JP4738963B2 - Ink set for ink jet recording, ink for ink jet recording, and ink jet image recording method - Google Patents

Description

  The present invention relates to an ink set for ink jet recording, an ink for ink jet recording, and an ink jet image recording method, and more particularly, an ink set for ink jet recording and an ink for ink jet recording used in a multi-liquid aggregation type ink jet image recording method, and The present invention relates to an inkjet image recording method capable of forming a high-quality image.

  An ink jet system that discharges ink from an ink discharge 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 the drying of the solvent is very slow, and it is necessary to dry the recorded material without overlapping immediately after printing. The droplet ejection interference is a phenomenon in which droplets ejected adjacent to each other are united 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 for recording an ink containing a dye (for example, see Patent Document 3), a method for applying an ink containing an anionic compound and a colorant after applying a liquid composition containing a cationic substance (for example, a patent) Reference 4), and a recording method using an ink containing a photocurable resin on one side and a photopolymerization initiator on the other (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.
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

An object of the present invention is to provide an ink set for inkjet recording capable of forming a high-quality image while maintaining long-term storage stability and excellent fixing properties, and suppressing bleeding and droplet ejection interference between adjacent jet inks. And providing an ink for inkjet recording.
Another object of the present invention is to provide an ink jet image recording method capable of forming a high-quality image by suppressing bleeding and droplet ejection interference between adjacent jet inks while maintaining excellent fixability. There is.

The above object is achieved by the present invention described below.
That is, the ink set for inkjet recording of the present invention is
<1> An ink set for inkjet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having at least one selected from the group consisting of N-vinylimidazole, 2-vinylpyridine, and 4-vinylpyridine,
Wherein at least one of a plurality of types of liquids, but Ru jet recording ink set der characterized in that it contains a polymerizable compound.
<2> An ink set for inkjet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having a unit represented by the following general formula (1) or general formula (2),
An ink set for ink jet recording, wherein at least one of the plurality of liquids contains a polymerizable compound.
[In General Formula (1) and General Formula (2), 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. ]
<3> An ink set for inkjet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having a unit represented by the following general formula (3),
An ink set for ink jet recording, wherein at least one of the plurality of liquids contains a polymerizable compound.

[In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group, Y represents O or NR ¹⁵ , R ¹⁵ represents a hydrogen atom 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. ]
(Hereinafter, <1> to <3> are referred to as the first aspect of the present invention.)

< 4 > The ink set for ink jet recording according to any one of <1> to <3>, wherein the first liquid does not substantially contain a colorant.

< 5 > The ink set for ink-jet recording according to any one of <1> to < 4 >, wherein the second liquid contains a colorant.

< 6 > The ink set for inkjet recording according to any one of <1> to < 5 >, wherein the second liquid does not substantially contain an oil-soluble polymer.

< 7 > The ink set for inkjet recording according to any one of <1> to < 6 >, wherein the second liquid contains a polymerizable compound.

< 8 > The ink for inkjet recording according to any one of <1> to < 6 >, wherein each of the first liquid and the second liquid contains a polymerizable compound. Is a set.

< 9 > The ink set for ink jet recording according to any one of <1> to < 8 >, wherein the oil-soluble polymer has a weight average molecular weight of 1,000 to 50,000.

< 10 > The high-boiling organic solvent is contained in at least one of the liquids containing the oil-soluble polymer, and any one of the above <1> to < 9 > It is an ink set for inkjet recording.

< 11 > The inkjet according to any one of <1> to < 10 >, wherein when the plurality of liquids contain a solvent, the solvent does not substantially contain a water-soluble liquid. This is a recording ink set.

< 12 > The ink set for ink jet recording according to < 10 >, wherein the high-boiling organic solvent has a boiling point of 100 ° C. or higher.

< 13 > The ink set for ink-jet recording according to any one of < 5 > to < 12 >, wherein the colorant is an oil-soluble dye or pigment.

< 14 > The ink set for inkjet recording according to < 13 >, wherein the colorant is a pigment.

< 15 > Using the ink set for inkjet recording according to any one of <1> to < 14 >, which includes at least a first liquid and a second liquid and includes a plurality of types of liquids.
Forming an image by applying the first liquid and the second liquid simultaneously on the recording medium, or applying either one first and the other after that so that both liquids are in contact with each other. An ink jet image recording method is characterized. (Hereinafter referred to as the second aspect of the present invention)

< 16 > The inkjet according to < 15 >, wherein the second liquid is ejected by an inkjet nozzle at the same time as or after the first liquid is applied on the recording medium. This is an image recording method.

< 17 > The means for applying the first liquid onto the recording medium is coating using a coating apparatus, and the second liquid is ejected by an inkjet nozzle after coating the first liquid. The inkjet image recording method according to < 15 > or < 16 >.

< 18 > The inkjet image recording method according to < 15 > or < 16 >, wherein the means for applying the first liquid and the second liquid onto the recording medium is ejection by an inkjet nozzle. is there.

< 19 > The inkjet image recording method according to any one of < 15 > to < 18 >, further comprising a step of fixing energy by applying energy to an image formed on a recording medium. It is.

< 20 > The inkjet image recording method according to < 19 >, wherein the application of energy is performed by light irradiation or heating.

< 21 > Contains at least a high-boiling organic solvent and an oil-soluble polymer ,
The ink for ink jet recording, wherein the oil-soluble polymer is a polymer having at least one selected from the group consisting of N-vinylimidazole, 2-vinylpyridine, and 4-vinylpyridine .
<22> At least a high-boiling organic solvent and an oil-soluble polymer,
In the ink for ink jet recording, the oil-soluble polymer is a polymer having a unit represented by the following general formula (1) or general formula (2).
[In General Formula (1) and General Formula (2), 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. ]
<23> Contains at least a high-boiling organic solvent and an oil-soluble polymer,
In the ink for ink jet recording, the oil-soluble polymer is a polymer having a unit represented by the following general formula (3).

[In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group, Y represents O or NR ¹⁵ , R ¹⁵ represents a hydrogen atom 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. ]
(Hereinafter, <21> to <23> are referred to as a third aspect of the present invention.)

< 24 > The ink for inkjet recording according to any one of <21> to <23>, further comprising a polymerization initiator.

< 25 > The ink for inkjet recording according to any one of < 21 > to < 24 >, wherein the ink does not substantially contain a colorant.

< 26 > The ink for inkjet recording according to any one of < 21 > to < 25 >, wherein the polymerizable compound does not substantially contain a polymerizable compound.

< 27 > The above < 21 > to < 26 >, wherein the ink composition is used for an ink set for ink-jet recording, which is composed of a plurality of types of liquids and at least one of the plurality of liquids contains a polymerizable compound. The inkjet recording ink according to any one of the above.

According to the present invention, while maintaining long-term storage stability and excellent fixing properties, an ink set for inkjet recording capable of forming a high-quality image while suppressing bleeding and droplet ejection interference between adjacent jet inks, Ink jet recording ink can also be provided.
In addition, it is possible to provide an inkjet image recording method capable of forming a high-quality image by suppressing bleeding and droplet ejection interference between adjacent jetted inks while maintaining excellent fixability.

  Hereinafter, the ink jet recording ink set according to the first aspect of the present invention will be described first, and then the ink jet recording ink according to the third aspect of the present invention will be subsequently described in the second aspect of the present invention. A certain inkjet image recording method will be described.

<Ink set for inkjet recording: first embodiment of the present invention>
The ink set for ink jet recording of the present invention (hereinafter sometimes simply referred to as “ink set”) includes at least a first liquid and a second liquid, and is composed of a plurality of types of liquids. The first liquid is obtained by dissolving an oil-soluble polymer, and at least one of the plurality of liquids contains a polymerizable compound.
Here, “dissolved” means that 0.05 g / cm ³ or more dissolves in the first liquid at 25 ° C. Thus, in order to dissolve the oil-soluble polymer in the first liquid, it is preferable that the first liquid itself is oily, and if the first liquid contains a solvent, as the solvent, It is preferable to use a high-boiling organic solvent, and it is preferable that substantially no water-soluble solvent is contained.

By using such a first liquid, the oil-soluble polymer contained therein suppresses the diffusion of the colorant on the recording medium, and as a result, it is possible to effectively suppress bleeding and droplet ejection interference, and color An image without division can be obtained.
The oil-soluble polymer is preferably at least one selected from the group consisting of a polymer having a nitrogen-containing heterocycle, a polymer having an onium group, and a polymer having an amino group.

Further, from the feature of the present invention that the oil-soluble polymer suppresses the diffusion of the colorant on the recording medium, the oil-soluble polymer and the colorant are preferably contained in separate liquids, and contain the oil-soluble polymer. It is preferable that the first liquid contains substantially no colorant, while the second liquid preferably contains a colorant. Therefore, it is preferable that the second liquid containing the colorant does not substantially contain an oil-soluble polymer.
It is also preferable to contain a polymerizable compound in the second liquid. In addition, when both the 1st liquid and the 2nd liquid contain a polymeric compound, since the familiarity between both liquids becomes favorable, it is a preferable aspect.

  In the present invention, from the viewpoint of obtaining excellent fixability, at least one of a plurality of types of liquids (including the first liquid and the second liquid) constituting the ink set is polymerizable. It is preferable to contain a polymerization initiator for curing the compound. The polymerization initiator is preferably contained in a liquid containing no polymerizable compound from the viewpoint of storage stability of the liquid.

  Hereinafter, in describing the present invention in detail, first, components constituting the above-mentioned plural kinds of liquids will be described.

[Oil-soluble polymer]
In the present invention, the oil-soluble polymer refers to a polymer having a water solubility of 0.01 g / cm ³ or less. As described above, it is presumed that the oil-soluble polymer suppresses the diffusion of the colorant on the recording medium. The oil-soluble polymer is not particularly limited as long as it falls within the above definition. Specifically, the oil-soluble polymer according to the present invention includes, for example, a (meth) acrylic acid alkyl ester as a monomer. [For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) (Meth) acrylic acid C1 such as t-butyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate -18 alkyl ester etc.], (meth) acrylic acid cycloalkyl ester [(meth) acrylic acid cyclohexyl Etc.], (meth) acrylic acid aryl ester [(meth) acrylic acid phenyl etc.], aralkyl ester [(meth) acrylic acid benzyl etc.], substituted (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid 2- Hydroxyethyl etc.], (meth) acrylamides [eg (meth) acrylamide, dimethyl (meth) acrylamide etc.], aromatic vinyls [styrene, vinyltoluene, α-methylstyrene etc.], vinyl esters [vinyl acetate, Vinyl propionate, vinyl versatate, etc.], allyl esters [eg, allyl acetate], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.], vinyl cyanide [(meth) acrylonitrile, etc.], olefins [ethylene, propylene Oil-soluble high content Child polymer.

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 case selected from the group consisting of the above-mentioned polymer having a nitrogen-containing heterocycle, a polymer having an onium group, and a polymer having an amino group.

  The weight average molecular weight of the oil-soluble polymer is preferably 1,000 or more and 50,000 or less, and more preferably 2,000 or more and 30,000 or less. In the present invention, the measurement of the weight 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.

In the present invention, the oil-soluble polymer is contained in the first liquid. The amount of the oil-soluble polymer used in the present invention is preferably 0.05% by mass to 90% by mass, more preferably 1% by mass to 75% by mass, and 1.5% by mass with respect to the whole of the plurality of liquids. ˜50 mass% is particularly preferred. If the amount used is less than the above-mentioned amount, the effect of the present invention may not be exhibited effectively. If the amount is too large, the viscosity becomes high, which may cause a problem in the dischargeability of the ink liquid.
Further, liquids other than the first liquid (such as the second liquid) may or may not contain the oil-soluble polymer, but in the present invention, it is preferably not substantially contained. Specifically, the content of the oil-soluble polymer, particularly the content of the oil-soluble polymer in the liquid containing the colorant is preferably 0% by mass to 10% by mass, and more preferably 0% by mass to 5% by mass. .

(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.

[Colorant]
In the present invention, among a plurality of types of liquids including the first liquid and the second liquid, any liquid may be a colorless ink that does not contain a colorant, and at least one of the liquids is colored. An agent may be contained.
In the first liquid containing the oil-soluble polymer, the content of the colorant is preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. More preferably, as described above, it is particularly preferable that the first liquid contains substantially no colorant. The phrase “substantially free” does not exclude the inclusion of a colorless and transparent dye / pigment, or a very small amount that cannot be visually recognized.
On the other hand, the second liquid may not contain a colorant, but preferably contains a colorant. When the second liquid contains a colorant and the first liquid contains an oil-soluble polymer, the colorant and the oil-soluble polymer are contained in separate liquids. One of them is preferable because it exhibits the effect of preventing color separation.
The colorant can also be contained in other liquids other than the first liquid and the second liquid. However, as described above, it is preferable that the liquid containing the colorant does not contain an oil-soluble polymer even if it is another liquid.

  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 intended use of the ink. be able to. In particular, as described above, it is preferable that the liquid itself constituting the ink set for inkjet recording of the present invention including the first liquid and the second liquid is a water-insoluble liquid, and a solvent is used. Even if it is a case, it is preferable not to contain an aqueous solvent from the viewpoint of ink ejection stability and quick drying, and from such a viewpoint, oil-soluble dyes and pigments that are easily dispersed and dissolved in a water-insoluble liquid are preferable. It is preferable to use a pigment, and it is more preferable to use a pigment from the viewpoint that the image quality that is the effect of the present invention can be made particularly good and that the weather resistance is good.

(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.

  When the oil-soluble dye is used as the colorant, the content of the dye in the second liquid is preferably in the range of 0.05 to 20% by mass in terms of solid content, and 0.1 to 15% by mass. More preferably, 0.2-6 mass% is especially preferable. Moreover, as content in the case where it contains in other liquids other than a 1st liquid and a 2nd liquid, the range of 0-1 mass% in conversion of solid content in this liquid is preferable.

(Pigment)
An embodiment in which a pigment is used as the colorant is also preferable from the viewpoint that aggregation easily occurs when a plurality 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 30 to 250 nm, more preferably 50 to 200 nm, from the viewpoint of balance between optical density and storage stability. . Here, the volume average particle diameter of the pigment particles can be measured by a measuring device such as LB-500 (manufactured by HORIBA).

The content in the case of using a pigment as the colorant is preferably in the range of 0.1% by mass to 20% by mass in terms of solid content in the second liquid, from the viewpoint of optical density and jet stability. More preferably, it is in the range of 1% by mass to 10% by mass. Moreover, as content in the case where it contains in other liquids other than a 1st liquid and a 2nd liquid, the range of 0-1 mass% in conversion of solid content in this liquid 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.

[Polymerizable compound]
In the present invention, a polymerizable compound is contained in at least one of the plurality of types of liquids including the first liquid and the second liquid. Preferably, the second liquid contains a polymerizable compound, but when both the first liquid and the second liquid contain a polymerizable compound, the familiarity between the two liquids becomes good. This is a preferred embodiment. Although it is one of the suitable aspects to contain a colorant in the second liquid, the colorant contained in the second liquid is effectively captured by the familiarity between the two liquids. I guess that.
The polymerizable compound has a function of causing a polymerization reaction and curing by an initiating species such as a radical generated from a polymerization initiator described later. By containing such a polymerizable compound in any liquid, it is possible to fix the image formed by polymerization and solidification by energy such as light or heat.

  As the 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. When a polymerizable compound is contained in a plurality of types of liquids, different types of polymerizable compounds may be used in the respective liquids, or the same type of polymerizable compound may be used. Is preferably used, the same kind of polymerizable compound is preferably used.

  The content of the polymerizable compound contained in any one or more of the plurality of types of liquids is preferably in the range of 50 to 99.6% by mass in terms of solid content in one type of liquid, The range of 70-99.0 mass% is more preferable, and the range of 80-99.0 mass% is further 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 further more preferable.

  Further, when both the first liquid and the second liquid contain a polymerizable compound, when the content of the polymerizable compound contained in the second liquid is 100 parts by weight, the polymerizability contained in the first liquid. The content of the compound is preferably 1 to 1,000 parts by weight, more preferably 5 to 100 parts by weight, and still more preferably 10 to 50 parts by weight.

[Polymerization initiator]
In the present invention, as described above, at least one of a plurality of types of liquids (including the first liquid and the second liquid) to be used contains a polymerization initiator that cures the polymerizable compound. preferable. In addition, from the viewpoint of storage stability of the liquid, the polymerization initiator is preferably contained in a liquid that does not contain a polymerizable compound, and the polymerization / curing reaction is performed when both are given active energy on the recording medium. Will occur.

  Further, when the polymerizable compound is contained in both the first liquid and the second liquid, as described above, from the viewpoint of storage stability of the liquid, the polymerization initiator contains no polymerizable compound. It is also preferable to make it contain in this liquid. The content of the polymerization initiator in the third liquid is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 10% by mass in the liquid from the viewpoint of stability over time. preferable. On the other hand, in the case of an ink set for ink jet recording consisting of only two liquids, the first liquid and the second liquid, both liquids contain a polymerizable compound. From the viewpoint of stability over time, the colorant It is preferable to contain a polymerization initiator in the second liquid to which is added. It is believed that the colorant acts as a filter and suppresses curing over time.

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.
Examples of such radical generators 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-ethylhexanoyldiphenylphosphine 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.

[Ink set]
In the present invention, there is no particular limitation as long as the oil-soluble polymer (a) is dissolved in the first liquid and the polymerizable compound (c) is contained in at least one of the plurality of types of liquids. A first liquid substantially free of the agent (b) and containing the oil-soluble polymer (a), and substantially free of the oil-soluble polymer (a) and a colorant ( It is preferable to use a plurality of kinds of liquids including at least a second liquid containing b), and to contain the polymerizable compound (c) in at least one of the plurality of kinds of liquids.

Here, a two-liquid type consisting of a first liquid and a second liquid will be described as an example.
(1) A combination in which the oil-soluble polymer (a) and the polymerizable compound (c) are contained in the first liquid, and the colorant (b) is contained in the second liquid,
(2) A combination in which the oil-soluble polymer (a) is contained in the first liquid and the colorant (b) and the polymerizable compound (c) are contained in the second liquid,
(3) A combination in which the oil-soluble polymer (a) and the polymerizable compound (c) are contained in the first liquid, and the colorant (b) and the polymerizable compound (c) are contained in the second liquid,
Is mentioned.

In each of (1) to (3), it is preferable to further contain a polymerization initiator in the first liquid and / or the second liquid. In this case, from the viewpoint of storage stability, In the embodiment of (1) or (2), it is also preferable to use a liquid that does not contain the polymerizable compound (c).
In the case of using three or more liquids such as a three-liquid type, the first liquid and / or the second liquid may contain a polymerization initiator, and the first liquid and / or the second liquid. The liquid may not contain a polymerization initiator in other liquids. Alternatively, the polymerization initiator may be contained in the first liquid and / or the second liquid and contained in the other liquid.

[Other ingredients]
In addition to the components described above, the following additives can be used in combination with the liquids of the present invention in accordance with the purpose.

(solvent)
In the present invention, ink polarity, viscosity, surface tension, improvement in solubility / dispersibility of coloring materials, adjustment of conductivity and printing in any one or more of a plurality of liquids A solvent can be used for performance adjustment. The solvent is preferably a water-insoluble liquid, and is preferably substantially free of an aqueous solvent from the viewpoints of ink droplet ejection stability and quick drying.
Moreover, it is preferable to use the following high boiling point organic solvent for at least one of the liquids containing an oil-soluble polymer such as the first liquid. The high boiling point organic solvent can also be used for a liquid that does not contain an oil-soluble polymer.
Examples of the solvent include a low-boiling organic solvent that is an organic solvent at 100 ° C. or lower, but there is a concern of affecting the curability, and it is desirable not to use the low-boiling organic solvent in consideration of environmental pollution. When used, it is preferable to use a highly safe solvent, and a highly safe solvent is a solvent having a high management concentration (an index indicated by the work environment evaluation criteria), preferably 100 ppm or more, More preferably, it is 200 ppm or more. Specific examples include alcohols, ketones, esters, ethers, hydrocarbons, and the like, and specific examples include methanol, 2-butanol, acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran.

  The solvent may be used alone or in combination, but when water and / or the above low-boiling organic solvent is used, the amount of both used is preferably 0 to 20% by mass in each liquid, and 0 to 10% by mass. Is more preferred, and 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.

-High boiling point organic solvent-
In the present invention, a high-boiling organic solvent can be contained in any one or more of a plurality of types of liquids. The high boiling point organic solvent in the present invention means (1) an organic solvent having a boiling point of 100 ° C. or higher.
The boiling point which is the condition of (1) is more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. Further, the high boiling point organic solvent preferably has a melting point of 80 ° C. or lower, more preferably 25 ° C. or lower.
By containing the high boiling organic solvent, it is possible to more effectively prevent bleeding and droplet ejection interference.
In a high boiling point organic solvent that does not satisfy the boiling point condition of (1), the boiling point becomes too low and evaporates during image formation, which may hinder the effect of avoiding droplet ejection interference according to the present invention. Also, it is not preferable from the environmental aspect that it is evaporated and released into the atmosphere.
From the viewpoint of further suppressing the occurrence of bleeding and droplet ejection interference, the high boiling point organic solvent is preferably contained in a liquid containing an oil-soluble polymer, and is contained in a liquid not containing a polymerizable compound. More preferably.

The high-boiling organic solvent is preferably (2) one having a viscosity at 25 ° C. of 100 mPa · s or less or a viscosity at 60 ° C. of 30 mPa · s or less. A high boiling point organic solvent that does not satisfy any of the viscosity conditions of (2) has a high viscosity, which may not be preferable for applying a liquid onto a recording medium.
Of 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. The high boiling point organic solvent preferably has a water solubility (25 ° C.) of 4 g or less. 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. The measurement was performed using the number 1 rotor at a rotation speed of 10 rpm. However, the viscosity higher than 60 mPa · s was measured by changing the number of revolutions 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. .

The amount of the high-boiling organic solvent added in the liquid is preferably in the range of 50% to 100% by mass, more preferably 70% to 100% by mass, and more preferably 90% by mass with respect to the total mass of the liquid. The amount is particularly preferably 100% by mass or less.
In the ink set of the present invention, the amount of the high-boiling organic solvent used is preferably from 5 to 2000 mass%, more preferably from 10 to 1000 mass%, in terms of the coating amount, based on the colorant to be used.

  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 _{11 to} R ₂₁ , Ar is an aryl group or a group containing an aryl group, the aryl group is a halogen atom, aliphatic group, aryl It may be substituted with a substituent such as a 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 is a cyclic structure (for example, a benzene ring, a cyclopentane ring, A cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Hereinafter, among the high boiling point organic solvents represented by the formulas [S-1] to [S-9], 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 more preferably an alkoxycarbonyl group, and particularly preferably n-butoxycarbonyl.
d is 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 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} -,

] Or an e-valent hydrocarbon group having 4 to 24 (preferably 4 to 18) carbon atoms and bonded to each other by 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 -,

] Is preferable. 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 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. Among these, R ₉ is particularly 2-ethylhexyl, 2-hexyldecyl, 1-methyl-2. -Methoxyethyl,

Is preferred.

In the formula [S-5], g is 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 —,

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

Is preferred.
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 a hydrogen atom or an aliphatic group having 1 to 24 (preferably 1 to 18) carbon atoms (eg, methyl, ethyl, isopropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl). , N-dodecyl, n-tetradecyl, cyclopentyl, cyclopropyl) or an aryl group having 6 to 18 carbon atoms (preferably 6 to 15) (for example, phenyl, 1-naphthyl, p-tolyl), among these, R ₁₃ and R ₁₄ are particularly preferably methyl, ethyl, n-butyl, n-octyl, n-tetradecyl and phenyl.
R ₁₃ and R ₁₄ may be bonded to each other to form a pyrrolidine ring, piperidine ring or morpholine ring together with N, and R ₁₂ and R ₁₃ may be bonded to each other to form a pyrrolidone ring or piperidine ring together with N. Also good.
X is —CO— or —SO ₂ —, and preferably X is —CO—.

In the formula [S-7], R ₁₅ 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, p- dodecyloxy-phenoxy). Among them, R ₁₆ is further more preferably an aliphatic group having 1 to 24 carbon atoms, particularly preferably an aliphatic group having 1 to 12 carbon atoms.
h is an integer of 1-2.

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

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

  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.

  In the present invention, the mass ratio between the colorant and the high-boiling organic solvent is preferably 1: 0.01 to 1: 1, and 1: 0.05 to the colorant: high-boiling organic solvent. More preferably, it is 1: 0.5.

  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.

(Storage stabilizer)
In the present invention, a storage stabilizer can be added for the purpose of suppressing undesirable polymerization during storage of a plurality of types of liquids. 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 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.

(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.
As for the surface tension adjusting agent, the ultraviolet absorber, the antioxidant, the fading preventing agent, and the pH adjusting agent, known compounds may be appropriately selected and used. 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.

<Ink for inkjet recording: Third aspect of the present invention>
The ink for inkjet recording which is a 3rd aspect of this invention contains the said high boiling-point organic solvent and the said oil-soluble polymer at least. Furthermore, although the said polymerization initiator can be contained, it is preferable not to contain the said coloring agent and the said polymeric compound substantially. That is, the ink composition for ink jet recording of the present invention can be applied with the preferred composition and aspect of the first liquid in the first aspect of the present invention.
The ink for ink jet recording of the present invention is preferably used as the first liquid of the ink set for ink jet recording which is the first aspect of the present invention. By using the ink for ink jet recording of the present invention in such a manner, it is possible to suppress bleeding and droplet ejection interference as in the case of the ink set.

<Inkjet image recording method: second embodiment of the present invention>
Next, an ink jet image recording method according to the second aspect of the present invention will be described.
The inkjet image recording method of the present invention (hereinafter sometimes simply referred to as “image recording method”) uses the inkjet recording ink set of the present invention, which is the first aspect of the present invention described above, and An image is formed by simultaneously applying one liquid and a second liquid onto a recording medium, or by applying one liquid first and the other liquid so that both liquids are in contact with each other. To do.
By applying the first liquid containing the oil-soluble polymer and the second liquid containing the colorant so as to come into contact with each other, it is possible to effectively prevent bleeding and droplet ejection interference. An image that can be suppressed and has no color separation can be obtained.

(Liquid application means)
In the above image recording method, it is not always necessary to apply a plurality of types of liquids including the first liquid and the second liquid onto the recording medium by jetting with an inkjet nozzle, but by other means such as coating. However, it is preferable that the second liquid containing the colorant is applied onto the recording medium by jetting with an ink jet nozzle. Further, the second liquid is applied at the same time or when the first liquid is applied. It is preferable from the viewpoint of suppressing bleeding and droplet ejection interference that the second liquid is ejected by an inkjet nozzle later.

Here, the means for applying the first liquid onto the recording medium in the image recording method will be described. As described above, the second liquid applying means will be described by way of example of jetting with an ink jet nozzle, which is a preferred embodiment.
The providing means is not particularly limited, but specific examples include the following two points.

(I) Coating using a coating device In the inkjet image recording method of the present invention, a first liquid is coated on a recording medium using a coating device, and then the second liquid is ejected by an inkjet nozzle. A mode of forming an image is preferable.
The coating device is not particularly limited and can be appropriately selected from known coating devices according to the purpose. For example, an air doctor coater, a blade coater, a lot coater, a knife coater, a squeeze coater, an impregnation coater, a reverse roll coater. , Transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, extrusion coater and the like. For details, please refer to “Coating Engineering” written by Yuji Harasaki.
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.
The liquid other than the first liquid and the second liquid may be applied to the recording medium by any method, such as application by the application apparatus or injection by an inkjet nozzle, and the application timing is also particularly high. Although it is not necessarily limited, when it contains a coloring agent, the means by the injection with an inkjet nozzle is preferable, and it is preferable to apply | coat after apply | coating a 1st liquid.

(Ii) Injection by inkjet nozzle In addition, a mode in which an image is formed by ejecting the first liquid by an inkjet nozzle and simultaneously or subsequently ejecting the second liquid by an inkjet nozzle is preferable. .
The inkjet nozzle is the same as described above.
Similarly to the above, the liquid other than the first liquid and the second liquid may be applied to the recording medium by any method such as application by the above-described application apparatus or injection by an inkjet nozzle. The timing is not particularly limited, but when a colorant is contained, means by jetting with an ink jet nozzle is preferable, and it is preferable that the coloring liquid is applied after the first liquid is applied.

  The above-described ink set for ink jet recording of the present invention is the means (ii) above, and is excellent in its effect when used in an ink jet image recording method in which all other liquids are ejected by ink jet nozzles. Is remarkably exhibited.

Here, the ejection method (inkjet recording method) using the inkjet nozzle will be described. In the present invention, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electric signal is converted into an acoustic beam into ink. Known systems such as an acoustic ink jet system that irradiates and discharges ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating ink and generate pressure 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 case of the above means (i), at least the second liquid is applied onto the recording medium already coated with the first liquid by such an ink jet recording method, and an image is formed. On the other hand, in the case of the above means (ii), at least the first liquid and the second liquid are applied onto the recording medium simultaneously or sequentially by such an ink jet recording method to form an image.
When two or more kinds of liquids are ejected onto the recording medium by the above-described ink jet recording method, the liquids are applied so as to contact each other. There is no restriction | limiting in particular in the aspect which 2 or more types of liquids contact, You may spray so that it may mutually adjoin, You may spray so that it may become the same area | region as the application | coating area | region of one liquid.
The timing of jetting is arbitrary and may be simultaneous or sequential. However, in the case of jetting sequentially, the next liquid may be jetted within 1 second after jetting the first liquid. preferable. The mass of the droplet is not particularly limited and is selected according to the sharpness of the image to be formed. In general, the mass per droplet of one liquid is about 0.5 pl to 10 pl. Is preferred.

In the above means (i), when the first liquid is ejected by the ink jet nozzle prior to the second liquid, the first liquid itself directly contacts the recording medium, so that droplet ejection interference occurs and the droplet is ejected. The peripheral portion of the droplets is jagged. However, since the first liquid does not contain a colorant, the occurrence of droplet ejection interference is not a problem.
In any case of the above means (i) and (ii), the second liquid is the same as the first liquid or on the recording medium to which the first liquid has already been applied. The droplets are ejected so as to come into contact with each other, so that no droplet ejection interference occurs and the dot shape is maintained. From the viewpoint of better dot shape maintenance, it is preferable that the first liquid applied onto the recording medium before the second liquid is applied in a wider range than the range in which the second liquid is to be ejected.

  In addition, in the case of the two-liquid type, the balance of the amount of liquid applied per droplet hitting the image forming unit is the first liquid application amount (per unit area) when the second liquid application amount is 1. Is preferably in the range of 0.05 to 5, more preferably in the range of 0.07 to 1, and particularly preferably in the range of 0.1 to 1. When the ratio of the first liquid to the second liquid is 5 or less, good image quality can be obtained from the viewpoint of relief, and when it is 0.05 or more, the effect of the present invention is achieved. The droplet interference is sufficiently avoided.

Incidentally, the liquid (ink: the first liquid and the second liquid in the first aspect of the present invention, the ink for ink jet recording in the second aspect of the present invention) ejected onto the recording medium by the above-described ink jet recording method. Although preferable physical properties differ depending on the printing apparatus, generally, the viscosity of each liquid at 25 ° C. is preferably 5 to 100 mPa · s, and more preferably 10 to 80 mPa · s. The surface tension of the ink composition is preferably 20 to 60 mN / m, and more preferably 30 to 50 mN / m.
More preferable physical properties are that the difference in viscosity is within 25 mPa · s and the surface tension is within 20 mN / m in the relationship between the first liquid and the second liquid.

(Energy application process)
In the image recording method, from the viewpoint of obtaining excellent fixability, a step of fixing an image by applying active energy after image formation can be provided. By applying active energy, polymerization and curing reaction in the aggregate 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.

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-permeable recording medium and an ink non-permeable to slow-permeable recording medium can be used. Examples of the ink-permeable recording medium include plain paper, inkjet exclusive paper, coated paper, electrophotographic co-paper, cloth, non-woven fabric, porous film, polymer absorber and the like. These are described as “recording materials” in Japanese Patent Application Laid-Open No. 2001-181549.

The excellent effect of the present invention is remarkably exhibited in an ink non-penetrating or slow penetrating recording medium. Examples of the ink non-permeable or slowly permeable recording medium include art paper, 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, 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.

  The support used in the inkjet image recording method of the present invention further includes read-only optical disks such as CD-ROM and DVD-ROM, write-once optical disks such as CD-R and DVD-R, and rewritable optical disks. Can also be used, and an ink receiving layer and a gloss imparting layer can be provided on the label surface side.

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

[Example 1]
1. Preparation of second liquid <Preparation of inkjet recording liquid (I-1)>
(A) Acid compound [compound (A-1) shown below] 3.56 g
(B) Polymerizable compound: DPCA60 (manufactured by Nippon Kayaku) 1.07 g
(C) Polymerizable compound: 8.53 g of 1,6-hexanediol diacrylate
(HDDA: manufactured by Daicel UCB)
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1) shown below] 0.46 g
The above components were mixed and dissolved with stirring to obtain a magenta inkjet recording liquid (I-1). The viscosity of the liquid (I-1) at 25 ° C. was 19.6 mPa · s.

2. Preparation of first liquid <Preparation of ink-jet recording liquid (II-1) containing polymer of the present invention>
(F) High-boiling organic solvent [specific example (S-6)] 10 g
(G) Polymerization initiator [TPO-L: (Initiator-1) below] 1.8 g
(H) Polymer of the present invention [said specific example (P1-1)] 2 g
The above components were mixed and dissolved with stirring to obtain an ink jet recording liquid (II-1).

<Inkjet recording liquids (II-2) to (II-7), (II-10) to (II-16), and (II-19) to (II-23) containing the polymer of the present invention , And Preparation of Inkjet Recording Liquid (II-8), (II-9), (II-17), (II-18), and (II-24) to (II-27) for Reference Example >
In the preparation of the liquid for ink jet recording (II-1), the polymer of the present invention was replaced with the equivalent weight as shown in Table 1 below, and the same as the liquid for ink jet recording (II-1). Liquids for ink jet recording containing a polymer (II-2) to (II-7), (II-10) to (II-16) and (II-19) to (II-23), and for reference examples Inkjet recording liquids (II-8), (II-9), (II-17), (II-18), and (II-24) to (II-27) were prepared.
Table 1 shows the polymers of the present invention used, the polymers for reference examples, and the viscosity of each liquid.

3. Preparation of one-component ink <Preparation of one-component ink jet recording liquid (I-0) for comparison>
(A) Acid compound [said compound (A-1)] 3.56 g
(B) Polymerizable compound: DPCA60 (manufactured by Nippon Kayaku) 1.07 g
(C) Polymerizable compound: 1,6 hexanediol diacrylate 7.67 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1)] 0.46 g
(G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
The above components were mixed and dissolved with stirring to obtain a magenta inkjet recording liquid (I-0). The viscosity of the liquid (I-0) at 25 ° C. was 19.6 mPa · s.

<Preparation of one-component type inkjet recording liquid (I-00)>
(A) Acid compound [said compound (A-1)] 3.56 g
(B) Polymerizable compound: DPCA60 (manufactured by Nippon Kayaku) 1.07 g
(C) Polymerizable compound: 1,6 hexanediol diacrylate 9.53 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1)] 0.46 g
(F) High-boiling organic solvent [specific example (S-6)] 13.10 g
(G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
The above components were mixed and dissolved with stirring to obtain a magenta inkjet recording liquid (I-00). The viscosity of the liquid (I-00) at 25 ° C. was 19.6 mPa · s.

<Preparation of one-component type inkjet recording liquid (I1-000)>
(A) Acid compound [said compound (A-1)] 3.56 g
(B) Polymerizable compound: DPCA60 (manufactured by Nippon Kayaku) 1.07 g
(C) Polymerizable compound: 8.53 g of 1,6-hexanediol diacrylate
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1)] 0.46 g
(F) High-boiling organic solvent [specific example (S-6)] 10.10 g
(G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
(H) Glycerin 2g

4). Evaluation <Printing method>
First, printing using a one-component liquid will be described.
The prepared ink jet recording liquid (I-0) was used as an ink jet printer (microjet experimental machine (trade name: ink jet experimental system IJET1000R), printing density: 300 dpi, droplet ejection frequency: 2 KHz, nozzle number: 64, two-row arrangement. ) Was printed on the recording medium.

  The prepared ink jet recording liquid (I-00) was printed in the same manner as the ink jet recording liquid (I-0). However, the droplet ejection frequency was 4 KHz.

Next, printing using a two-component liquid will be described.
First, the prepared inkjet recording liquids (II-1) to (II-27) were printed in the same manner as the inkjet recording liquid (I-0). Next, after the inkjet recording liquids (II-1) to (II-27) were applied to the inkjet recording liquid (I-1), printing was performed so as to overlap. All the liquids were recorded on the recording medium with an ink jet printer (microjet experimental machine (trade name: ink jet experiment system IJET1000R), printing density: 300 dpi, droplet ejection frequency: 2 KHz, number of nozzles: 64, two rows array). Printed on.

  Here, the above-mentioned printing is performed on a polyethylene terephthalate (PET) sheet having a thickness of 60 μm (trade name: PPL / Xerox FILM for laser printers (manufactured by Fuji Xerox)) and art paper (trade name: Tokuhishi art both sides) , Manufactured by Mitsubishi Paper Industries Co., Ltd.).

After printing, a metal halide lamp with a wavelength of 365 nm was used, and an ultraviolet ray was irradiated at an ultraviolet ray amount of 500 mJ / cm ² to form an image. The obtained image was evaluated on the following items.

<Evaluation of droplet ejection interference performance>
(Line quality)
In the above printing step, each liquid was overlaid in a line shape, and the degree of droplet formation overlap (bleeding) was evaluated according to the following criteria. Specifically, in the line-shaped overstrike, the first liquid is ejected in such a manner that the five lines touch each other, and after 10 seconds of the first liquid ejection, the second liquid is ejected from the first liquid by one line. did. However, in the case of (I-0), (I-00), and (I1-000), each of which is a one-liquid type, only one liquid was ejected in a line shape, and the degree of bleeding was evaluated.
A: The line thickness is uniform.
B: There are fine line thickness variations derived from the liquid puddle in some places on the line.
C: There is a clear line variation from the liquid pool on the line.

(Solid image quality)
In the printing process, each liquid was overprinted in a solid image, and the density unevenness was evaluated according to the following criteria. Specifically, solid image-like overstrike means that the first liquid is ejected so that the 60th line is in contact, and 10 seconds after the first liquid is deposited, the second liquid is ejected from the 50th line. The droplets were sprayed so that However, in the case of (I-0), (I-00), and (I1-000), each of which is a one-liquid type, only one liquid was ejected in a solid image shape, and the density unevenness was evaluated.
A: Density unevenness is hardly observed.
B: Slight density unevenness is observed, but the level is satisfactory as a whole.
C: The solid image has density unevenness and the quality is inferior.

<Line color separation evaluation>
In the printing step, each liquid was overlaid in a line shape, and the color separation of the lines was evaluated according to the following criteria. However, in the case of (I-0), (I-00), and (I1-000), which are one-liquid type, only one liquid was ejected in a line shape, and the color separation was evaluated.
A: There is no color separation.
B: A slight color separation is observed, and a slight white spot is observed in the center.
C: The color is largely separated and a thick white spot is observed at the center.

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

<Abrasion resistance evaluation>
After printing on the PET sheet / art paper, the printed part was rubbed 10 times with an eraser for 30 minutes, and the change was evaluated according to the following criteria.
A: No color fading (density reduction) B: Color fading occurs slightly C: Color fading occurs significantly

<Light resistance evaluation>
The PET sheet / art paper on which the image was formed was irradiated with xenon light (85000 Lux) using a weather meter (Atlas C.I65) for one week, and the density of the image area before and after the irradiation was measured with an X-rite 310 densitometer ( X-rite), and the dye residual ratio was determined from the measurement results and evaluated according to the following criteria. The reflection density was measured at -1.0.
A: Dye remaining ratio is 90% or more B: Dye remaining ratio is 80% or more and less than 90% C: Dye remaining ratio is 70% or more and less than 80% D: Dye remaining ratio is 50% or more and less than 70% E: Dye remaining rate is less than 50%

<Ozone resistance>
The PET sheet / art paper on which the image was formed was stored for 1 week under the condition of ozone concentration of 5.0 ppm, and the density of the image part before and after that was measured with an X-rite 310 densitometer (manufactured by X-rite). The dye residual ratio was obtained from the measurement results and evaluated according to the following criteria.
A: Dye remaining ratio is 90% or more B: Dye remaining ratio is 80% or more and less than 90% C: Dye remaining ratio is 70% or more and less than 80% D: Dye remaining ratio is 50% or more and less than 70% E: Dye remaining rate is less than 50%

  The results of the evaluation are shown in Tables 4-6.

As is apparent from Tables 4 to 6, as a two-pack type ink jet recording liquid, one liquid contains a colorant, and the other contains the oil-soluble polymer in the present invention, and the two liquids overlap. When printing was performed in this manner, image formation without ink-dropping interference and color separation occurred rapidly on a non-ink-absorbing PET sheet or art paper. Furthermore, in the present invention, a metal halide lamp having a wavelength of 365 nm is used, and the ultraviolet ray irradiation is performed at an ultraviolet light amount of ~ 500 mJ / cm ² , so that the curing reaction efficiently proceeds quickly, and the printing performance is excellent and there is no stickiness. It can be seen that an image having high scratch resistance, light resistance and ozone resistance can be obtained.
On the other hand, the sample ejected with one liquid has no stickiness and a stable image quality having high scratch resistance, light resistance and ozone resistance is obtained, but droplet ejection interference occurs on the PET sheet or art paper, and the image It can be seen that the formability is not sufficient and there is a problem from the viewpoint of high quality images.
Here, the color separation means that in a liquid containing fine particles such as a pigment, an overflow occurs due to a temperature difference, a solvent concentration difference, a curing speed difference, etc., and the difference in particle size, specific gravity, and electric charge This is a phenomenon in which the pigment and the solvent (monomer) are separated due to the difference in ease of movement. When the above-mentioned color separation occurs when ink droplets are ejected in a line shape, the dye collects only in the peripheral portion of the droplet, and the central portion is blanked out.

[Example 2]
In the preparation of the second liquid in Example 1, the same experiment was performed by replacing the dye (M-1) with a phthalocyanine pigment. Below, the formulation of the liquid using a pigment is shown.

<Preparation of Inkjet Recording Liquid (III-1)>
(A) Acid compound [said compound (A-1)] 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.38 g
(C) Polymerizable compound: 1,70 hexanediol diacrylate 11.70 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant [Pigment: Copper phthalocyanine (PB15: 3)] 1.40 g
(Product name: Irgalite Blue GLO, manufactured by Ciba Specialty Chemicals)
The above components were stirred, mixed, dissolved and dispersed to obtain a cyan inkjet recording liquid (III-1). The viscosity of the liquid (III-1) at 25 ° C. was 19.8 mPa · s.
However, the pigment was previously used in a ball mill (hard glass ball mill pot, one-stage ball mill rotating stand-A type: manufactured by Horie Shokai Co., Ltd.) and Solsperse 3200 (manufactured by Geneca Co., Ltd.) as a dispersant. , 6 hexanediol diacrylate was added in a dispersion of 20% by mass.
The amount added was such that the content was as described above.

<Preparation of one-component type inkjet recording liquid (III-0) for comparison>
(A) Acid compound [said compound (A-1)] 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.38 g
(C) Polymerizable compound: 1,89 hexanediol diacrylate 10.89 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant [Pigment: Copper phthalocyanine (PB15: 3)] 1.40 g
(Product name: Irgalite Blue GLO, manufactured by Ciba Specialty Chemicals) (G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
The above components were mixed, dissolved, and dispersed by stirring to obtain a cyan inkjet recording liquid (III-0). The viscosity of the liquid (III-0) at 25 ° C. was 19.8 mPa · s.
However, the pigment was previously used in a ball mill (hard glass ball mill pot, one-stage ball mill rotating stand-A type: manufactured by Horie Shokai Co., Ltd.) and Solsperse 3200 (manufactured by Geneca Co., Ltd.) as a dispersant. , 6 hexanediol diacrylate was added in a dispersion of 20% by mass.
The amount added was such that the content was as described above.

<Preparation of one-component type inkjet recording liquid (III-00)>
(A) Acid compound [said compound (A-1)] 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.38 g
(C) Polymerizable compound: 1,6 hexanediol diacrylate 12.70 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant [Pigment: Copper phthalocyanine (PB15: 3)] 1.40 g
(Product name: Irgalite Blue GLO, manufactured by Ciba Specialty Chemicals)
(F) High-boiling organic solvent [specific example (S-6)] 13.10 g
(G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
The above components were stirred, mixed, dissolved and dispersed to obtain a cyan inkjet recording liquid (III-00). The viscosity of the liquid (III-00) at 25 ° C. was 19.8 mPa · s.
However, the pigment was previously used in a ball mill (hard glass ball mill pot, one-stage ball mill rotating stand-A type: manufactured by Horie Shokai Co., Ltd.) and Solsperse 3200 (manufactured by Geneca Co., Ltd.) as a dispersant. , 6 hexanediol diacrylate was added in a dispersion of 20% by mass.
The amount added was such that the content was as described above.

<Preparation of one-component type inkjet recording liquid (III1-000)>
(A) Acid compound [said compound (A-1)] 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.38 g
(C) Polymerizable compound: 1,60 hexanediol diacrylate 11.60 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant [Pigment: Copper phthalocyanine (PB15: 3)] 1.40 g
(Product name: Irgalite Blue GLO, manufactured by Ciba Specialty Chemicals)
(F) High-boiling organic solvent [specific example (S-6)] 10.10 g
(G) Polymerization initiator [TPO-L, (Initiator-1)] 1.81 g
(H) Glycerin 2g

  Instead of the ink jet recording liquids (I-1), (I-0), (I-00), and (I1-000) used in Example 1, (III-1), (III-0), Evaluation was performed by printing on a recording medium in the same manner except that (III-00) and (III1-000) were used. The results are shown in Tables 7-9.

As is apparent from Tables 7 to 9, even when a pigment is used as the colorant, as a two-component ink jet recording liquid, one liquid contains the pigment, and the other is the oil according to the present invention. When a soluble polymer is contained and the two liquids are printed so as to overlap each other, image formation without ink-dropping interference and color separation occurs quickly on a non-ink-absorbing PET sheet or art paper. Furthermore, in the present invention, a metal halide lamp having a wavelength of 365 nm is used, and the ultraviolet ray irradiation is performed at an ultraviolet light amount of ~ 500 mJ / cm ² , so that the curing reaction efficiently proceeds quickly, and the printing performance is excellent and there is no stickiness. It can be seen that an image having high scratch resistance, light resistance and ozone resistance can be obtained.
In addition, when the pigment is used, not only the light resistance and ozone resistance are further improved, but also when the polymer of the present invention in which slight unevenness is observed in Example 1 using the dye is used. By using a pigment as the colorant, a uniform image can be obtained.

[Comparative example]
A liquid having the following composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 10.

<Comparison inkjet recording liquid I-X>
(A) Unidic SI-929 (Dainippon Ink Chemical Co., Ltd.) 20g
(B) 1.5 g of the following dye X
(C) Water 68.5cc
(D) Glycerin (manufactured by Wako Pure Chemical Industries) 10g

<Comparison inkjet recording liquid II-X>
(A) Water 97cc
(B) DairoCure 2529 (Merck) 3g

  As can be seen from Table 10, even in a recording method using a liquid containing a photocurable resin on one side and a liquid containing a photopolymerization initiator on the other side, the oil-soluble polymer in the present invention is not used, and water is used as a solvent. In the case of using, the thickness of the line varied, resulting in uneven density in the solid image, resulting in poor light resistance and ozone resistance.

[Example 3]
Among the liquids prepared in Example 2, the liquids (II-1) to (II-) for the two-component ink jet recording liquids (III-1) and (II-1) to (II-27) were used. 27) Printing on the recording medium was carried out in the same manner as in Example 2 except that the application was performed with a lot coater (manufactured by Matsubo Co., Ltd.). Evaluation similar to Example 2 was able to be obtained.

[Example 4]
<Inkjet recording liquids (IV-1) to (IV-7), (IV-10) to (IV-16), and (IV-19) to (IV-23) containing the polymer of the present invention , Preparation of Inkjet Recording Liquid (IV-8), (IV-9), (IV-17), (IV-18), and (IV-24) to (IV-27) for Reference Example >
Inkjet recording was carried out in the same manner as in the preparation of liquids (II-1) to (II-27) prepared in Example 1, except that the high-boiling organic solvent was removed and the amount of the polymer of the present invention was changed to 12 g. Liquids (IV-1) to (IV-27) for preparation were prepared.
Next, in Example 3, the same procedure as in Example 3 was used except that the above-described inkjet recording liquids (IV-1) to (IV-27) were used instead of the used inkjet recording liquids (II-1) to (II-27). Then, the same evaluation as in Example 3 was performed. Even in this case, the same excellent effect as in Example 3 was obtained.

[Example 5]
In Example 1, it was prepared by containing the polymerizable compound only in the second liquid, but in Example 5, the first liquid and the second liquid were prepared by containing the polymerizable compound. The same experiment as 1 was performed. Furthermore, the experiment was performed by changing the type of the polymerizable compound in the second liquid. The prescriptions of the first liquid and the second liquid in Example 5 are shown below.

1. Preparation of second liquid <Preparation of inkjet recording liquid (I'-1)>
(A) Acid compound [said compound (A-1)] 3.56 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.87g
(C) Polymerizable compound: 1,6 hexanediol diacrylate (HDDA; manufactured by Daicel UBC) 6.93 g
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1)] 0.46 g
(F) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g
The above components were mixed and dissolved with stirring to obtain a magenta inkjet recording liquid (I′-1). The viscosity of the ink jet recording liquid (I′-1) at 25 ° C. was 19.6 cp. Hereinafter, the viscosity was measured at 25 ° C., and the value was described.

<Preparation of Liquid for Inkjet Recording (I'-11)>
-A partially modified polymerizable compound of the liquid for ink jet recording (I'-1)-
(A) Acid compound [said compound (A-1)] 3.56 g
(B) Polymerizable compound: DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) 0.87 g
(C) Polymerizable compound: ACMO (manufactured by Kojin) 6.93 g
(D) N-ethyldiethanolamine 0.29 g
(E) Colorant [Dye (M-1)] 0.46 g
(F) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g
The above components were mixed and dissolved with stirring to obtain a magenta ink jet recording liquid (I′-11). The viscosity of the liquid for ink jet recording (I′-11) at 25 ° C. was 23.5 cp.

2. Preparation of first liquid <Preparation of ink-jet recording liquid (II-31) containing the polymer of the present invention>
(G) High boiling point organic solvent (specific example (S-32)) 2 g
(H) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g
(I) Polymer of the present invention (specific example P1-1) 2 g
(J) Polymerizable compound: DPCA60 (Nippon Kayaku) 1.1g
(K) Polymerizable compound: 1,6 hexanediol diacrylate (HDDA; manufactured by Daicel UBC) 8.7 g

<Preparation of Inkjet Recording Liquids (II-32) to (II-36) Containing the Polymer of the Present Invention>
In the preparation of the ink jet recording liquid (II-31), the weight of the ink jet recording liquid (II-31) was the same as that of the ink jet recording liquid (II-31) except that the polymer of the present invention was replaced with the same weight as shown in Table 10 below. Inkjet recording liquids (II-32) to (II-36) containing the coalesced were produced.

<Preparation of liquid for ink jet recording (II-41) containing the polymer of the present invention>
(G) High boiling point organic solvent (specific example (S-1)) 2 g
(H) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g
(I) Polymer of the present invention (specific example P1-1) 2 g
(J) Polymerizable compound: DPCA-60 (Nippon Kayaku Co., Ltd.) 1.1 g
(K) Polymerizable compound: ACMO (manufactured by Kojin) 8.7 g

<Preparation of Inkjet Recording Liquids (II-42) to (II-43) Containing the Polymer of the Present Invention>
In the production of the ink jet recording liquid (II-41), the colorant was added in the same manner as the ink jet recording liquid (II-41) except that the polymer of the present invention was replaced by the same weight as shown in Table 10 below. Inkjet recording liquids (II-42) to (II-43) not containing were prepared.
Table 11 shows the types of the polymer and polymerizable compound used for the preparation of the first liquid, and the viscosity at 25 ° C. of the first liquid.

  Inkjet recording was performed using (I′-1) and (I′-11), respectively, instead of the inkjet recording liquids (I-1), (I-0), and (I-00) used in Example 1. In the same manner except that (II-31) to (II-36) and (II-41) to (II-43) were used instead of the liquids for use (II-1) to (II-29), respectively. It printed on the recording medium and evaluated. The results are shown in Table 12.

As is apparent from Table 12, as a two-component ink jet recording liquid, one liquid contains a colorant, the other contains the oil-soluble polymer in the present invention, and both liquids contain a polymerizable compound. Even when printing is performed so that the two liquids overlap each other, image formation that does not cause droplet ejection interference and does not cause color separation occurs quickly on a non-ink-absorbing PET sheet or art paper. Furthermore, in the present invention, a metal halide lamp having a wavelength of 365 nm is used, and the ultraviolet ray irradiation is performed at an ultraviolet light amount of 500 mJ / cm ² , so that the curing reaction proceeds efficiently and quickly, the printing performance is excellent, no stickiness, and high It can be seen that an image having scratch resistance, light resistance and ozone resistance can be obtained. When ink jet recording was performed using an ink composition containing both such a polymerizable compound and a polymerization initiator, nozzle clogging was observed when printing was performed for a long time. When the ink containing the polymerizable compound and the polymerization initiator further contained a colorant, the nozzle clogging was suppressed.

[Example 6]
In the preparation of the second liquid in Example 5, the dye (M-1) was replaced with a phthalocyanine pigment, and the same experiment was performed except that the polymerization initiator was removed in the preparation of the first liquid. Below, the formulation of the liquid using a pigment is shown.
1. Preparation of second liquid <Preparation of inkjet recording liquid (III'-1)>
(A) Acid compound [said compound (A-1)] 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku) 0.32 g
(C) Polymerizable compound: 1,86 hexanediol diacrylate 9.86 g
(Made by HDDA Daicel UCB)
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant [Pigment: Copper phthalocyanine (PB15: 3)] 1.40 g
(Product name: Irgalite Blue GLO, manufactured by Ciba Specialty Chemicals)
(F) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g
The above components were stirred, mixed, dissolved and dispersed to obtain a cyan inkjet recording liquid (III′-1). The viscosity of the liquid (III′-1) at 25 ° C. was 19.8 mPa · s.
However, the pigment was previously used in a ball mill (hard glass ball mill pot, one-stage ball mill rotating stand-A type: manufactured by Horie Shokai Co., Ltd.) and Solsperse 3200 (manufactured by Geneca Co., Ltd.) as a dispersant. , 6 hexanediol diacrylate was added in a dispersion of 20% by mass.
The amount added was such that the content was as described above.

<Preparation of liquid for ink jet recording (III'-2)>
(A) Acid compound <said compound (A-1)> 0.22 g
(B) Polymerizable compound: DPCA60 (Nippon Kayaku Co., Ltd.) 0.32 g
(C) Polymerizable compound: ACMO (manufactured by Kojin Co., Ltd.) 9.86 g
(D) N-ethyldiethanolamine 0.20 g
(E) Colorant <Pigment: Phthalocyanine> 1.40 g
(Product name: Irgulite Blue GLO, manufactured by Ciba Specialty Chemicals)
(F) Polymerization initiator (TPO-L, said (Initiator-1)) 1.8 g

The above components were mixed and dispersed with stirring to obtain cyanin inkjet recording liquid (III′-2). The viscosity at 25 ° C. of the inkjet recording liquid (III′-2) was 23.5 cp.
However, the pigment was previously used in a ball mill (hard glass ball mill pot, ball mill rotating base one-stage type-A type: manufactured by Horie Shokai Co., Ltd.), and Solsperse 3200 (manufactured by Geneca Co., Ltd.) was used as a dispersant. What was dispersed in 1,6 hexanediol diacrylate so as to be 20% by mass was added. The addition amount was added as a pigment to the above amount.

2. Preparation of first liquid <Preparation of ink-jet recording liquid (II'-31) containing the polymer of the present invention>
(G) High boiling point organic solvent (specific example (S-32)) 2 g
(I) Polymer of the present invention (specific example P1-1) 2 g
(J) Polymerizable compound: DPCA60 (Nippon Kayaku) 1.1g
(K) Polymerizable compound: 1,6 hexanediol diacrylate (HDDA; manufactured by Daicel UBC) 10.5 g

<Preparation of Inkjet Recording Liquids (II′-32) to (II′-36) Containing the Polymer of the Present Invention>
In the production of the ink jet recording liquid (II′-31), the present invention was carried out in the same manner as the ink jet recording liquid (II′-31) except that the polymer of the present invention was replaced by the same weight as shown in Table 13 below. Inkjet recording liquids (II′-32) to (II′-36) containing the above polymer were prepared.

<Preparation of liquid for ink-jet recording (II′-41) containing the polymer of the present invention>
(G) High boiling point organic solvent (specific example (S-1)) 2 g
(I) Polymer of the present invention (specific example P1-1) 2 g
(J) Polymerizable compound: DPCA-60 (Nippon Kayaku Co., Ltd.) 1.1 g
(K) Polymerizable compound: ACMO (manufactured by Kojin) 10.5 g

<Preparation of Inkjet Recording Liquids (II′-42) to (II′-43) Containing the Polymer of the Present Invention>
In the production of the ink jet recording liquid (II′-41), coloring was performed in the same manner as the ink jet recording liquid (II′-41), except that the polymer of the present invention was replaced with the equivalent weight as shown in Table 13 below. Inkjet recording liquids (II′-42) to (II′-43) containing no agent were prepared.
Table 13 shows the types of the polymer and polymerizable compound used for the preparation of the first liquid, and the viscosity at 25 ° C. of the first liquid.

  Instead of the inkjet recording liquids (I′-1) and (I′-11) used in Example 5, (III′-1) and (III′-2) were used, respectively, and the inkjet recording liquid (II -31) to (II-36), (II-41) to (II-43) instead of (II'-31) to (II'-36), (II'-41) to (II '), respectively. In the same manner except that -43) was used, printing was performed on a recording medium for evaluation. The results are shown in Table 12.

As can be seen from Table 14, even when a pigment is used as the colorant, as a two-component ink jet recording liquid, one liquid contains the colorant, and the other contains the oil-soluble polymer in the present invention. Even when both liquids contain a polymerizable compound and printing is performed so that the two liquids overlap, there is no ink jetting interference or color separation on a non-ink-absorbing PET sheet or art paper. Image formation occurs quickly. Furthermore, in the present invention, a metal halide lamp having a wavelength of 365 nm is used, and the ultraviolet ray irradiation is performed at an ultraviolet light amount of 500 mJ / cm ² , so that the curing reaction proceeds efficiently and quickly, the printing performance is excellent, no stickiness, and high It can be seen that an image having scratch resistance, light resistance and ozone resistance can be obtained.
Further, when a pigment is used, light resistance and ozone resistance are further improved, and an image having no unevenness can be obtained.

[Example 7]
Among the liquids prepared in Example 6, two-component ink jet recording liquids (III′-1) and (II′-31) to (II′-36) were used, and the liquid (II′-31) (II′-36) was printed and evaluated in the same manner as in Example 6 except that application to a recording medium was performed by application with a lot coater (manufactured by Matsubo Co., Ltd.). Evaluation similar to Example 6 was able to be obtained.

[Example 8]
<Preparation of Inkjet Recording Liquids (IV-31) to (IV-36) Containing the Polymer of the Present Invention>
Inkjet recording was carried out in the same manner as in the preparation of liquids (II-31) to (II-36) prepared in Example 5, except that the high-boiling organic solvent was removed and the amount of the polymer of the present invention was changed to 12 g. Preparation liquids (IV-31) to (IV-36) were prepared.
Next, in Example 7, the above inkjet recording liquids (IV-31) to (IV-36) were used in place of the inkjet recording liquids (II′-31) to (II′-36) used. Similarly, a sample was prepared. The obtained sample was evaluated in the same manner as in Example 7. Even in this case, the same excellent effect as in Example 7 was obtained.

Claims (27)

An ink set for ink jet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having at least one selected from the group consisting of N-vinylimidazole, 2-vinylpyridine, and 4-vinylpyridine,
An ink set for ink jet recording, wherein at least one of the plurality of liquids contains a polymerizable compound. An ink set for ink jet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having a unit represented by the following general formula (1) or general formula (2),
An ink set for ink jet recording, wherein at least one of the plurality of liquids contains a polymerizable compound.
[In General Formula (1) and General Formula (2), R represents a hydrogen atom or a methyl group; ^{twenty one} ~ R ^{twenty three} , R ^{twenty five} ~ R ²⁷ Each independently represents an alkyl group, an aralkyl group, or an aryl group. R ^{twenty four} 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. ] An ink set for ink jet recording comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids,
The first liquid is obtained by dissolving an oil-soluble polymer;
The oil-soluble polymer is a polymer having a unit represented by the following general formula (3),
An ink set for ink jet recording, wherein at least one of the plurality of liquids contains a polymerizable compound.

[In general formula (3), R ¹¹ Represents a hydrogen atom or a methyl group, Y represents O or NR ¹⁵ Represents R ¹⁵ Represents a hydrogen atom or an alkyl group, R ¹² Represents a divalent linking group and R ¹³ And R ¹⁴ Each independently represents an alkyl group, an aralkyl group or an aryl group. ] The ink set for ink jet recording according to any one of claims 1 to 3, wherein the first liquid does not substantially contain a colorant. The ink set for inkjet recording according to any one of claims 1 to 4 , wherein the second liquid contains a colorant. The ink set for ink jet recording according to any one of claims 1 to 5 , wherein the second liquid does not substantially contain an oil-soluble polymer. The ink set for inkjet recording according to any one of claims 1 to 6 , wherein the second liquid contains a polymerizable compound. The ink set for inkjet recording according to any one of claims 1 to 6 , wherein each of the first liquid and the second liquid contains a polymerizable compound. The ink set for ink jet recording according to any one of claims 1 to 8 , wherein the oil-soluble polymer has a weight average molecular weight of 1,000 to 50,000. The ink for inkjet recording according to any one of claims 1 to 9 , wherein a high boiling point organic solvent is contained in at least one of the liquids containing an oil-soluble polymer. set. When the plurality of kinds of liquids containing solvent, inkjet recording ink set according to any one of claims 1 to 10, characterized in that the solvent is substantially free of water-soluble liquid . The ink set for inkjet recording according to claim 10 , wherein the high-boiling organic solvent has a boiling point of 100 ° C or higher. The ink set for inkjet recording according to any one of claims 5 to 12 , wherein the colorant is an oil-soluble dye or pigment. 14. The ink set for ink jet recording according to claim 13 , wherein the colorant is a pigment. The ink set for ink jet recording according to any one of claims 1 to 14 , comprising at least a first liquid and a second liquid, and comprising a plurality of types of liquids.
Forming an image by applying the first liquid and the second liquid simultaneously on the recording medium, or applying either one first and the other after that so that both liquids are in contact with each other. An ink jet image recording method. The inkjet image recording method according to claim 15 , wherein an image is formed by ejecting the second liquid through an inkjet nozzle at the same time as or after applying the first liquid onto the recording medium. Means for applying said first liquid on the recording medium is a coating using a coating apparatus, according to claim 15, characterized in that injecting the second liquid by an ink jet nozzle after coating the first liquid Or the inkjet image recording method of Claim 16 . The inkjet image recording method according to claim 15 or 16 , wherein the means for applying the first liquid and the second liquid onto the recording medium is ejection by an inkjet nozzle. The inkjet image recording method according to any one of claims 15 to 18 , further comprising a step of applying energy to an image formed on a recording medium to fix the image. The inkjet image recording method according to claim 19 , wherein the energy is imparted by light irradiation or heating. At least a high-boiling organic solvent and an oil-soluble polymer ,
An ink for ink jet recording, wherein the oil-soluble polymer is a polymer having at least one selected from the group consisting of N-vinylimidazole, 2-vinylpyridine, and 4-vinylpyridine . At least a high-boiling organic solvent and an oil-soluble polymer,
An ink for ink jet recording, wherein the oil-soluble polymer is a polymer having a unit represented by the following general formula (1) or general formula (2).
[In General Formula (1) and General Formula (2), R represents a hydrogen atom or a methyl group; ^{twenty one} ~ R ^{twenty three} , R ^{twenty five} ~ R ²⁷ Each independently represents an alkyl group, an aralkyl group, or an aryl group. R ^{twenty four} 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. ] At least a high-boiling organic solvent and an oil-soluble polymer,
An ink for inkjet recording, wherein the oil-soluble polymer is a polymer having a unit represented by the following general formula (3).

[In general formula (3), R ¹¹ Represents a hydrogen atom or a methyl group, Y represents O or NR ¹⁵ Represents R ¹⁵ Represents a hydrogen atom or an alkyl group, R ¹² Represents a divalent linking group and R ¹³ And R ¹⁴ Each independently represents an alkyl group, an aralkyl group or an aryl group. ] The ink for inkjet recording according to any one of claims 21 to 23, further comprising a polymerization initiator. The ink for inkjet recording according to any one of claims 21 to 24 , wherein the ink is substantially free of a colorant. The ink for inkjet recording according to any one of claims 21 to 25 , wherein the ink contains substantially no polymerizable compound. It is composed of a plurality of types of liquids, one of claims 21 to claim 26, characterized by using the ink-jet recording ink set comprising a polymerizable compound with at least one liquid of the liquid the plurality of 1 The ink for inkjet recording as described in the item.