droplet ejection, the ink droplet that has been ejected is prevented from diffusing without being cured.
The oil-soluble polymer compound of the present invention is a polymer compound obtained by polymerization from monomers as described later, and is preferably a polymer compound having a solubility in water of 1 g or less with respect to 100 ml of water. . The oil-soluble polymer compound preferably has a polar group in the molecule. The polar group may be a group directly bonded to the molecular main chain of the oil-soluble polymer compound, Even if it is bonded to the main chain via a side chain, it is not particularly limited. Examples of the polar group include C—O bond, C═O bond, C—N bond, C═N bond, C≡N bond, C—S bond, C═S bond and the like.
Specific examples of the monomer used for the oil-soluble polymer compound include, for example, (meth) acrylic acid alkyl ester [for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate , (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid (C1-18) alkyl ester such as stearyl acrylate, etc.], (meth) acrylic acid cycloalkyl ester [( Meth) acrylic acid cyclohexyl etc.], (meth) acrylic acid aryl ester [(meth) acrylic acid Phenyl oxalate], aralkyl esters [benzyl (meth) acrylate], substituted (meth) acrylic acid alkyl esters [for example, 2-hydroxyethyl (meth) acrylate], (meth) acrylamides [for example, ( Meth) acrylamide, dimethyl (meth) acrylamide, etc.], aromatic vinyls [styrene, vinyltoluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [ Allyl acetate, etc.], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.], vinyl cyanide [(meth) acrylonitrile, etc.], olefins [ethylene, propylene, etc.] and the like.
Among these copolymerizable monomers, (meth) acrylic acid alkyl esters, (meth) acrylamides, and aromatic vinyls are preferable, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate Particularly preferred are 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene. An oil-soluble polymer compound obtained by copolymerizing a monomer having a nitrogen-containing heterocyclic group, a monomer having an onium group, or a monomer having an amino group with these polymers is also a preferred embodiment. More preferably, it is at least one selected from the group consisting of a polymer having a nitrogen-containing heterocycle having the above polarizability, a polymer having an onium group, and a polymer having an amino group.
The amount of the oil-soluble polymer compound added depends on the components of the ink A1 and the ink B1, but from the viewpoint of exhibiting the effects of the present invention and preventing the viscosity from becoming too high, the ink (liquid X ) To 0.1% by mass to 50% by mass, more preferably 0.1% to 15% by mass, still more preferably 0.5% to 10% by mass, Mass% to 5 mass% is particularly preferable.
The oil-soluble polymer compound may be used alone or in combination.

  The mass average molecular weight of the oil-soluble polymer compound is preferably 80,000 or less from the viewpoint of diffusion preventing ability and viscosity, and can effectively exhibit the diffusion preventing ability of the present invention at a low viscosity. More preferably, 2000-15000 is still more preferable, and 3000-12000 is especially preferable. In the present invention, the measurement of the mass average molecular weight is defined as a value measured by a GPC (gel permeation chromatography) method. Specifically, using gel permeation chromatography (SCL-6B, manufactured by Shimadzu Corporation), Shodex-KF804 is used as a GPC column, and the solvent (tetrahydrofuran) is 0.8 ml per minute at 40 ° C. 15 μl of a sample having a concentration of 8 mg / ml (sample) / 20 ml (tetrahydrofuran) was injected while flowing at a flow rate of 5 and measured using polystyrene as a standard substance.

(Polymer having nitrogen-containing heterocycle)
A polymer having a nitrogen-containing heterocycle is a copolymer of a monomer having a nitrogen-containing heterocycle and another monomer, even if it is a homopolymer of only a monomer having a nitrogen-containing heterocycle. May be. In the constitution of the polymer having a nitrogen-containing heterocycle, the monomer having a nitrogen-containing heterocycle is preferably 10 mol% or more, and more preferably 20 mol% or more.

Here, specific examples of the nitrogen-containing heterocycle include saturated heterocycles (for example, aziridine, azetidine, pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine, caprolactam, valerolactam), and unsaturated heterocycles ( Examples thereof include imidazole, pyridine, pyrrole, pyrazole, pyrazine, pyrimidine, indole, purine, quinoline, and triazine.
These nitrogen-containing heterocycles may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group, a carbamoyl group, and an amino group. It is done.

  The polymer according to the present invention is preferably a polymer obtained from a vinyl monomer having these nitrogen-containing heterocycles. Specifically, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acryloylthiomorpholine, N-vinylimidazole, 2-methyl-1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, N-vinylcarbazole N-methylmaleimide, N-ethylmaleimide, 2-isopropenyl-2-oxazoline and the like. Of these, N-vinylimidazole, 2-vinylpyridine, and 4-vinylpyridine are particularly preferable.

  Furthermore, the polymer according to the present invention may be a copolymer of the monomer and a monomer copolymerizable therewith. Examples of the copolymerizable monomer include (meth) acrylic acid alkyl esters [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl (carbon number 1 to 18) ester such as lauryl acrylate and stearyl (meth) acrylate], (meth) acrylic acid cycloalkyl ester [(meth) acrylic acid cyclohexyl etc.], (meth) Acrylic acid aryl ester [phenyl (meth) acrylate, etc.], aralkyl ester (Meth) acrylic acid benzyl etc.], substituted (meth) acrylic acid alkyl esters [eg (meth) acrylic acid 2-hydroxyethyl etc.], (meth) acrylamides [eg (meth) acrylamide, dimethyl (meth) acrylamide Etc.], aromatic vinyls [styrene, vinyl toluene, α-methyl styrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [eg, allyl acetate], halogen-containing single amount Examples thereof include vinyl [vinylidene chloride, vinyl chloride and the like], vinyl cyanide [(meth) acrylonitrile and the like], olefins [ethylene, propylene and the like] and the like.

  Among these copolymerizable monomers, (meth) acrylic acid alkyl esters, (meth) acrylamides, and aromatic vinyls are preferable, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate Particularly preferred are 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene.

In the structure of the polymer having a nitrogen-containing hetero ring, the monomer having a nitrogen-containing hetero ring is preferably 10 mol% or more and 100 mol% or less, and 20 mol% or more and 100 mol% or less. Is more preferable.
These polymers can be synthesized by radical (co) polymerization of the monomers. As the radical polymerization, known methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Further, if necessary, a polymerization initiation catalyst known to those skilled in the art can be used.

  Furthermore, the polymer according to the present invention may be obtained by polycondensation. 2,4-dichlorotriazine (for example, 2,4-dichloro-6-butylamino-1,3,5-triazine) and diamine (for example, N, N′-dimethylethylenediamine, N, N′-dimethylhexamethylenediamine, N, N′-dibutylhexamethylenediamine, N, N′-dioctylhexamethylenediamine, etc.) or a polycondensation obtained by polycondensation of piperazine and a dicarboxylic acid (for example, adipic acid) ester. A coalescence can also be mentioned.

  The following specific examples can be given as preferred nitrogen-containing heterocyclic polymers.

  Furthermore, the following polymers can also be mentioned as preferable specific examples.

(Polymer having onium group)
The polymer having an onium group may be a homopolymer of only a monomer having an onium group, or may be a copolymer of a monomer having an onium group and another monomer. In the constitution of the polymer having an onium group, the monomer having an onium group is preferably 10 mol% or more, and more preferably 20 mol% or more.
Examples of the onium group include an ammonium group, a phosphonium group, and a sulfonium group, and an ammonium group is preferable. The polymer having an ammonium group can be obtained as a homopolymer of a monomer having a quaternary ammonium base, a copolymer of the monomer and another monomer, or a condensation polymer.

  In the present invention, the polymer having an ammonium group is particularly preferably a polymer having at least a unit represented by the following general formula (1) or (2).

In the formula, R represents a hydrogen atom or a methyl group, and R ^{21 to} R ²³ and R ^{25 to} R ²⁷ each independently represents an alkyl group, an aralkyl group, or an aryl group. R ²⁴ represents an alkylene group, an aralkylene group, or an arylene group. Y represents O or NR ′, and R ′ represents a hydrogen atom or an alkyl group. X ⁻ represents a counter anion.

The alkyl group represented by R ^{21 to} R ²³ and R ^{25 to} R ²⁷ preferably has 18 or less carbon atoms, more preferably 16 or less carbon atoms, and particularly preferably 12 or less carbon atoms. The alkyl group may be linear or cyclic, and may have a substituent. Examples of the substituent include an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group, a carbamoyl group, and an amino group.
Specific examples of the (substituted) alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, and 2-ethylhexyl. Group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group, N, N-dimethylaminoethyl group, methoxyethyl group, A chloroethyl group etc. are mentioned.
Among these alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group , N-nonyl group and n-decyl group are preferable, and methyl group, ethyl group, n-propyl group, n-butyl group and n-hexyl group are particularly preferable.

The aryl group represented by R ^{21 to} R ²³ and R ^{25 to} R ²⁷ preferably has 18 or less carbon atoms, more preferably 16 or less carbon atoms, and particularly preferably 12 or less carbon atoms. The aryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group, a carbamoyl group, a cyano group, and an amino group.
Specific examples of the (substituted) aryl group include phenyl group, alkylphenyl group (for example, methylphenyl group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, cumenyl group, mesityl group, tolyl group, Xylyl group, etc.), naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, acetoxyphenyl group, cyanophenyl group and the like.
Among these (substituted) aryl groups, a phenyl group and a naphthyl group are particularly preferable.

The aralkyl group represented by R ^{21 to} R ²³ and R ^{25 to} R ²⁷ preferably has 18 or less carbon atoms, more preferably 16 or less carbon atoms, and particularly preferably 12 or less carbon atoms. Examples of the alkyl part of the aralkyl group include the above alkyl groups, and examples of the aryl part of the aralkyl group include the above aryl groups. The alkyl part and / or aryl part of the aralkyl group may have a substituent, and the substituent is the same as the substituents exemplified for the alkyl group and aryl group.
Specific examples of the (substituted) aralkyl group include a benzyl group, a phenylethyl group, a vinylbenzyl group, a hydroxyphenylmethyl group, a diphenylmethyl group, a trityl group, and a styryl group.
Of these (substituted) aralkyl groups, a benzyl group is particularly preferred.

R ^{21 to} R ²³ and R ^{25 to} R ²⁷ are particularly preferably each independently an alkyl group or an aralkyl group, and among them, a methyl group, an ethyl group, a hexyl group, and a benzyl group are preferable.

R ²⁴ represents a divalent linking group, preferably an alkylene group, an aralkylene group, or an arylene group.
The alkylene group represented by R ²⁴ preferably has 8 or less carbon atoms, more preferably 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. The alkylene group may be linear or cyclic, and may have a substituent. Examples of the substituent include an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group, and a carbamoyl group. And amino groups.
Specific examples of the (substituted) alkylene group include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, 2-hydroxyethylene group, 2-hydroxypropylene group, 2- A methoxypropylene group etc. are mentioned.
Of these (substituted) alkylene groups, a methylene group, an ethylene group, a propylene group, a trimethylene group, and a 2-hydroxypropylene group are particularly preferable.

The arylene group represented by R ²⁴ preferably has 12 or less carbon atoms, more preferably 10 or less carbon atoms, and particularly preferably 8 or less carbon atoms. The arylene group may have a substituent, and the substituent is the same as the substituent exemplified for the aryl group.
Specific examples of the (substituted) arylene group include a phenylene group, an alkylphenylene group (for example, 2-ethyl-1,4-phenylene group, 2-propyl-1,4-phenylene group, etc.), 2-chloro-1 , 4-phenylene group, alkoxyphenylene group (for example, 2-methoxy-1,4-phenylene group, etc.), among which phenylene group is particularly preferable.

The aralkylene group represented by R ²⁴ preferably has 12 or less carbon atoms, more preferably 10 or less carbon atoms, and particularly preferably 8 or less carbon atoms. Examples of the alkyl portion of the aralkylene group include the above alkyl groups, and examples of the aryl portion of the aralkylene group include the above aryl groups. The aralkylene group may have a substituent, and the substituent is the same as the substituents exemplified for the alkyl group and aryl group.
Specific examples of the (substituted) aralkylene group include a xylylene group and a benzylidene group, and a benzylidene group is particularly preferable.

R ²⁴ is particularly preferably an alkylene group, and among them, an ethylene group or a propylene group is preferable.

The alkyl group represented by R ′ is preferably the same as the alkyl group represented by R ^{21 to} R ²³ and R ^{25 to} R ²⁷ . The same applies to preferred embodiments.

  —Y— is particularly preferably —O— or —NH—.

X ⁻ is a counter anion, halogen ion (Cl ⁻ , Br ⁻ , I ⁻ ), sulfonate ion, alkyl sulfonate ion, aryl sulfonate ion, alkyl carboxylate ion, aryl carboxylate ion, PF ₆ ⁻ , BF _4- ^{and the} like can be mentioned. Of these, Cl ⁻ , Br ⁻ , toluenesulfonic acid ions, methanesulfonic acid ions, PF ₆ ⁻ and BF ₄ ⁻ are particularly preferable.

  In the case of a polymer having a unit represented by the general formula (1) or (2), the unit represented by the general formula (1) or (2) is preferably contained in an amount of 10 to 100 mol% in the polymer. The case where it contains 20-100 mol% is more preferable.

  Preferable specific examples of the polymer having a unit represented by the general formula (1) or (2) include the following polymers.

Examples of the polymer having an onium group according to the present invention other than the polymer having a unit represented by the general formula (1) or (2) include an epichlorohydrin-dimethylamine addition polymer, a dihalide compound ( For example, xylylene dichloride, xylylene dibromide, 1,6-dibromohexane) and diamine (N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine), N, N′-dimethylpiperazine, diazabicyclooctane) addition polymerization products, and the like.
Further, polymers having amino groups (for example, polyallylamine, polyvinylamine, polyethyleneimine, polydiallylamine, poly (N-methyldiallylamine), poly (N-ethyldiallylamine), diisocyanates (for example, hexamethylene diisocyanate, isophorone diisocyanate, toluene) Diisocyanate, xylylene diisocyanate) and diols having tertiary amino groups (for example, polyadducts of N-methyldiethanolamine, N-ethyldiethanolamine, N, N′-3-hydroxypropylpiperazine, etc.)) with methyl chloride, ethyl Chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate, p-toluene sulfate It can also be obtained by adding ethyl fonate.
Among these, preferred examples include the following specific examples.

  The polymer having a unit represented by the general formula (1) or (2) can be obtained as a homopolymer of a monomer having the following ammonium group or a copolymer containing the monomer.

  Examples of the monomer having an ammonium group include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N , N-dimethyl-N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-N -P-vinylbenzylammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N Diethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N- (4-methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-N -P-vinylbenzylammonium chloride, trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzyl Ammonium acetate, trimethyl-m-vinylbenzylammonium acetate, N, N, N-triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N- Liethyl-N-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl- N-2- (4-vinylphenyl) ethylammonium acetate, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, Triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride Trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, Trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (acryloylamino) propylammonium chloride, triethyl-3- (acryloylamino) propylammonium chloride, N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride, N, N-die -N-methyl-2- (methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl-3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium bromide, trimethyl-3 -(Acryloylamino) propylammonium bromide, trimethyl-2- (methacryloyloxy) ethylammonium sulfonate, trimethyl-3- (acryloylamino) propylammonium acetate, monomethyldiallylammonium chloride, dimethyldiallylammonium chloride, allylamine hydrochloride, etc. Can do.

Examples of monomers copolymerizable with these monomers include (meth) acrylic acid alkyl esters [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid C1-18 alkyl ester such as ethylhexyl, (meth) acrylic acid lauryl, stearyl (meth) acrylate], (meth) acrylic acid cycloalkyl ester [(meth) acrylic acid cyclohexyl etc.], ( (Meth) acrylic acid aryl esters [phenyl (meth) acrylate etc.], aralkyl Steal [benzyl (meth) acrylate, etc.], substituted (meth) acrylic acid alkyl ester [eg, 2-hydroxyethyl (meth) acrylate, etc.], (meth) acrylamides [eg, (meth) acrylamide, dimethyl (meth) ) Acrylamide, etc.], aromatic vinyls [styrene, vinyl toluene, α-methyl styrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [eg, allyl acetate], halogen-containing Monomers [vinylidene chloride, vinyl chloride, etc.], vinyl cyanides [(meth) acrylonitrile, etc.], olefins [ethylene, propylene, etc.] and the like.
Among these copolymerizable monomers, (meth) acrylic acid alkyl esters, (meth) acrylamides, and aromatic vinyls are preferable, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate Particularly preferred are 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene.

  These polymers can be synthesized by radical (co) polymerization of the monomers. As the radical polymerization, known methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Further, if necessary, a polymerization initiation catalyst known to those skilled in the art can be used.

(Polymer having amino group)
The polymer having an amino group may be a homopolymer only of a monomer having an amino group, or may be a copolymer of a monomer having an amino group and another monomer. In the polymer having an amino group, the monomer having an amino group is preferably 10 mol% or more and 100 mol% or less, and more preferably 20 mol% or more and 100 mol% or less.
Examples of the monomer having an amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-diethylamino. Propyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) Acrylamide, diallylamine, N-methyldiallylamine, N-vinylbenzyl-N, N-dimethylamine, N-vinylbenzyl-N, N-diethylamine, N-vinylbenzyl-N-ethyl-N-methylamine, N-vinylbenzyl -N, N-dihexyl N-vinylbenzyl-N-octadecyl-N-methylamine, N-vinylbenzyl-N′-methyl-piperazine, N-vinylbenzyl-N ′-(2-hydroxyethyl) -piperazine, N-benzyl-N -Methylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate and the like.
Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide are more preferable, Furthermore, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylamide are particularly preferable.

Examples of monomers copolymerizable with these monomers include (meth) acrylic acid alkyl esters [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl moiety, such as ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.], (meth) acrylic acid cycloalkyl ester [( Meth) acrylic acid cyclohexyl etc.], (meth) acrylic acid aryl ester [(meth) acrylic Phenyl etc.], (meth) acrylic acid aralkyl esters [(meth) benzyl benzyl etc.], substituted (meth) acrylic acid alkyl esters [eg (meth) acrylic acid 2-hydroxyethyl etc.], (meth) acrylamides [ For example, (meth) acrylamide, dimethyl (meth) acrylamide, etc.], aromatic vinyl [styrene, vinyl toluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl Examples include esters [such as allyl acetate], halogen-containing monomers [such as vinylidene chloride and vinyl chloride], vinyl cyanides [such as (meth) acrylonitrile], and olefins [such as ethylene and propylene].
Among these copolymerizable monomers, alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms, benzyl (meth) acrylate, and styrene are preferable, ethyl (meth) acrylate, ( Particularly preferred are propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Furthermore, other polymers having an amino group include polyallylamine, polyvinylamine, polyethyleneimine, polydiallylamine, poly (N-methyldiallylamine), poly (N-ethyldiallylamine), and modified products thereof (polyallylamine Benzyl chloride adducts, phenylglycidyl ether adducts, acrylonitrile adducts), diisocyanates (eg hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate) and diols having tertiary amino groups (eg N-methyldiethanolamine) , N-ethyldiethanolamine, N, N′-3-hydroxypropylpiperazine) and the like.
Among these, polyallylamine, polyvinylamine, polyethyleneimine, and modified products thereof are more preferable, and further, a modified product of polyallylamine is particularly preferable.

  In the present invention, the polymer having an amino group is particularly preferably a polymer having a unit represented by the following general formula (3).

In General Formula (3), R ¹¹ represents hydrogen or a methyl group, Y represents O or NR ¹⁵ , R ¹⁵ represents hydrogen or an alkyl group, R ¹² represents a divalent linking group, R ¹³ and R ¹⁴ each independently represents an alkyl group, an aralkyl group or an aryl group.
R ¹¹ is more preferably hydrogen, Y is more preferably O or NH, further preferably O, R ¹³ and R ¹⁴ are more preferably alkyl groups or aralkyl groups, and further preferably alkyl groups. .

The divalent linking group represented by R ¹² is preferably an alkylene group or an arylene group, more preferably an alkylene group.
Specific examples of the divalent linking group include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, phenylene group, 2-hydroxypropylene group, etc. Among these, an ethylene group, a propylene group, and a trimethylene group are particularly preferable.

The alkyl group represented by R ¹³ , R ¹⁴ and R ¹⁵ is preferably an alkyl group having 18 or less carbon atoms, more preferably an alkyl group having 12 or less carbon atoms, and particularly preferably an alkyl group having 8 or less carbon atoms. The alkyl group may be linear or cyclic and may have a substituent. Examples of the substituent include a hydroxy group, an alkoxy group (for example, a methoxy group, an ethoxy group, Propoxy group etc.), aryloxy group (eg phenoxy group etc.), amino group, carbamoyl group, halogen atom and the like.
Specific examples of the (substituted) alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, and 2-ethylhexyl. Group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, hydroxyethyl group, 1-hydroxypropyl group, N, N-dimethylaminoethyl group, methoxyethyl group, A chloroethyl group etc. are mentioned. Among these, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, n -Nonyl group and n-decyl group are more preferable, and methyl group, ethyl group, n-propyl group, n-butyl group and n-hexyl group are particularly preferable.

The aryl group represented by R ¹³ and R ¹⁴ is preferably an aryl group having 18 or less carbon atoms, more preferably an aryl group having 16 or less carbon atoms, and particularly preferably an aryl group having 12 or less carbon atoms. The aryl group may have a substituent.
Specific examples of the (substituted) aryl group include phenyl group, alkylphenyl group (for example, methylphenyl group, ethylphenyl group, n-propylphenyl group, n-butylphenyl group, cumenyl group, mesityl group, tolyl group, Xylyl group, etc.), naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, acetoxyphenyl group, cyanophenyl group, etc., among which phenyl group, naphthyl group Is particularly preferred.

The aralkyl group represented by R ¹³ and R ¹⁴ is preferably an aralkyl group having 18 or less carbon atoms, more preferably an aralkyl group having 16 or less carbon atoms, and particularly preferably an aralkyl group having 12 or less carbon atoms. Examples of the alkyl part of the aralkyl group include the above alkyl groups, and examples of the aryl part of the aralkyl group include the above aryl groups. The aralkyl group may have a substituent.
Specific examples of the (substituted) aralkyl group include a benzyl group, a phenylethyl group, a vinylbenzyl group, a hydroxyphenylmethyl group, a diphenylmethyl group, a trityl group, and a styryl group. Among these, a benzyl group is particularly preferable. preferable.

  Preferable specific examples of the polymer having a unit represented by the general formula (3) include the following polymers.

  Preferred polymers other than the polymer having an amino group according to the present invention and having a unit represented by the general formula (3) include the following polymers.

  The polymer having the unit represented by the general formula (3) can be synthesized using radical (co) polymerization. Examples of the radical (co) polymerization include bulk polymerization, solution polymerization, and emulsion polymerization. These known methods can be used. In addition, it is not limited to this method, Other well-known methods can also be employ | adopted.

(Lipophilic solvent)
The lipophilic solvent used in the present invention will be described.
In the present invention, the first liquid X contains a lipophilic solvent together with the oil-soluble polymer compound. By containing the lipophilic solvent, the above-described droplet ejection interference can be avoided. In addition, the use of the lipophilic solvent of the present invention has an effect that the viscosity of the ink can be lowered.
In the present invention, the lipophilic solvent is contained in the liquid X, but may be contained in the second liquid A, the third liquid B, or the like as long as the effects of the present invention are not impaired.

  The lipophilic solvent is not particularly limited as long as it has a function as a solvent having affinity for oil, and examples thereof include organic solvents and ethylenically unsaturated monomers. Among them, a high boiling point organic solvent having a boiling point higher than 100 ° C. is preferable from the viewpoint of volatility during image formation and production environment. By using a high boiling point organic solvent, the boiling point becomes too low to evaporate during image formation, and the droplet ejection interference avoidance of the present invention is effective. Also, it is not preferable from the environmental aspect that it is evaporated and released into the atmosphere. It is also a preferred embodiment to use a polymerizable compound described in detail later.

-High boiling point organic solvent-
In the present invention, the high-boiling organic solvent is required to be (1) a boiling point higher than 100 ° C., and (2) the viscosity at 25 ° C. is 100 mPa · s or less or the viscosity at 60 ° C. is 30 mPa · s. More preferably, it is as follows.
A high-boiling organic solvent that satisfies this viscosity condition keeps the viscosity low, and the application to the recording medium is less likely to be hindered.
In addition, the boiling point which is the condition of (1) is more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher.
Among the conditions (2), the viscosity at 25 ° C. is preferably 70 mPa · s or less, more preferably 40 mPa · s or less, and particularly preferably 20 mPa · s or less. The viscosity at 60 ° C. is further preferably 20 mPa · s or less, and particularly preferably 10 mPa · s or less.
Furthermore, the high-boiling organic solvent preferably has a melting point of 80 ° C. or lower and a water solubility (25 ° C.) of 4 g or lower. The solubility of water is further preferably 3 g or less, more preferably 2 g or less, and particularly preferably 1 g or less.

  Here, the “viscosity” in the present invention refers to a viscosity obtained using a RE80 viscometer manufactured by Toki Sangyo Co., Ltd. The RE80 type viscometer is a conical rotor / plate type viscometer corresponding to the E type. Measurement was carried out at a rotation speed of 10 rpm using the first rotor. However, for those having a viscosity higher than 60 mPa · s, the measurement was performed by changing the number of rotations to 5 rpm, 2.5 rpm, 1 rpm, 0.5 rpm, or the like as necessary.

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

In the present invention, the content of the lipophilic solvent is preferably 50 to 99.5% by mass, more preferably 60 to 97.5% by mass, and more preferably 70 to 95% by mass with respect to the total mass of the liquid X. Is particularly preferred.
By being in the said range, the effect of this invention can be exhibited favorably.

  In the present invention, the high-boiling organic solvent is preferably a compound represented by the following formulas [S-1] to [S-9].

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 (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 an 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 or 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 a straight chain, 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, aliphatic 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 may contain a cyclic structure or an unsaturated bond. Often (for example, a benzene ring, a cyclopentane ring, a cyclohexane ring) or 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], particularly preferred high boiling point organic solvents 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) are preferred Yes. 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- 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 (eg, methyl, isopropyl, t-butyl, n-dodecyl), an alkoxy group having 1 to 18 carbon atoms (eg, 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 (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 —, a hydrocarbon group having the following structure:

Or an e-valent hydrocarbon group having 4 to 24 (preferably 4 to 18) carbon atoms bonded to each other via an ether bond [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 —, a hydrocarbon group having the following structure] is preferred.

Among these, R ₇ is more preferably an alkyl group, and particularly preferably n-butyl, n-octyl and 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 (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) are preferable, and among these, R ₉ is particularly 2-ethylhexyl, 2-hexyldecyl, 1-methyl-2 -Methoxyethyl, a hydrocarbon group having the following structure is preferred.

In the formula [S-5], g is preferably 2 to 4 (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 —, A hydrocarbon group having a structure of

Among these, R ₁₀ is particularly preferably — (CH ₂ ) ₄ —, — (CH ₂ ) ₈ —, or a hydrocarbon group having the following structure.

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

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, N-di Ji carbamoyl octyl, 3-methylphenyl, 2-(N, N-di -n- octylcarbamoyl) phenyl are preferred.
R ₁₃ and R ₁₄ are each independently 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) are preferable. 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 is 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 ( For example, methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), arylsulfonyl groups having 6 to 30 carbon atoms (preferably 6 to 24) (for example, p-tolylsulfonyl, p-dodecylphenylsulfonyl, p-hexadecyloxy) Phenylsulfonyl), 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. An aliphatic group and an alkoxycarbonyl group having 1 to 24 carbon atoms are 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), 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 Is an aryloxy group (for example, phenoxy, pt-butylphenoxy, pt-octylphenoxy, m-pen) Decylphenoxy, a p- dodecyloxy-phenoxy) Of these, R ₁₆ is further more preferably an aliphatic group having 1 to 24 carbon atoms, particularly preferably an aliphatic group having 1 to 18 carbon atoms.
h is preferably an integer of 1 to 2.

In Formula [S-8], preferred examples of R ₁₇ and R ₁₈ are independently the same as the examples other than the hydrogen atom in R ₁₃ and R ₁₄ , and among these, R ₁₇ and R ₁₈ are more A group is more preferable, and n-butyl, n-octyl and n-dodecyl are particularly preferable. 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 independently the same as 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 is preferably 1.

  Specific examples (S-1 to 53) of high boiling point organic solvents used in the present invention, the viscosity of each high boiling point organic solvent (values measured at 25 ° C. and 60 ° C. by the aforementioned means) and boiling points Indicates. Here, the boiling point of the high-boiling organic solvent described in the present specification is a value converted from the boiling point during vacuum distillation to normal pressure. In the following specific examples, it has been confirmed that those having no boiling point are not boiled at 170 ° C. Moreover, the thing without description of the viscosity in 25 degreeC represents that it is a solid in 25 degreeC.

  In the present invention, the high-boiling organic solvent may be used alone or in combination of two or more [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (Nt-butylacrylamide)] may be used.

  Examples of other high boiling point organic solvents used in the present invention 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 No.711, No.4,239,851, No.4,278,75 No. 4,353,979, No. 4,363,873, No. 4,430,421, No. 4,430,422, No. 4,464,464, No. 4 No. 4,483,918, No. 4,540,657, No. 4,684,606, No. 4,728,599, No. 4,745,049, No. 4,935,321. 5,013,639, European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309, No. 160A, No. 509,311A, No. 510,576A, East German Patent Nos. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2 , 091,124A, etc. 47335, 50-26530, 51-25133, 51-26036, 51-27921, 51-27922, 51-149028, 52-46816, 53-1520 53-1521, 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84441, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 64 -9452, 64-9454, 64-68745, JP-A-1-101543, 1-102454 No. 2-792, No. 2-4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338, etc. ing.

(Polymerizable compound)
The second liquid A and the third liquid B in the present invention contain a polymerizable or crosslinkable material (hereinafter referred to as a polymerizable compound).
These polymerizable compounds have a function of causing polymerization or cross-linking reaction and curing by initiating species such as radicals generated from a polymerization initiator described later.
The polymerizable compound can be contained in a liquid other than the second liquid A and the third liquid B. For example, in addition to the liquid X, a fourth liquid C having a hue different from that of the second liquid A or the third liquid B may be used.

  As such a polymerizable compound, known polymerizable compounds such as a radical polymerization reaction, a cationic polymerization reaction, and 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

  The polymerizable compound preferably has a polymerizable group such as an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, or an internal double bond group (such as maleic acid) in the molecule, and among them, an acryloyl group or a methacryloyl group. A compound having a group is preferable because a curing reaction can be caused with low energy.

As the polyfunctional polymerizable compound that can be used in the present invention, a vinyl group-containing aromatic compound, a (meth) acrylate that is an ester of a divalent or higher alcohol and (meth) acrylic acid, a divalent or higher amine, and a ) (Meth) acrylamide, which is an amide with acrylic acid, polyester (meth) acrylate in which (meth) acrylic acid is introduced into an ester or polycaprolactone obtained by combining polybasic acid and dihydric alcohol, alkylene oxide and polyhydric alcohol It is obtained by introducing (meth) acrylic acid into the ether obtained by bonding of (meth) acrylic acid into the ether obtained by introducing the (meth) acrylic acid into the epoxy resin, or by reacting a divalent or higher alcohol with an epoxy-containing monomer. Epoxy (meth) acrylate, urethane acrylic with urethane bond , Amino resin acrylate, acrylic resin acrylate, alkyd resin acrylate, spirane resin acrylate, silicone resin acrylate, reaction product of unsaturated polyester and photopolymerizable monomer, and reaction product of wax and polymerizable monomer. (Meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, epoxy acrylate, urethane acrylate, acrylic resin acrylate, silicone resin acrylate, reaction product of unsaturated polyester and photopolymerizable monomer are preferred. Acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, and urethane acrylate are particularly preferable.
In this specification, when referring to either or both of acrylic acid and methacrylic acid, “(meth) acrylic acid” may be used.

  Specific examples of the polyfunctional polymerizable compound include, for example, divinylbenzene, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate. 1,6-acryloylaminohexane, hydroxypivalate ester neopentylglycol diacrylate, polyester acrylate having a (meth) acryloyl group at the molecular chain end of a polyester having a molecular weight of 500 to 30,000 consisting of a dibasic acid and a dihydric alcohol, polyethylene Glycol diacrylate, epoxy acrylate containing bisphenol (A or S, F) skeleton having a molecular weight of 450 to 30,000, skeleton of phenol novolac resin Epoxy acrylate with a molecular weight of 600 to 30,000 with the reaction of a polyvalent isocyanate and a hydroxyl group (meth) acrylate monomer having a molecular weight of 350 to 30,000, also urethane-modified product having a urethane bond in the molecule.

  Examples of the monofunctional polymerizable monomer that can be used in the present invention include (meth) acrylate, styrene, acrylamide, vinyl group-containing monomers (vinyl esters, vinyl ethers, N-vinyl amide, etc.), (meth) acrylic acid, and the like. (Meth) acrylate, acrylamide, vinyl esters and vinyl ethers are preferable, and (meth) acrylate and acrylamide are particularly preferable. These polymerizable monomers may have a substituent, and examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, an amide group, and a carboxylic acid group.

  Specific examples of the monofunctional polymerizable monomer include, for example, hydroxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, 2-acryloyloxyethyl phosphate, allyl acrylate, N, N-dimethylaminoethyl acrylate. N, N-dimethylacrylamide, N, N-diethylaminopropylacrylamide, N-butoxymethylacrylamide, acryloylmorpholine, 2-hydroxyethyl vinyl ether, N-vinylformamide, N-vinylacetamide, 2-cyclohexylcarbamoyloxyethyl acrylate, ester Acrylate containing polybutyl acrylate moiety in the ester and acrylate containing polydimethylsiloxane moiety in the ester Such as theft and the like.

Only 1 type may be used for a polymeric compound and it may use it in combination of 2 or more type.
As content of the polymeric compound contained in the 2nd liquid A or the 3rd liquid B, the range of 50-99.6 mass% is preferable in conversion of solid content in this liquid, 70-99.0 mass% Is more preferable, and the range of 80 to 99.0% by mass is more preferable. Moreover, as content in all the liquids, the range of 20-98 mass% is preferable in conversion of solid content, The range of 40-95 mass% is more preferable, The range of 50-90 mass% is especially preferable.

<Polymerization initiator>
In the present invention, from the viewpoint of storage stability of the liquid, the liquid X preferably contains a polymerization initiator that cures the polymerizable compound. A polymerization / curing reaction occurs when energy is applied to both on the recording medium.
The polymerization initiator used in the present invention refers to a compound that initiates and accelerates the polymerization of the polymerizable compound by generating initiating species such as radicals by energy of light, heat, or both. As the polymerization initiator in the present invention, a known thermal polymerization initiator, a compound having a bond with small bond dissociation energy, a photopolymerization initiator, or the like can be selected and used. A photopolymerization initiator is preferred.
Examples of such radical generator include organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oniums. Examples thereof include salt compounds.

  Preferred examples of the polymerization initiator in the present invention include the following photopolymerization initiators. For example, light of acetophenone derivative, benzophenone derivative, benzyl derivative, benzoin derivative, benzoin ether derivative, benzyldialkyl ketal derivative, thioxanthone derivative, acylphosphine oxide derivative, metal complex, p-dialkylaminobenzoic acid, azo compound, peroxide compound, etc. Examples of the polymerization initiator include acetophenone derivatives, benzyl derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, thioxanthone derivatives, and acyl phosphine oxide derivatives, and acetophenone derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, acyl phosphine oxide derivatives. Is particularly preferred.

  Examples of specific compounds of such photopolymerization initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, p, p′-dichloro. Benzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzyldimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, tetramethyl Thiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,2-dimethylpropioyl diphenyl phosphite Oxide, 2-methyl-2-ethylhexanoyl diphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,3,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, 2,4,6-trichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzo Irnaphthyl phosphonate, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylamino Examples include benzoic acid, p-diethylaminobenzoic acid, azobisisobutyronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), benzoin peroxide, and di-tert-butyl peroxide.

Examples of other preferable photopolymerization initiators include the photopolymerization initiators described on pages 65 to 148 of “UV Curing System” (published by General Technology Center Co., Ltd .: 1989) by Kiyosuke Kato. Can be mentioned.
As the polymerization initiator, those having excellent sensitivity are preferable. However, for example, it is not preferable to use those which cause thermal decomposition at a temperature of 80 ° C. or lower, from the viewpoint of storage stability. It is preferable to select a polymerization initiator that does not cause decomposition.
A polymerization initiator can be used 1 type or in combination of 2 or more types. Further, as long as the effects of the present invention are not impaired, a known sensitizer can be used in combination for the purpose of improving sensitivity.

  The polymerization initiator is preferably contained in a liquid different from the polymerizable compound, but the amount added to the liquid is 0.5 to 20 from the viewpoints of stability over time, curability, and curing speed. % By mass is preferable, 1 to 15% by mass is more preferable, and 3 to 10% by mass is particularly preferable. If the content is too large, precipitation or separation with time may occur, or performance such as strength and rubbing resistance of the ink after curing may be deteriorated.

<Colorant>
In the present invention, the second liquid A and the third liquid B preferably contain a colorant, and more preferably contain the second liquid A. Further, the colorant can be contained in a liquid other than the second liquid A and the third liquid B.
That is, since the second and third droplets in the present invention can each independently contain a colorant, a variety of colors ranging from colorless and transparent containing no colorant to colors containing a colorant are included. An image can be formed.

The colorant used in the present invention is not particularly limited, and can be appropriately selected from known water-soluble dyes, oil-soluble dyes and pigments as long as they can achieve a hue and color density suitable for the purpose. .
Among these, the liquid constituting the ink for ink jet recording of the present invention is preferably a water-insoluble liquid and does not contain an aqueous solvent from the viewpoint of ink droplet stability and quick drying, and from such a viewpoint It is preferable to use an oil-soluble dye or pigment that is easily dispersed and dissolved in a water-insoluble liquid.

(Oil-soluble dye)
There is no restriction | limiting in particular in the oil-soluble dye which can be used for this invention, Arbitrary things can be used. Hereinafter, oil-soluble dyes that can be used in the present invention 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. Other dye species include quinophthalone dyes, nitro / nitroso dyes, 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, xanthenes Examples thereof include carbonium dyes such as 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 above-mentioned dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore group is dissociated. In this case, the counter cation may be an alkali metal or ammonium. It may be an inorganic cation, may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having them in a partial structure.

  The content of the dye in the case of using an oil-soluble dye as the colorant is in the range of 0.05 to 20% by mass in the second liquid A and the third liquid B with respect to the total mass of the respective liquids. It is preferably 0.1 to 15% by mass, more preferably 0.2 to 6% by mass. Moreover, as content in the case where it contains in the said liquid X, the range of 0-1 mass% with respect to the total mass of this liquid X is preferable.

(Pigment)
An embodiment in which a pigment is used as the colorant is also preferable from the viewpoint that cohesive curing is likely to occur when a plurality of types of liquids are mixed.
As the pigment used in the present invention, either an organic pigment or an inorganic pigment can be used, and as the black pigment, a carbon black pigment or the like is preferably exemplified. In general, pigments of three primary colors of black and cyan, magenta, and yellow are used, but pigments having other hues such as red, green, blue, brown, white, gold, silver, etc. The metallic luster pigment, colorless or light-colored extender pigment, and the like can also be used depending on the purpose.
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 is also available as a commercial product from Dainippon Ink and Chemicals, Toyo Ink, etc.

  The volume average particle diameter of the pigment particles contained in the liquid in the present invention is preferably in the range of 10 to 250 nm, more preferably 50 to 200 nm, from the viewpoint of the 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 content in the case of using a pigment as the colorant is 0.1 mass with respect to the total mass of each of the second liquid A and the third liquid B from the viewpoint of optical density and jetting stability. % To 20% by mass is preferable, and 1% to 10% by mass is more preferable.
Moreover, as content in the case where it contains in the said liquid X, the range of 0-1 mass% with respect to the total mass of this liquid X is preferable. The colorant may be used alone or in combination of two or more. Further, different colorants may be used for each liquid, or the same may be used.

  In addition, it is preferable to further contain a polymerization initiator, but in this case, from the viewpoint of storage stability, it is preferably contained in the liquid X that does not contain a polymerizable compound.

In the liquid X, liquid A, and liquid B in the present invention, known additives can be used in combination with the above-described components according to the purpose.
<Other ingredients>
(Storage stabilizer)
In the present invention, a storage stabilizer can be added for the purpose of suppressing undesired polymerization during storage of the liquid A and liquid B. The storage stabilizer is preferably used in the same liquid as the polymerizable compound, and it is preferable to use a storage stabilizer that is soluble in the liquid or other coexisting components.
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 addition amount of the storage stabilizer is preferably adjusted as appropriate based on the activity of the polymerization initiator used, the polymerizability of the polymerizable compound, and the type of the storage stabilizer. However, the storage stability and the curability of the ink during liquid mixing are preferred. From the standpoint of balance, the amount is preferably 0.005 to 1% by mass in terms of solid content in the liquid, more preferably 0.01 to 0.5% by mass, and still more preferably 0.01 to 0.2% by mass. .

(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 conductive salts include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like.

(solvent)
The solvent can be used for the polarity of the liquids A, B, and X, the viscosity, the surface tension, the improvement of the solubility / dispersibility of the coloring material, the adjustment of the conductivity and the adjustment of the printing performance. The solvent is preferably a water-insoluble liquid and does not contain an aqueous solvent from the viewpoint of ink droplet ejection stability and quick drying, and the above-described high boiling point organic solvents are particularly preferable.
Moreover, although the low boiling point organic solvent which is an organic solvent of 100 degrees C or less is also mentioned, there exists a possibility of affecting sclerosis | hardenability, and it is desirable not to use a low boiling point organic solvent when environmental pollution is considered. 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.

  The solvent may be used alone or in combination, but when water and / or the above lipophilic solvent is used, the amount of both used is preferably 0 to 20% by mass in each liquid, and 0 to 10% by mass. More preferably, it is particularly preferred that it is substantially free. When water is contained in the liquid, the time stability that the liquid becomes turbid due to non-uniformity over time, precipitation of the dye, etc., and the viewpoint of the drying property when using a non-water-absorbing recording medium Is not preferable. Here, “substantially not containing” means accepting the existence of inevitable impurities.

(Other additives)
As other additives, known additives such as polymers, surface tension adjusters, ultraviolet absorbers, antioxidants, fading inhibitors and pH adjusters can be used in combination.
Regarding the surface tension adjusting agent, ultraviolet absorber, antioxidant, anti-fading agent, and pH adjusting agent, known compounds may be appropriately selected and used. For example, JP-A-2001-181549 discloses a specific example. The additives described can be used.

In addition to the above, a set of compounds that react by mixing to form aggregates or thicken can be contained in different liquids. The one set of compounds has a feature of rapidly forming aggregates or rapidly thickening the liquid, thereby more effectively suppressing occurrence of droplet ejection interference with adjacent droplets. be able to.
Examples of reaction of a set of compounds that react by the above mixing to form aggregates or thicken are acid / base reactions, hydrogen bonding reactions with carboxylic acid / amide group-containing compounds, and boronic acids / diols. Crosslinking reaction, reaction by electrostatic interaction with cations / anions, and the like.

<Inkjet recording method>
Next, the ink jet recording method of the present invention will be described.
In the ink jet recording method of the present invention (hereinafter also referred to simply as “recording method”), after the first liquid X is applied onto the recording medium, the second liquid is applied to a part or the entire area of the droplet X applied. A droplet a1 and droplet a2 of A are ejected so as to have an overlapping portion.
In particular, after the application of the first liquid X, before the application of the second liquid A, at the same time or after the application, the third liquid B having a hue different from that of the second liquid A is at least the droplet b1 and the droplet. It is preferable to deposit b2 on the recording medium so as to have an overlapping portion.
The liquid X contains an oleophilic solvent and an oil-soluble polymer compound, and is applied onto a recording medium, and a part or the entire area of the application (the same area as the applied area or an area narrower than the area) The droplet a1 and the droplet a2 are adhered to each other by ejecting the droplet a1 and then ejecting the droplet a2 so as to have an overlapping portion on the first droplet a1 after the droplet ejection. Droplet interference can be effectively suppressed. Further, the lateral diffusion of the droplets a1 and a2 can be effectively suppressed.

(Means for applying liquid X, liquid A and liquid B)
In the ink jet recording method, it is necessary to apply the liquid X to a recording medium in advance in the same or wider range than the image on which the second droplet a1 and the droplet a2 are formed by droplet ejection.
By applying the liquid to the recording medium in advance in the same or wider range than the image on which the second droplet a1 and droplet a2 are formed by droplet ejection, a good line quality can be obtained.
If the application area of the liquid X is narrow, a portion where the liquid droplet a1 and the liquid droplet a2 do not overlap occurs, and the effect of the present invention cannot be obtained. If the range to which the liquid X is applied is at least the same as or wider than the range of the droplets a1 and a2, droplet ejection interference based on the droplets a1 and a2 can be improved, and the hue of the liquid A is different. If the third liquid B is ejected, the liquid X is also applied to the droplets such as the droplet b1 and the droplet b2 in order to prevent droplet ejection interference. preferable. The same applies to such regions if liquids with other hues are applied.

  In the ink jet recording method of the present invention, the second liquid droplet a1 and the liquid droplet a2 are ejected and applied by an ink jet nozzle, but the application of the liquid X is not necessarily performed on the recording medium by the ink jet nozzle. It is not necessary and may be applied by other means such as coating. However, from the viewpoint that the ink liquid supply means does not come into contact with the medium, it is preferable to apply by jetting with an ink jet nozzle.

The application of the liquid X needs to be the same as or wider than the image in which the droplets a1 and a2 are formed by droplet ejection. Examples of the method include the following methods.
(1) The droplets are applied in a one-to-one relationship with respect to the droplet ejection areas of the droplets a1 and a2.
(2) The droplets are ejected 1 to 10 pixels wider than the droplet ejection areas of the droplets a1 and a2.

In the ink jet recording method of the present invention, the droplets a1 and a2 need to be ejected with overlapping portions from the viewpoint of drawing with high definition.
The overlapping rate (%) is preferably 10 to 90%, more preferably 20 to 80%, and particularly preferably 30 to 70%. The overlapping rate is an index indicating at what rate the adjacent droplets (droplet a1, droplet a2) overlap. Assuming that the diameter of the droplet after landing on the recording medium is a, the overlap ratio is 50% when ½ 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 droplets is c, 100 × [(2b−c) / 2b] [%].

  The time interval between droplets when droplets a1 and a2 are ejected is not particularly limited, but preferably 5 μs to 400 μs from the viewpoint of image formation time and image quality (droplet shape). It is milliseconds, More preferably, it is 10 microseconds-200 milliseconds, Especially preferably, they are 20 microseconds-100 milliseconds. If the time is less than 5 μs, it is difficult to produce an apparatus capable of performing adjacent droplet ejection within 5 μs, and if it exceeds 400 milliseconds, the image forming speed becomes slow and sufficient productivity may not be ensured. is there.

  The droplet ejection size of the droplet a1 and / or the droplet a2 is preferably 0.1 μL to 10 μL, more preferably 0.1 pL to 100 pL, from the viewpoint of high quality and fineness of the obtained image. Particularly preferably, it is 0.5 pL to 50 μL. When the droplet size is within the above range, it is effective in that an image with high sharpness can be drawn with density. The same applies to the droplet ejection size of the droplet b1 and / or the droplet b2.

In the ink jet recording method of the present invention, the means for applying the liquid X onto the recording medium is not particularly limited, but (i) coating using a coating apparatus, which will be described later, and (ii) jetting using an ink jet nozzle. They can be used and will be described.
In addition, as a droplet ejection unit for the droplet a1 and the droplet a2, (ii) it is necessary to perform ejection by an inkjet nozzle.

Here, the means for applying the liquid onto the recording medium in the recording method will be described. Note that the means for applying the first liquid X, the second liquid A, and the third liquid B will be described by way of example of ejection from an inkjet nozzle.
The means for applying the liquid is not particularly limited, but specific examples include the following two points.

(I) Application using coating apparatus In the inkjet recording method of the present invention, the liquid X is applied onto a recording medium using a coating apparatus, and then the second liquid A (and the third liquid B) is applied. A mode in which an image based on the second liquid A (and the third liquid B) is formed by spraying with an inkjet nozzle is preferable.
The coating device is not particularly limited and may be appropriately selected from known coating devices according to the purpose. For example, an air doctor coater, blade coater, lot coater, knife coater, squeeze coater, impregnation coater, reverse roll coater , Transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, extrusion coater and the like. For details, see Yuji Harasaki's “Coating Engineering”.
Moreover, there is no restriction | limiting in particular as said inkjet nozzle, A well-known nozzle can be suitably selected according to the objective. The ink jet nozzle (ink jet system) will be described in detail later.

(Ii) Injection by inkjet nozzle In the present invention, the application of the liquid X and the application of the second liquid A, such as the droplet a1, etc., are performed in order to avoid droplet ejection interference. Must be granted first. Further, it is preferable that the droplets a1 and a2 are ejected onto the recording medium by ejecting the droplet a1 by an inkjet nozzle and subsequently ejecting the droplet a2.
The inkjet nozzle is the same as described above.

  The ink jet recording method of the present invention remarkably exhibits its excellent effect by using the ink jet recording method according to the above (ii) for applying the liquid X, liquid A, and liquid B droplets. be able to.

A method of jetting by the inkjet nozzle (inkjet recording method) will be described below.
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 Are preferably used.
The ink jet 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 using a plurality of inks having substantially the same hue and different concentrations, and a colorless and transparent type. A method using ink is included.

In the ink jet recording method of the present invention, when the liquid X is applied by means of the above (i), the liquid droplet a1 and the liquid droplet a2 are already recorded on the liquid X by such an ink jet recording method. Applied above, an image is formed.
Further, in the case where the application of the liquid X is performed by the means (ii) above, the recording timing of the liquid X and the ejection of the liquid droplets a1 and a2 is the recording medium at least before the ejection of the liquid X. If it is given to, it will not be limited in particular.

  The preferred physical properties of the ink ejected onto the recording medium by the ink jet recording method of the present invention vary depending on the printing apparatus. In general, the viscosity of each droplet at 25 ° C. is independently from 5 to 100 mPa · s. Preferably, 10 to 80 mPa · s is more preferable. Further, the surface tensions of the first droplet n1 and the second droplet n2 are preferably independently from 20 to 60 mN / m, and more preferably from 30 to 50 mN / m.

  The viscosity of the liquid X is preferably 5 mPa · s to 100 mPa · s, more preferably 10 mPa · s to 80 mPa · s from the viewpoint that the liquid X may be discharged from an inkjet nozzle. The surface tension of the liquid X is preferably 20 mN / m to 60 mN / m, more preferably 30 mN / m to 50 mN / m from the viewpoint of wettability with respect to the recording medium. More preferable physical properties are that the difference in viscosity (25 ° C.) between the droplets a1 and a2 is within 25 mPa · s, and the surface tension is within 20 mN / m.

(Energy application process)
The inkjet recording method of the present invention can be provided with a step of fixing an image by applying active energy after image formation from the viewpoint of obtaining excellent fixability. By imparting active energy, polymerization and curing reactions in the droplets a1 and a2 can be promoted, and a stronger image can be formed more efficiently. Such application of active energy is preferably performed by light irradiation or heating.

By applying energy such as exposure and heating, the generation of active species due to decomposition of the polymerization initiator in the mixed liquid is promoted, and the increase in the active species and the temperature increase cause the polymerization of the polymerizable compound resulting from the active species. The polymerization curing reaction is accelerated.
The irradiation of the active energy (for example, light) is preferably performed within 5 minutes after the first droplet a1 and droplet a2 are deposited from the viewpoint of suppressing diffusion, and is preferably within 3 minutes. More preferred is 2 minutes, and particularly preferred is within 60 seconds.
By setting the irradiation of the active light within 5 minutes, it is preferable from the viewpoint that it is possible to draw a good fine line with suppressed spread.

In the present invention, ultraviolet light, visible light, or the like can be used as an exposure light source for proceeding polymerization of the polymerizable compound. In addition, energy can be applied by irradiating radiation other than light, for example, α rays, γ rays, X rays, electron beams, etc. Among them, it is cost and safety to use ultraviolet rays and visible rays. In view of the above, it is more preferable to use ultraviolet rays. The amount of energy required for the curing reaction varies depending on the type and content of the polymerization initiator, but is generally about 1 to 500 mJ / cm ² .

In addition, when energy is applied by heating, it is preferable to heat for 0.1 s to 1 s under the condition that the temperature of the recording medium surface is in a temperature range of 40 to 80 ° C.
This heating is performed using a non-contact type heating means, and preferably a heating means for passing through a heating furnace such as an oven, a heating means for performing whole surface exposure with ultraviolet light to visible light to infrared light, and the like. Used. Here, examples of the light source used for the exposure as the heating means include a metal halide lamp, a xenon lamp, a tungsten lamp, a carbon arc lamp, and a mercury lamp.

(recoding media)
In the present invention, both an ink non-permeable recording medium and an ink permeable recording medium can be used. Of these, from the viewpoint of being able to be cured with a small amount of energy, the ink non-permeable to the ink slowly permeable. A recording medium is preferred.
Here, the permeable recording medium is a medium in which when a 10 pl (picoliter) droplet is dropped on the recording medium, the time until the entire liquid amount permeates is 100 milliseconds or less. 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.

The excellent effect of the present invention is remarkably exhibited in an ink-impermeable recording medium. Examples of the ink-impermeable recording medium include synthetic resin, rubber, resin-coated paper, glass, metal, earthenware, and wood. In addition, in order to add a function, a base material obtained by combining and combining a plurality of these materials can also 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- Examples include styrene copolymer, diacetate, triacetate, polyimide, cellophane, celluloid, etc. The thickness and shape of these synthetic resin substrates may be in the form of a film, card or block, and are not limited in any way. Never happen. These synthetic resins may be transparent or opaque.
As a usage form of the synthetic resin, it is also preferable to use a film used for so-called soft packaging, and various non-absorbable plastics and films thereof can be used. Examples of various plastic films include PET films and OPS films. , OPP film, PNy film, PVC film, PE film, TAC film and the like. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubbers and the like can be used.

  Examples of the resin-coated paper include a transparent polyester film, an opaque polyester film, an opaque polyolefin resin film, and a paper support obtained by laminating both sides of a paper with a polyolefin resin. Particularly preferred is a polyolefin resin on both sides of the paper. It is a paper support laminated with.

  Any metal can be used as the metal, but these composite materials such as aluminum, iron, gold, silver, copper, nickel, titanium, chromium, molybdenum, silicon, lead, zinc, etc., or stainless steel are preferable. Used.

  Examples of the slow ink permeable recording medium include art paper.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these.

Example 1
<Preparation of dispersion P-1>
16 g of PB15: 3 (IRGALITE BLUE GLO Ciba Specialty Chemicals Co., Ltd.), 48 g of 1,6-hexanediol diacrylate (manufactured by HDDA Daicel Cytec Co., Ltd.), and 16 g of BYK-168 (manufactured by BYK Chemie) are mixed. Stirred for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain pigment dispersion P-1. Dispersion conditions were as follows: 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 cyan pigment (for second liquid A)>
(A) Dispersion P-1 10 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.54 g
(C) Polymerizable compound: 9.46 g of 1,6-hexanediol diacrylate
(HDDA manufactured by Daicel-Cytec)

<Preparation of dispersion P-2>
16g of PV19 (Hostaprem Red E5B02 manufactured by Clariant), 48g of 1,6-hexanediol diacrylate (manufactured by HDDA Daicel-Cytec) and 16g of BYK-168 (manufactured by BYK Chemie) were mixed and stirred for 1 hour. did. The mixture after stirring was dispersed with an Eiger mill to obtain a pigment dispersion P-2. Dispersion conditions were as follows: 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 liquid (II-1) for inkjet recording containing magenta pigment (for third liquid B)>
(A) Dispersion P-2 10 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.54 g
(C) Polymerizable compound: 9.46 g of 1,6-hexanediol diacrylate
(HDDA manufactured by Daicel-Cytec)

<Preparation of liquid (III-1) for ink jet recording ink not containing pigment (for first liquid X)>
(D) High boiling point organic solvent (Exemplary Compound (S-30)) 17.4 g
(E) Polymerization initiator (TPO-L (the following polymerization initiator-1)) 2.6 g

<Preparation of Liquids (III-2) to (III-13) for Inkjet Recording Inks not Containing Pigment>
The above (III-) except that the high-boiling organic solvent in <Liquid (III-1) of inkjet recording ink not containing pigment> was replaced with the high-boiling organic solvent and oil-soluble polymer compound shown in Table 1 below. Samples (III-2) to (III-13) were prepared in the same manner as in 1). The amount of the oil-soluble polymer compound added was 0.34 g with respect to dispersion P-1: 10 g.

<Compared Ink Liquid I-0 for Inkjet Recording of One-Part Type>
(A) Dispersion P-1 20 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.54 g
(D) High boiling point organic solvent: (S-30) 16.86 g
(E) Polymerization initiator (TPO-L (the polymerization initiator-1)) 2.6 g
(F) Oil-soluble polymer compound (P1-1 average molecular weight 8000) 0.34 g

<Comparative ink liquid II-0 for one-component ink jet recording>
(A) Dispersion P-2 20 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.54 g
(D) High boiling point organic solvent: (S-30) 16.86 g
(E) Polymerization initiator (TPO-L (the polymerization initiator-1)) 2.6 g
(F) Oil-soluble polymer compound (P1-1 average molecular weight 8000) 0.34 g

<Comparative ink liquid I-01>
Aqueous pigment dispersion PB15: 3 10.5 g
Styrene / acrylic polymer (mass average molecular weight 7000) 3.15 g
N-methylpyrrolidone 5g
Isopropyl alcohol 5g
76.3g of water

<Comparative Ink Liquid II-01>
Aqueous pigment dispersion PR122 10.5g
Styrene / acrylic polymer (mass average molecular weight 7000) 3.15 g
N-methylpyrrolidone 5g
Isopropyl alcohol 5g
76.3g of water

<Comparative Ink Liquid III-01>
A-TMPT-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10g
60g of water
Isopropyl alcohol 30g

<Evaluation>
An experimental jig using a head CB1 manufactured by Toshiba Tec Corporation (nozzle number 318, nozzle density 150 npi, drop size 6 pl, drive frequency, 4.8 kHz) was prepared.
The ink liquids (I-1), (II-1) and (III-1) obtained above were inserted into the experimental jig. (III-1) The liquid was ejected with a solid, and (I-1) was ejected with a solid on it. (II-1) was further ejected in a line form on it. Adjusting the head moving speed and the angle with respect to the scanning direction, (III-1) is the droplet ejection of (I-1) and (II-1) so that the overlapping rate of adjacent droplet ejection intervals is 5%. The interval was set to 50% overlap.
The droplet ejection interval between the liquid (III-1) and the liquid (I-1) and the liquid (II-1) is 400 milliseconds, and the droplet ejection interval between the liquid (I-1) and the liquid (II-1) is 400 milliseconds. The droplet was ejected.
As the recording medium, a polyethylene terephthalate (PET) sheet having a thickness of 60 μm, (trade name: PPL / Xerox film for laser printer, OHP FILM, manufactured by Fuji Xerox Co., Ltd.) and art paper (trade name: Tokuhishi art both sides, Mitsubishi Paper Industries) Used).

Samples 1 and 2 were obtained 60 seconds after the printing (droplet ejection), using a metal halide lamp with a wavelength of 365 nm and irradiating with ultraviolet rays at 500 mJ / cm ² to form an image.

The obtained image was evaluated on the following items. The results are shown in Table 2.
Further, (II-1) 1 second after the droplet ejection, UV irradiation was performed to cure.

  Samples 1 and 2 were prepared in the same manner as above except that (III-2) to (III-13) and (III-00) were used instead of (III-1). 3-26 were obtained.

  In the preparation of Samples 1 and 2, (I-01), (II-01), and (III-01) are used instead of (I-1), (II-1), and (III-1). Except that, samples 29 to 30 were obtained in the same manner as above.

Furthermore, in the preparation of the above samples 1 and 2, (I-0) and (II-0) are used instead of (I-1) and (II-2), and (III-1) is not ejected. Were performed in the same manner as above to obtain Samples 27 to 28.
Each image sample obtained above was evaluated according to the following items. The results are shown in Tables 2-4.

<Image quality when it takes time to cure after droplet ejection>
The quality of the lines (II-1), (II-01) and (II-0) obtained above was evaluated according to the following criteria.
A: The thickness of the line is uniform and is 0.3 mm or less.
(The spread degree is approximately three times as large as 0.3 mm. Here, the spread degree is a ratio to the diameter of the ink droplet just before reaching the recording medium.)
B: The line thickness is uniform, but the line thickness is greater than 0.3 mm.
C: There is a clear line variation from the liquid pool on the line.

<Evaluation of color mixing>
The bleeding (color mixing) state of cyan ink and magenta ink was evaluated by visual observation according to the following criteria.
A: There is no intercolor bleeding between cyan and magenta.
B: There is almost no intercolor bleeding between cyan and magenta.
C: The magenta droplet is slightly broken and intercolor bleeding occurs.
D: There is no magenta dot shape and it is completely mixed.

<Sticky evaluation>
The printed surface was touched with a finger and evaluated according to the following criteria.
A: No stickiness B: Slightly sticky C: Remarkably sticky

<Abrasion resistance evaluation>
On the PET or art paper on which the image was formed, the image that had passed 30 minutes after printing was rubbed 10 times with an eraser, the change was visually observed, and evaluated according to the following criteria.
A: No decrease in density B: Slight decrease in density C: Remarkable decrease in density

<Light resistance evaluation>
The PET sheet on which the image was formed was irradiated with xenon light (85000 Lux) for 1 week using a weather meter (Atlas C.I65), and the concentration before and after irradiation was measured using a microdensitometer (model name: MICRO-PHOTOMETER MPM-No. 172, manufacturer name: Union Optical Co., Ltd.), and the dye residual ratio was determined. Evaluation was made according to the following 5 levels. The light resistance test was conducted only for PET.
A: Dye remaining ratio is 90% or more B: Dye remaining ratio is less than 90% to 80% or more C: Dye remaining ratio is less than 80% to 70% or more D: Dye remaining ratio is less than 70% to 50% or more E: Dye remaining rate is less than 50%

<Ozone resistance>
Concerning ozone resistance, the density of the pigment sheet was determined by measuring the density of the PET sheet on which the above-mentioned image had been stored for 1 week under a condition of ozone concentration of 5.0 ppm with a microdensitometer. Evaluation was made according to the following 5 levels. The ozone resistance test was performed only with PET.
A: Dye remaining ratio is 90% or more B: Dye remaining ratio is less than 90% to 80% or more C: Dye remaining ratio is less than 80% to 70% or more D: Dye remaining ratio is less than 70% to 50% or more E: Dye remaining rate is less than 50%

As can be seen from the above Tables 2 to 4, by adding the oil-soluble polymer compound in the present invention to the (III) liquid, the (I) liquid is added on the (III) liquid by one application of the (III) liquid. When droplets are ejected, the line width is narrow and good image quality is maintained even when time has passed since the droplet ejection.
However, when the one having a molecular weight exceeding 50000 (samples 11, 12, 23, and 24) is used as in the case of using (III-6), the line quality may be slightly deteriorated.
On the other hand, when the oil-soluble polymer compound according to the present invention is added to the I-liquid type ink liquids I-0 and II-0 (samples 27 and 28), the effect of the present invention is not exhibited, and the object of the present invention is achieved. In order to achieve this, it is understood that the oil-soluble polymer in the present invention needs to be added to the ink liquid (III) different from the I liquid type ink liquids I-0 and II-0.
Further, when I-01 / II-01 not containing a polymerizable compound and III-01 not containing a lipophilic solvent and an oil-soluble polymer compound (samples 29 and 30), the effects of the present invention are exhibited. You can't do that.

Claims (14)

At least the first liquid X and the second liquid A having a different composition are used, and a desired image is recorded by ejecting the second liquid A onto the recording medium with at least the droplets a1 and a2. In the inkjet recording method, the recording medium is a non-permeable or slow-permeable recording medium, the second liquid A contains a polymerizable or crosslinkable material, and the first liquid X is an oleophilic solvent. An oil-soluble polymer compound is contained, and after applying the first liquid X onto the recording medium, the liquid droplet a1 and the liquid droplet a2 are overlapped on a part or the entire area on the application of the liquid droplet X. An ink jet recording method comprising ejecting droplets onto the ink. After the application of the first liquid X, and before or simultaneously with the application of the second liquid A, the third liquid X has a hue different from that of the second liquid A and contains a polymerizable or crosslinkable material. 2. The ink jet recording method according to claim 1, wherein at least the droplet b1 and the droplet b2 of the liquid B are ejected onto a recording medium so as to have an overlapping portion. The inkjet recording method according to claim 1 or 2, wherein the oil-soluble polymer compound has a mass average molecular weight of 80,000 or less. 4. The ink jet recording method according to claim 3, wherein the oil-soluble polymer compound has a mass average molecular weight of 1,000 to 20,000. The ink jet recording method according to claim 1, wherein the oil-soluble polymer compound has a group that is polarized in the molecule. 6. The ink jet recording method according to claim 1, wherein the content of the oil-soluble polymer compound is 0.1 to 50 mass% with respect to the total mass of the liquid X. 6. 7. The ink jet recording method according to claim 1, wherein the content of the oleophilic solvent is 50 to 99.5 mass% with respect to the total mass of the liquid X. 8. The ink-jet recording method according to claim 1, wherein the lipophilic solvent is a high-boiling organic solvent having a boiling point higher than 100 ° C. The ink jet recording method according to any one of claims 1 to 8, wherein an overlapping rate of the droplets a1 and a2 is 10 to 90%. The ink jet recording method according to claim 1, wherein an interval between the droplets a <b> 1 and a <b> 2 is 5 to 400 milliseconds. The inkjet recording method according to claim 1, wherein the second liquid A contains a colorant. 12. The inkjet recording method according to claim 1, wherein a droplet size of at least one of the droplet a <b> 1 and the droplet a <b> 2 is 0.1 μL to 10 μL. The at least one droplet a1 and droplet a2 are ejected to form a desired image, and then an active energy is applied to the image to polymerize or crosslink the polymerizable or crosslinkable material. The inkjet recording method according to any one of 1 to 12. 14. The ink jet recording method according to claim 13, wherein the application of the active energy is performed within 5 minutes after the droplets a1 and a2 or the droplets b1 and b2 are deposited.