JP2018016662A - Recording liquid set, and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording liquid set excellent in homogeneity of an image and excellent in glossiness and adhesiveness also, and a recording method.SOLUTION: The recording liquid set comprises a recording ink at least containing an anionic dispersion pigment, one or more kinds of organic solvent, and water; and a process liquid at least containing a cationic resin fine particle, and water where the recording ink does not contain a resin fine particle, or, when containing a resin fine particle, contains by a weight concentration less than a weight concentration of the cationic resin fine particle contained in the process liquid. The recording method comprises recording on a recording medium of a non-water-absorbing film using the recording liquid set.SELECTED DRAWING: None

Description

  The present invention relates to a recording liquid set and a recording method, and more particularly to a recording liquid set and a recording method that can be suitably used for a non-water-absorbing film.

  Patent Document 1 discloses that an ink set composed of two types of ink is used to record an image on a plastic film.

Japanese Patent No. 5500410

  In Patent Document 1, two types of ink constituting an ink set are applied onto a plastic film by an ink jet method, and components derived from the respective inks are aggregated and quickly fixed, thereby causing image disturbance due to bleeding. In other words, a printed matter having excellent abrasion resistance immediately after printing is obtained.

  However, when the ink set of Patent Document 1 is used, it is difficult to obtain smoothness such as spots formed in the recorded image due to aggregation of the ink components, and there is room for further improvement in image uniformity. It was issued. As a result, it has also been found that a decrease in gloss and a decrease in adhesion tend to be induced.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a recording liquid set and a recording method that are excellent in image uniformity and excellent in gloss and adhesion.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1.
A recording ink containing at least an anionic dispersed pigment, one or more organic solvents, and water;
A treatment liquid containing at least cationic resin fine particles and water;
A recording liquid set comprising:
The recording ink does not contain resin fine particles, or if resin fine particles are contained, the recording ink contains a weight concentration lower than the weight concentration of the cationic resin fine particles contained in the treatment liquid. set.

2.
2. The processing liquid according to 1 above, wherein the treatment liquid does not contain an organic solvent, or if it contains an organic solvent, the treatment liquid contains a weight concentration lower than the weight concentration of the organic solvent contained in the recording ink. Recording liquid set.

3.
3. The recording liquid set according to 1 or 2, wherein the cationic resin fine particles contained in the treatment liquid have a polyurethane structure.

4).
4. The recording liquid set according to any one of 1 to 3, wherein the recording ink contains resin fine particles having a polyurethane structure when the resin fine particles are contained.

5).
5. A recording method, wherein recording is performed on a non-water-absorbing film, which is a recording medium, using the recording liquid set according to any one of 1 to 4 above.

6).
6. The recording method as described in 5 above, wherein the recording medium is a film subjected to an antifogging process.

7).
7. The recording method according to 5 or 6, wherein the surface of the recording medium is precoated with the treatment liquid, and then recording is performed on the surface with the recording ink.

  According to the present invention, it is possible to provide a recording liquid set and a recording method that are excellent in image uniformity and excellent in gloss and adhesion.

  Below, the form for implementing this invention is demonstrated.

  The recording liquid set according to the present invention includes a recording ink and a processing liquid.

  The recording ink contains at least an anionic dispersed pigment, one or more organic solvents, and water.

  The treatment liquid contains at least cationic resin fine particles and water.

  Furthermore, the recording ink does not contain resin fine particles, or when it contains resin fine particles, it is contained at a weight concentration less than the weight concentration of the cationic resin fine particles contained in the treatment liquid.

  By using such a recording liquid set, for example, an image can be recorded with recording ink on the surface of a recording medium precoated with a treatment liquid.

  At this time, by containing the cationic resin fine particles in the treatment liquid, the anionic dispersion pigment in the recording ink is aggregated on the precoat, and the liquid deviation of the recording ink on the recording medium can be suppressed.

  In addition, when the anionic dispersion pigment in the recording ink is agglomerated on the precoat, it is possible to prevent the formation of spots in the recorded image and the like, thereby preventing a decrease in smoothness. The reason for this is that the viscosity of the resin fine particles in the recording liquid ink is lower than that of the processing liquid (or does not include the resin fine particles), so that the structural viscosity is suppressed and the formation of irregularities during aggregation is alleviated. Etc. are estimated. By maintaining smoothness at the time of agglomeration, an effect that is excellent in gloss and adhesion can be obtained.

  The recording liquid set of the present invention is suitably used when the recording medium is a non-water-absorbing film, and is particularly effective for, for example, a non-water-absorbing film subjected to an antifogging process.

  First, the recording ink constituting the recording liquid set of the present invention will be described in detail.

  As the anionic dispersion pigment contained in the recording ink, an anionic self-dispersing pigment or a pigment dispersed with an anionic polymer dispersing agent can be used, and in particular, an anionic polymer dispersing agent. Those obtained by dispersing the pigment by the above are preferred.

  As the pigment, conventionally known pigments can be used without particular limitation, and any of water-dispersible pigments, solvent-dispersible pigments and the like can be used. For example, organic pigments such as insoluble pigments and lake pigments, and inorganic pigments such as carbon black A pigment can be preferably used. These pigments can be used by being present in a state of being dispersed in the ink by a polymer dispersant.

  The insoluble pigment is not particularly limited, for example, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, Dioxazine, thiazole, phthalocyanine, diketopyrrolopyrrole and the like are preferable.

  Specific pigments that can be preferably used include the following pigments.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 15: 3, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. And CI Pigment Yellow 155. Especially in the balance between color tone and light resistance, C.I. I. Pigment Yellow 155 is preferable.

  In addition, in the conventional method, particularly for yellow pigments, when recorded on a non-water-absorbing medium such as a film, the glossiness between the image-recording portion and the non-recording portion is measured. The inventors found that the difference was conspicuous. With respect to this problem as well, it can be suitably improved by using the ink set of the present invention.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  Examples of black pigments include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.

  The polymer dispersant used for dispersing the pigment is not particularly limited as long as it is anionic, but those having a molecular weight of 5000 or more and 200000 or less can be suitably used.

  Examples of the polymer dispersant include 2 selected from styrene, styrene derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives. Examples thereof include a block copolymer comprising at least one kind of monomer, a random copolymer and salts thereof, polyoxyalkylene, and polyoxyalkylene alkyl ether.

  The polymer dispersant is preferably added after neutralization with a neutralizing base. Here, the neutralizing base is not particularly limited, but is preferably an organic base such as ammonia, monoethanolamine, diethanolamine, triethanolamine, or morpholine.

  The amount of the polymer dispersant added is preferably 10 to 100% by weight, more preferably 10 to 40% by weight, based on the pigment.

  The anionic dispersed pigment is particularly preferably in the form of a so-called capsule pigment in which the pigment is coated with a resin. As a method of coating the pigment with the resin, various known methods can be used. For example, the phase inversion emulsification method, the acid precipitation method, or the pigment is dispersed with a polymerizable surfactant, and the monomer is added thereto. Preferred examples include a method of coating while supplying and polymerizing.

  As a particularly preferred method, the water-insoluble resin is dissolved in an organic solvent such as methyl ethyl ketone, and the acidic group in the resin is partially or completely neutralized with a base, and then the pigment and ion-exchanged water are added and dispersed. After that, a method of removing the organic solvent and adding water as necessary can be mentioned.

  The average particle diameter of the dispersed state of the anionic dispersed pigment in the recording ink is preferably 50 nm or more and less than 200 nm. Thereby, the stability of the anionic dispersion pigment can be improved, and the storage stability of the recording ink can be improved.

  The particle size measurement of the anionic dispersion pigment can be obtained by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method or the like, but the measurement by the dynamic light scattering method is simple, and the above particles The diameter region can be measured with high accuracy.

  The anionic dispersion pigment can be used after being dispersed by a disperser together with a dispersant and other additives necessary for various desired purposes.

  As the disperser, a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used. In particular, an ink produced by dispersion using a sand mill is preferable because of its sharp particle size distribution.

  The material of the beads used for sand mill dispersion is not particularly limited, but zirconia or zircon is preferable from the viewpoint of preventing generation of bead fragments and contamination of ionic components. Furthermore, the bead diameter is preferably 0.3 mm to 3 mm.

  The content of the anionic dispersed pigment in the recording ink is not particularly limited, but is preferably in the range of 1% by weight to 15% by weight.

  The organic solvent contained in the recording ink is not particularly limited, but a water-soluble organic solvent is preferable.

  Preferred examples of the water-soluble organic solvent include alcohols, polyhydric alcohols, amines, amides, glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and the like.

  Preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tertiary butanol.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol. Preferred examples can be given.

  Examples of amines include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, Preferred examples include pentamethyldiethylenetriamine and tetramethylpropylenediamine.

  Preferred examples of amides include formamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Examples of glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol. Preferred examples include monomethyl ether.

  As the 1,2-alkanediols having 4 or more carbon atoms, for example, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol and the like are preferable. It can be illustrated.

  The recording ink may contain one or a combination of two or more selected from these organic solvents.

  The recording ink preferably contains one or more organic solvents having a boiling point of preferably 150 ° C. or higher, more preferably 180 ° C. or higher, whereby the effects of the present invention are more remarkably exhibited.

  The content of the organic solvent in the recording ink is not particularly limited, but is preferably in the range of 15% by weight to 60% by weight.

  The recording ink does not contain resin fine particles, or if it contains resin fine particles, it is contained at a weight concentration lower than the weight concentration of the cationic resin fine particles contained in the treatment liquid.

  When the recording ink contains resin fine particles, the resin fine particles are not particularly limited, but preferred examples include resin fine particles having a polyurethane structure, resin fine particles having a polyolefin structure such as polypropylene, and the like. Fine particles are preferred.

  When the recording ink contains fine resin particles, the fine resin particles preferably contain anionic resin fine particles.

  When the recording ink contains resin fine particles, the average particle diameter of the resin fine particles is not particularly limited, but is preferably in the range of 10 nm to 300 nm. The average particle diameter can be easily measured using a commercially available measuring device using a light scattering method or a laser Doppler method. Alternatively, the dispersion of resin fine particles can be freeze-dried, and the average particle diameter can be converted from the particles observed with a transmission microscope.

  When the recording ink contains fine resin particles, it is preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 2% by weight, and less than the weight concentration of the cationic resin fine particles contained in the treatment liquid. It is preferable to contain by weight concentration.

  It is also preferable that the recording ink contains a surfactant. Accordingly, when applying the recording ink to the recording medium, the ejection stability can be improved when a droplet ejection method such as an inkjet method is used.

  The surfactant is not particularly limited, and anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols , And nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; silicon surfactants; fluorine surfactants, etc. 1 type or 2 types or more can be contained in combination.

  The content of the surfactant in the recording ink is not particularly limited, but is preferably in the range of 0.1% by weight to 3.0% by weight.

  The water content in the recording ink is not particularly limited, but is preferably in the range of 25 wt% to 80 wt%.

  Next, the processing liquid constituting the recording liquid set of the present invention will be described in detail.

  The cationic resin fine particles contained in the treatment liquid are not particularly limited, but cationic resin fine particles having a polyurethane structure, cationic resin fine particles having a polyolefin structure such as polypropylene, etc. can be preferably exemplified, and in particular, having a polyurethane structure. Cationic resin fine particles are preferred.

  The average particle diameter of the cationic resin fine particles is not particularly limited, but is preferably in the range of 10 nm to 500 nm. The average particle diameter can be measured using the method described above for the resin fine particles of the recording ink.

  The content of the cationic resin fine particles in the treatment liquid is not particularly limited, but is preferably in the range of 3% by weight to 30% by weight.

  The treatment liquid does not contain an organic solvent, or when it contains an organic solvent, it is preferably contained in a weight concentration less than the weight concentration of the organic solvent contained in the recording ink.

  As a result, the effect of the present invention is particularly remarkable when recording is performed on a non-water-absorbing film that has been subjected to anti-fogging processing.

  Generally, a film containing a surfactant is used as the antifogging film, but the weight concentration of the organic solvent in the treatment liquid is lower than that of the recording ink (or the organic solvent). ), The bleed-out of the surfactant from the film can be more suitably suppressed. Therefore, even when a non-water-absorbing film, particularly a film subjected to an antifogging process is used as a recording medium, the effects of the present invention can be suitably exhibited. Further, as a result of suppressing the bleed-out of the surfactant, the wettability of the recording ink with respect to the recording medium can be stabilized. In particular, even when an organic solvent having a relatively high boiling point is used, the movement of the surfactant during drying is suppressed, and the recording ink is prevented from being repelled on the recording medium.

  When the treatment liquid contains an organic solvent, for example, one or two or more kinds selected from the organic solvents described for the recording ink can be contained.

  The treatment liquid may contain an organic solvent having a relatively low boiling point, but can also suitably contain an organic solvent having a relatively high boiling point. For example, the treatment liquid preferably contains one or more organic solvents having a boiling point of preferably 100 ° C. or higher, more preferably 150 ° C. or higher.

  When the treatment liquid contains an organic solvent, it is preferably less than 30% by weight, more preferably less than 25% by weight, most preferably less than 20% by weight, and less than the weight concentration of the organic solvent contained in the recording ink. It is preferable to contain by weight concentration.

  It is also preferable that the treatment liquid contains a surfactant. The surfactant to be contained in the treatment liquid can contain, for example, one or a combination of two or more selected from the surfactants described for the recording ink.

  The content of the surfactant in the treatment liquid is not particularly limited, but is preferably in the range of 0.1% by weight to 3.0% by weight.

  The content of water in the treatment liquid is not particularly limited, but is preferably in the range of 40% by weight to 95% by weight.

  In the recording method of the present invention, recording is performed on a recording medium using the recording liquid set of the present invention described above.

  As the recording medium, a non-water-absorbing film can be suitably used. As the non-water-absorbing film, for example, a resin film can be preferably exemplified.

  As the resin film, for example, known resin films can be used. Specific examples include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, and polyvinyl alcohol films. And biodegradable films such as polyvinyl chloride film, polycarbonate film, polyacrylonitrile film and polylactic acid film. Particularly preferred are polyolefin film, nylon and the like.

  The resin film may be an unstretched film, but is preferably stretched in a uniaxial or biaxial direction.

  The surface of the resin film may be untreated, but may be subjected to various treatments such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like.

  In addition, it is also preferable to use a film subjected to an antifogging process as the non-water-absorbing film. As the film subjected to the antifogging process, a film containing a surfactant is suitable.

  As the surfactant, generally used surfactants can be used. For example, nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, etc. Can be illustrated.

  In the recording method of the present invention using the recording liquid set described above, it is preferable to perform recording on the surface with a recording ink after pre-coating the surface of the recording medium with the treatment liquid.

  As a preferred example of the recording method, for example, using a liquid application method such as a roller coating method, a treatment liquid is applied to the surface of the recording medium and dried to form a precoat. Next, it is preferable that a recording ink is applied to the surface of the recording medium on which the precoat is formed, for example, using a liquid application method such as an ink jet method, and dried to form an image.

  The method for applying the treatment liquid to the recording medium is not particularly limited. For example, an inkjet method is preferably used, but more preferably, a method other than the inkjet method is used. As methods other than the inkjet method, methods such as a roller coating method, a curtain coating method, and a spray coating method can be preferably exemplified.

  As a method of applying the treatment liquid to the recording medium, a method other than the ink jet method can be preferably used because the formation region of the precoat with the treatment liquid can be set with a high degree of freedom. For example, the image formation area formed with the recording ink thereafter may coincide with the precoat formation area, but it is also preferable to set the precoat formation area over a wider range. Therefore, the application of the treatment liquid for forming the precoat does not necessarily require accuracy as in the ink jet method. For example, a relatively simple liquid application method such as a roller coating method, a curtain coating method, or a spray coating method. Can be preferably used, and thereby productivity can be increased. In particular, in the present invention, it is possible to prevent a difference in glossiness between the precoat formed with the treatment liquid and the image formed with the recording ink on the precoat, so that the precoat formation region is formed in the image formation area. It is preferable to set it wider than the area.

  By using a method other than the inkjet method as a method for applying the treatment liquid to the recording medium, it is possible to set the prescription of the treatment liquid without being restricted by the droplet discharge stability in the inkjet method. .

  That is, the treatment liquid in particular contains more resin fine particles than the recording ink. In addition, the treatment liquid preferably contains no organic solvent or less than the recording ink. The viscosity range in which the droplet discharge stability in the ink jet method is easily obtained is approximately 15 mPa · s or less, but achieving this viscosity range can be a limitation in the setting of the treatment liquid formulation as described above. In addition, from the viewpoint of preventing drying of the droplet discharge nozzle when using the ink jet method, it is desirable that the ink contains a high boiling point organic solvent of approximately 15% or more. It can be a restriction in setting the prescription. By using a method other than the inkjet method, the prescription of the treatment liquid can be appropriately set according to the type of the recording medium and the like without being restricted.

  In addition, it is preferable to set the prescription of the treatment liquid within the scope of the present invention according to the type of the recording medium, and thus recording can be performed with high versatility on various recording media. . It is also preferable to prepare a plurality of treatment liquids in advance and select a treatment liquid from these according to the type of the recording medium. In this case, if the inkjet method is used, the inkjet head and the flow path must be cleaned each time the treatment liquid is changed, or a system equipped with the number of heads corresponding to the type of the treatment liquid is required, which reduces productivity. In some cases, the system load may increase, but these can be suitably improved by using a method other than the inkjet method.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

1. Preparation of ink set << Ink set 1 >>
<Preparation of pigment dispersion>
Styrene-acrylic acid copolymer (Johncrill 678, molecular weight 8500, acid value 215) 3.0% by weight, pigment (Pigment Yellow 155) 15% by weight as a polymer dispersant, mixed solution with ion-exchanged water added as the balance Was premixed and then dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to prepare a pigment dispersion having a pigment content of 15% by weight. The average particle diameter of the pigment particles contained in this pigment dispersion was 122 nm. The particle size was measured using a Zetasizer 1000HS manufactured by Malvern.

<Preparation of recording ink>
While stirring 26.7 parts by weight of the pigment dispersion prepared above, the following additives were sequentially added to prepare an ink composition, which was then filtered through a 0.8 μm filter to obtain a recording ink. It was. There was no substantial change in composition before and after filtration. The viscosity of the prepared recording ink at 25 ° C. was 5.2 mPa · s.

-26.7 parts by weight of pigment dispersion-24.0 parts by weight of ethylene glycol-10.0 parts by weight of propylene glycol-0.3 parts by weight of silicon surfactant ("KF-351A" manufactured by Shin-Etsu Chemical Co., Ltd.)-Ion exchange Amount that total 100 parts by weight of water

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-1: cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 60.0 parts by weight (solid content 18.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<Ink set 2>
<Preparation of recording ink>
While stirring 26.7 parts by weight of the pigment dispersion prepared above, the following additives were sequentially added to prepare an ink composition, which was then filtered through a 0.8 μm filter to obtain a recording ink. It was. There was no substantial change in composition before and after filtration. The viscosity of the prepared recording ink at 25 ° C. was 5.1 mPa · s.

Pigment dispersion 26.7 parts by weight Resin fine particles A-1; anionic urethane emulsion, particle diameter 40 nm, solid content concentration 35% by weight (Daiichi Kogyo Seiyaku "Superflex 210") 4.3 parts by weight (solid 1.5 parts by weight)
-24.0 parts by weight of ethylene glycol-8.2 parts by weight of propylene glycol-0.3 parts by weight of silicon-based surfactant ("KF-351A" manufactured by Shin-Etsu Chemical Co., Ltd.)-Amount that the total amount of ion-exchanged water is 100 parts by weight

<Preparation of treatment solution>
A treatment liquid similar to that of ink set 1 was used.

<Ink set 3>
<Preparation of recording ink>
While stirring 26.7 parts by weight of the pigment dispersion prepared above, the following additives were sequentially added to prepare an ink composition, which was then filtered through a 0.8 μm filter to obtain a recording ink. It was. There was no substantial change in composition before and after filtration. The viscosity of the prepared recording ink at 25 ° C. was 5.3 mPa · s.

Pigment dispersion 26.7 parts by weight Resin fine particles A-1; anionic urethane emulsion, particle size 40 nm, solid content concentration 35% by weight (Daiichi Kogyo Seiyaku "Superflex 210") 11.4 parts by weight (solid (4.0 parts by weight)
・ Ethylene glycol 24.0 parts by weight ・ Propylene glycol 6.8 parts by weight ・ Silicon surfactant (“KF-351A” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by weight ・ Ion-exchanged water A total amount of 100 parts by weight

<Preparation of treatment solution>
A treatment liquid similar to that of ink set 1 was used.

<Ink set 4>
<Preparation of recording ink>
The recording ink similar to ink set 3 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-1; cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 16.7 parts by weight (solid content 5.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<Ink set 5>
<Preparation of recording ink>
The recording ink similar to ink set 2 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-1: cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 60.0 parts by weight (solid content 18.0 parts by weight)
-22.0 parts by weight of ethylene glycol-7.4 parts by weight of propylene glycol-1.0 part by weight of acetylene glycol-based surfactant-An amount that makes the total amount of ion-exchanged water 100 parts by weight

<Ink set 6>
<Preparation of recording ink>
The recording ink similar to ink set 2 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-2: Cationic polyolefin emulsion, particle diameter 70 nm, solid content concentration 27 wt% (Unitika “Arrow Base”) 66.7 parts by weight (solid content 18.0 parts by weight)
-26.0 parts by weight of ethylene glycol-9.0 parts by weight of propylene glycol-1.0 part by weight of acetylene glycol-based surfactant-An amount that makes the total amount of ion-exchanged water 100 parts by weight

<Ink set 7>
<Preparation of recording ink>
While stirring 26.7 parts by weight of the pigment dispersion prepared above, the following additives were sequentially added to prepare an ink composition, which was then filtered through a 0.8 μm filter to obtain a recording ink. It was. There was no substantial change in composition before and after filtration. The viscosity of the prepared recording ink at 25 ° C. was 5.2 mPa · s.

-Pigment dispersion 26.7 parts by weight-Resin fine particles A-2; anionic polyolefin emulsion, particle size (unmeasured), solid content concentration 30% by weight (Nippon Paper "Auroren AE-301") 5.0 weight Parts (solid content 1.5 parts by weight)
-24.0 parts by weight of ethylene glycol-8.2 parts by weight of propylene glycol-0.3 parts by weight of silicon-based surfactant ("KF-351A" manufactured by Shin-Etsu Chemical Co., Ltd.)-Amount that the total amount of ion-exchanged water is 100 parts by weight

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-1: cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 60.0 parts by weight (solid content 18.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<Ink set 8>
<Preparation of recording ink>
The recording ink similar to ink set 2 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-2: Cationic polyolefin emulsion, particle diameter 70 nm, solid content concentration 27 wt% (Unitika “Arrow Base”) 66.7 parts by weight (solid content 18.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight

<Ink set 9>
<Preparation of recording ink>
The recording ink similar to ink set 3 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

-Resin fine particle B-1: Cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 11.7 parts by weight (solid content 3.5 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<Ink set 10>
<Preparation of recording ink>
While stirring 26.7 parts by weight of the pigment dispersion prepared above, the following additives were sequentially added to prepare an ink composition, which was then filtered through a 0.8 μm filter to obtain a recording ink. It was. There was no substantial change in composition before and after filtration. The viscosity of the prepared recording ink at 25 ° C. was 5.1 mPa · s.

Pigment dispersion 26.7 parts by weight Resin fine particles A-1; anionic urethane emulsion, particle size 40 nm, solid content concentration 35% by weight (Daiichi Kogyo Seiyaku "Superflex 210") 14.3 parts by weight (solid (5.0 parts by weight)
・ Ethylene glycol 24.0 parts by weight ・ Propylene glycol 5.3 parts by weight ・ Silicon surfactant (“KF-351A” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 part by weight ・ Ion-exchanged water A total amount of 100 parts by weight

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle B-1: cationic urethane emulsion, particle size 20 nm, solid content concentration 30 wt% (Daiichi Kogyo Seiyaku "Superflex 620") 16.6 parts by weight (solid content 5.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<Ink set 11>
<Preparation of recording ink>
The recording ink similar to ink set 2 was used.

<Preparation of treatment solution>
Each additive shown below was added sequentially with stirring to prepare a treatment liquid, and then filtered through a 5.0 μm filter to obtain a treatment liquid. There was no substantial change in composition before and after filtration.

Resin fine particle A-1: anionic urethane emulsion, particle size 40 nm, solid content concentration 35 wt% (Daiichi Kogyo Seiyaku "Superflex 210") 51.4 parts by weight (solid content 18.0 parts by weight)
・ Acetylene glycol surfactant 1.0 part by weight ・ Amount of ion exchange water to be 100 parts by weight

<< Ink 1 >>
As the ink 1, the same ink as the recording ink of the ink set 2 was used alone without being used in combination with the treatment liquid.

2. Evaluation of ink set Each of the ink sets 1 to 11 and ink 1 prepared above was evaluated according to the following methods.

(1) Preparation of a print sample By a roller coating method, a treatment liquid of an ink set was applied to a recording medium at a size of 70 × 70 mm under the condition of a coating amount of 3 g / m ² to form a precoat.

  Next, the recording ink of the ink set is scanned at the head scanning speed by an ink jet printer equipped with a drop-on-demand piezo type ink jet head (nozzle number 1024 (512 × 2 rows), nozzle interval 70.5 μm (141 μm × 2 rows)). A 45 × 45 mm square image was recorded in one scan on a part of the recording medium to which the treatment liquid was applied (on the precoat) under the conditions of 500 mm / second, ink droplet volume 42 pl, and recording density 360 × 360 dpi. In this specification, dpi represents the number of dots per 2.54 cm.

  For Ink 1, the formation of a precoat was omitted, and a 45 × 45 mm square image was recorded in one scan directly on the recording medium.

  As a recording medium, a biaxially stretched polypropylene film (made by Futamura Chemical Co., Ltd.) (hereinafter sometimes referred to as an antifogged PP film) that has been subjected to double-side antifogging and corona treatment, and a biaxially stretched nylon that has been subjected to double-side corona treatment. Both films (manufactured by Toyobo) (hereinafter sometimes simply referred to as nylon films) were tested.

  With respect to the print sample on which the square image was formed as described above, the uniformity of the recorded image, the gloss difference between the printed portion and the non-printed portion, and the abrasion resistance of the recorded image were evaluated.

(2) Uniformity evaluation of recorded image The above printed sample was visually evaluated for the occurrence of spots in the formed image, and the uniformity was evaluated according to the following criteria.

<Evaluation criteria>
◎: generation of spots is not observed at all, and the quality is good ◯: spots are partially seen, but in a practically possible range ×: spots are generated on the entire surface, and the quality is not preferable for practical use

  In the above evaluation criteria, ◎ to ○ are practically preferable ranges.

  The uniformity of the recorded image was the same whether the recording medium was an anti-fogging PP film or a nylon film.

(3) Evaluation of Glossiness Difference between Printed Section and Non-Printed Section The glossiness of the above printed sample was measured using a variable angle glossmeter (VGS-1001DP) manufactured by Nippon Denshoku Industries Co., Ltd. The incident and reflection angles were measured at 20 °.

  Here, the glossiness of only the precoat (non-printed portion) formed with the treatment liquid and the glossiness of the image (printed portion) formed with the recording ink on the precoat were measured. The glossiness (%) of the printed portion when the non-printed portion was taken as 100% was determined, and the difference (glossiness of the non-printed portion−glossiness of the printed portion) was defined as the glossiness difference (%).

  Moreover, based on the glossiness difference (%), evaluation was performed according to the following criteria.

<Evaluation criteria>
A: Glossiness difference (absolute value) is 1% or less ◯: Glossiness difference (absolute value) is 3% or less ×: Glossiness difference (absolute value) is greater than 3%

  If the evaluation criteria are ◎ to ◎, there is no sense of incongruity due to the difference in gloss between the printed portion and the non-printed portion, which is a practically preferable range.

  The difference in glossiness was the same whether the recording medium was an anti-fogging PP film or a nylon film.

  In addition, in the print samples obtained with the ink set 11 and the ink 1, a uniform ink layer was not obtained due to the liquid drop of the ink droplets, and it was impossible to evaluate the difference in glossiness.

(4) Evaluation of rubbing resistance The above-mentioned print sample was allowed to stand at 23 ° C. and 55% relative humidity for 12 hours, and then the image was rubbed with dry cotton (Kanakin No. 3), and rubbing resistance was evaluated according to the following criteria.

  As the scratch resistance 1, the case where the recording medium was an anti-fogging PP film was evaluated, and as the scratch resistance 2, the case where the recording medium was a nylon film was evaluated.

<Evaluation criteria>
A: Transfer to cotton is not observed even after rubbing 50 times or more, and no change is observed in the image. ○: Rubbing 50 times or more causes slight transfer to cotton, but no change to the image. Δ: The image is scratched and the recording medium is exposed during rubbing 20 to 50 times. X: The image is scratched and the recording medium is exposed while rubbing less than 20 times.

  In the above evaluation criteria, ◎ to ○ are practically preferable ranges.

  The above evaluation results are shown in Tables 1 and 2.

Claims (7)

A recording ink containing at least an anionic dispersed pigment, one or more organic solvents, and water;
A treatment liquid containing at least cationic resin fine particles and water;
A recording liquid set comprising:
The recording ink does not contain resin fine particles, or if resin fine particles are contained, the recording ink contains a weight concentration lower than the weight concentration of the cationic resin fine particles contained in the treatment liquid. set.   2. The process liquid according to claim 1, wherein the treatment liquid does not contain an organic solvent, or if it contains an organic solvent, the treatment liquid contains a weight concentration less than the weight concentration of the organic solvent contained in the recording ink. The recording liquid set described.   The recording liquid set according to claim 1, wherein the cationic resin fine particles contained in the treatment liquid have a polyurethane structure.   The recording liquid set according to claim 1, wherein, when the recording ink contains the resin fine particles, the recording ink contains resin fine particles having a polyurethane structure.   5. A recording method comprising recording on a non-water-absorbing film as a recording medium using the recording liquid set according to claim 1.   6. The recording method according to claim 5, wherein the recording medium is a film subjected to an antifogging process.   The recording method according to claim 5 or 6, wherein after the surface of the recording medium is precoated with the treatment liquid, recording is performed on the surface with the recording ink.