JP2016175298A - Inkjet recording method and ink set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recording method which exhibits excellent color development even when plain paper is used as a printing medium, and enables recording where offset is reduced, by an inkjet recording device.SOLUTION: An inkjet recording method includes the steps of: sticking a first liquid onto a recording medium by an inkjet recording device; and sticking a second liquid to a region where the first liquid has been stuck in the recording medium by the inkjet recording device. The first liquid contains a pigment, and an organic solvent having a 50% distillation point of 280°C or lower. The second liquid contains at least one of a cellulose derivative and an urethane resin.SELECTED DRAWING: None

Description

  The present invention relates to an ink jet recording method and an ink set.

  Conventionally, a printing method using an ink jet recording method is performed by causing ink droplets to fly and adhere onto a recording medium such as paper. In addition, due to recent advances in ink jet recording system technology, ink jet recording apparatuses using an ink jet recording system are also being used in the field of high-definition image recording (image printing), which previously used photography and offset printing. Yes.

  Ink jet recording is also used for dyeing (printing) fabrics, as disclosed in Patent Document 1, for example. In the technique described in Patent Document 1, thickness is imparted by adding a salt of carboxymethylcellulose to the ink when printing on the fabric is performed by an ink jet method, and the bleeding of the edge of the pattern formed on the fabric is reduced. It is disclosed that the image becomes clear.

JP-A-11-166143

  However, if the concentration of a cellulose derivative such as carboxymethylcellulose (CMC) in the ink is not high to some extent, it is considered that the performance of the cellulose derivative cannot necessarily be sufficiently exhibited in the ink containing the cellulose derivative and the coloring material. For example, even in a permeable recording medium such as paper as well as a fabric, when the concentration of the cellulose derivative in the ink slows down when the ink lands, both the cellulose derivative and the coloring material are contained in the recording medium. It penetrates and flows and diffuses in the medium. As a result, the amount of the color material on the surface of the medium decreases, and the color developability of the image decreases, or the color material enters toward the back side of the medium, causing problems such as set-off.

  In general, ink jet ink used for ink jet recording is required to have a viscosity adjusted to a certain level, in order to eject ink droplets from fine ink flow paths and fine nozzles. However, when the cellulose derivative is blended with the ink, the viscosity of the ink increases if the blending amount or molecular weight is increased in order to exhibit the intended performance. Therefore, when a cellulose derivative is blended in advance with ink, the blending amount and molecular weight are limited.

  One of the objects according to some embodiments of the present invention is an inkjet recording apparatus that can perform recording with good color development and reduced offset even when plain paper is used as a printing medium. It is to provide a method and an ink set.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1] One aspect of the ink jet recording method according to the present invention is as follows.
Attaching the first liquid to the recording medium with an inkjet recording apparatus;
Attaching a second liquid to an area of the recording medium to which the first liquid is attached by an ink jet recording apparatus;
Including
The first liquid includes a pigment and an organic solvent having a 50% distillation point of 280 ° C. or lower,
The second liquid contains at least one of a cellulose derivative and a urethane resin.

  According to the ink jet recording method of this application example, the second liquid is attached while the pigment and the organic solvent contained in the first liquid are attached to the recording medium. Then, the pigment adhered by the first liquid is captured by at least one of the cellulose derivative and the urethane resin contained in the second liquid, and is kept near the surface of the recording medium. This makes it difficult for the pigment to move toward the back surface of the recording medium, and is fixed to the recording medium by at least one of a cellulose derivative and a urethane resin. Therefore, according to the inkjet recording method of this application example, it is possible to perform recording with good color development and reduced set-off (back-through). The 50% distillation point is a value according to JIS K2254 “Fuel oil distillation test method”.

[Application Example 2] In Application Example 1,
The second liquid may include at least one of the cellulose derivative and the urethane resin in an amount of 1% by mass to 15% by mass with respect to the entire second liquid.

  In this way, it is possible to perform recording with better color development and reduced offset.

[Application Example 3] In Application Example 1 or Application Example 2,
The cellulose derivative may be at least one selected from carboxymethylcellulose and a salt thereof, and nitrocellulose and a salt thereof.

  In this way, it is possible to perform better recording of pigment fixability and gloss.

[Application Example 4] In Application Example 3,
The cellulose derivative may have a mass average molecular weight of 1000 or more and 50000 or less.

  In this way, it is possible to perform better recording of pigment fixability and gloss.

[Application Example 5] In Application Example 3 or Application Example 4,
The degree of etherification of the cellulose derivative may be 0.5 or more and 1.5 or less.

  In this way, it is possible to perform recording with better fixability and color developability of the pigment.

[Application Example 6] In Application Example 1 or Application Example 2,
The urethane resin may be polyether-based or polyester-based.

  In this way, it is possible to perform better recording of pigment fixability and gloss.

[Application Example 7] In any one of Application Examples 1 to 6,
After the step of attaching the first liquid, the step of attaching the second liquid may be performed before the first liquid is dried.

  By doing so, it is possible to perform better recording of the fixability and gloss of the pigment.

Application Example 8 One aspect of the ink set according to the present invention is as follows.
Used in the ink jet recording method according to any one of Application Examples 1 to 7,
A first liquid containing a pigment and an organic solvent having a 50% distillation point of 280 ° C. or lower;
A second liquid containing at least one of a cellulose derivative and a urethane resin;
including.

  According to the ink set of this application example, the pigment contained in the first liquid is attached to the recording medium, and then the second liquid is attached, thereby at least one of the cellulose derivative and the urethane resin contained in the second liquid. Thus, the pigment can be captured and retained in the vicinity of the surface of the recording medium. Accordingly, it can be applied to the ink jet method, and the pigment is difficult to move toward the back surface of the recording medium, and is fixed to the recording medium by at least one of a cellulose derivative and a urethane resin. Therefore, according to the ink set of this application example, it is possible to perform ink jet recording with good color development and reduced offset.

  Embodiments of the present invention will be described below. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

<Inkjet recording method>
The ink jet recording method according to the present embodiment includes a step of attaching a first liquid to a recording medium and a step of attaching a second liquid. In the ink jet recording method according to the present embodiment, these steps are performed using an ink jet recording apparatus. The ink jet recording apparatus is not particularly limited, and a known apparatus can be appropriately used. The step of attaching the first liquid and the step of attaching the second liquid may be performed by the same ink jet recording apparatus or may be performed by different ink jet recording apparatuses.

  Further, the recording medium to which the ink jet recording method of the present embodiment is applied is not particularly limited, and can be applied to, for example, various fabrics, various papers, various films, and the like. In the case where the second liquid contains a cellulose derivative, it is more preferable that the recording medium contains cellulose fibers because the interaction with the cellulose derivative is strong and a more excellent effect can be obtained.

  The step of attaching the first liquid and the step of attaching the second liquid are performed in this order, but the number of such steps is not limited, and the time interval at which the steps are performed is not particularly limited. However, if the second liquid is adhered after the first liquid is adhered to the recording medium and before the organic solvent of the first liquid is dried, the fixability and gloss of the pigment are further improved. Can do. From the viewpoint of reducing the movement of the pigment contained in the first liquid into the recording medium as much as possible after the organic solvent of the first liquid is attached to the recording medium, the time until the second liquid is attached is as follows. Within 3 minutes, preferably within 1 minute, more preferably within 30 seconds, and even more preferably within 10 seconds. Further, when the first liquid and the second liquid are applied by the ink jet recording apparatus, the time interval can be further shortened by applying both in the same scan of the recording head.

  In addition to these steps, the ink jet recording method according to the present embodiment may include a step of attaching another liquid (such as ink), a heating step, a drying step, and the like as necessary. Further, these other steps are at least before the step of attaching the first liquid, after the step of attaching the second liquid, and between the step of attaching the first liquid and the step of attaching the second liquid. It can be done at one timing.

  Further, the viscosity of the first liquid and the second liquid is, for example, 2 mPa · s or more and 30 mPa · s or less and 2 mPa · s or more and 15 mPa · s or less at 20 ° C. in order to set the viscosity within an appropriate range in inkjet recording. It is preferably 2 mPa · s or more and 10 mPa · s or less. The viscosity is measured by, for example, using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

1. Step of attaching first liquid The first liquid to be attached in the step of attaching the first liquid contains a pigment and an organic solvent having a 50% distillation point of 280 ° C. or lower.

The amount of the first liquid attached to the recording medium in this step is not particularly limited. For example, it is 2 mg / inch ² (2 mg / in ² ) or more and 30 mg / inch ² or less, preferably 5 mg / inch ² or more and 25 mg / inch. ² , more preferably 7 mg / inch ² or more and 20 mg / inch ² . When the amount of the first liquid attached to the recording medium is within this range, good color developability (for example, high OD value) and drying property can be obtained.

1.1. Pigment The first liquid of this embodiment contains a pigment. The type of the pigment is not particularly limited, and one or more types that can be contained in a normal inkjet ink can be used.

  As the pigment, any of inorganic pigments and organic pigments can be used. Examples of the pigment include organic pigments such as azo, phthalocyanine, condensed polycyclic, nitro, nitroso, hollow resin particles, and polymer particles (brilliant carmine 6B, lake red C, watching red, disazo yellow, hansa). Yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, titanium oxide, zinc oxide, antimony oxide, Metal oxides and sulfides such as zinc sulfide and zirconium oxide, and carbon blacks (CI pigment black 7) such as furnace carbon black, lamp black, acetylene black, and channel black, as well as loess, ultramarine blue, And bitumen It is possible to use the machine pigment.

More specifically, as carbon black, No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Raven 5750, Raven
5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 and the like (manufactured by Columbia Carbon Co., Ltd.), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 880, Monarch 880 Monarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by Cabot), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black
FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6S Manufactured) and the like.

  Examples of white pigments include C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium mica), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (gypsum) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate), and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, and C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and C.I. I. Bat Blue 4, 60 and the like.

  Examples of pigments other than black, white, yellow, magenta and cyan include C.I. I. Pigment green 7, 10, and C.I. I. Pigment brown 3, 5, 25, 26, and C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

  A special color pigment can also be used. For example, a bright pigment that can form a metallic gloss image including aluminum flakes or a pearl gloss image including talc or the like may be used. Furthermore, the pigment used in this embodiment may be a self-dispersing pigment, or a dye containing a solid component such as a disperse dye or a sublimation dye.

  The content of the pigment in the first liquid is not particularly limited, and is 2.0% by mass or more and 50.0% by mass or less, preferably 3.0% by mass or more and 30.0% by mass or less. The content of the pigment (solid content) varies depending on the pigment type to be used, but from the viewpoint of obtaining good color developability, when the total mass of the first liquid is 100% by mass, preferably 1.0% by mass to It is 30.0 mass%, More preferably, it is 2.0 mass%-15.0 mass%.

  In addition, when preparing the 1st liquid, you may prepare using the pigment dispersion liquid which disperse | distributed the pigment beforehand. As a method of obtaining such a pigment dispersion, a method of dispersing a pigment in a dispersion medium using a polymer dispersant, a method of dispersing a self-dispersed pigment in a dispersion medium without using a dispersant, and a surface treatment There is a method of dispersing a pigment in a dispersion medium.

1.2. Organic solvent having a 50% distillation point of 280 ° C. or lower The first liquid of the present embodiment contains an organic solvent having a 50% distillation point of 280 ° C. or lower. 50%
The distillation point is a value according to JIS K2254 “Fuel oil distillation test method”. The 50% distillation point is, as a general rule, the temperature at which the organic solvent evaporates at 50% under normal pressure. When the 50% distillation point is low, the amount of evaporation of the organic solvent is relatively large, and when it is high, the organic solvent is relatively organic. The amount of solvent evaporation is small.

  The organic solvent having a 50% distillation point of 280 ° C. or less contained in the first liquid may be any of a polar organic solvent, a nonpolar organic solvent, and a mixed solvent of both.

  As an organic solvent having a 50% distillation point of 280 ° C. or lower, “AF-4, Naphthesol M, Naphthezol L, Teclean N-16, Teclean N-20, Teclean N-22, No. 0 Solvent L, manufactured by Nippon Petroleum Corporation, No. 0 Solvent M, No. 0 Solvent H, Isosol 300, Isosol 400, Clean Sol G ”,“ Exxol D80, Solvesso 200, Isopar G, Isopar H, Isopar M ”manufactured by Exxon Corporation, and the like.

  The organic solvent having a 50% distillation point of 280 ° C. or lower may be selected from ester solvents, alcohol solvents, higher fatty acid solvents, ether solvents, and mixed solvents thereof. Specifically, as the organic solvent having a 50% distillation point of 280 ° C. or less, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether or the like has a 50% distillation point of 280 ° C. The following can be selected.

  An organic solvent having a 50% distillation point of 280 ° C. or lower can be used alone or in combination of two or more. When two or more kinds of organic solvents having a 50% distillation point of 280 ° C. or lower are used, if the organic solvent having a distillation point of 280 ° C. or lower is used at least 10% by mass or more based on the total solvent, An organic solvent having a point higher than 280 ° C. may be contained. If the organic solvent having a distillation point of 280 ° C. or lower is 10% by mass or more based on the total amount of the second liquid, it is difficult for the solvent to remain on a medium such as paper, and the back-through can be reduced.

  Examples of the organic solvent having a 50% distillation point exceeding 280 ° C. include “Nisseki Naphthezol H, Nisseki Isosol AF-6, AF-7” manufactured by Japan Petroleum Corporation, “Isopar L, ExxolD40, ExxolD100” manufactured by Exxon. ExxolD130, ExxolD140 ”,“ Nisseki Cleansol G ”(alkyl benzene) manufactured by Nippon Oil Co., Ltd., and the like.

  On the other hand, the 1st liquid of this embodiment may contain the organic solvent whose 50% distillation point is 300 degreeC or more. Examples of organic solvents having a 50% distillation point of 300 ° C. or higher include methyl soybean oil, soybean oil isobutyl, ethyl oleate, isostearyl alcohol, oleyl alcohol, isopalmitic acid, isostearic acid, isoarachidic acid, isohexacic acid, and isopropyl isostearate. Among them, methyl linoleate, isobutyl linoleate, isobutyl tall oil and the like can be exemplified by those having a 50% distillation point of 300 ° C or higher.

  An organic solvent having a 50% distillation point of 300 ° C. or higher can be used alone or in combination of two or more. When two or more kinds of organic solvents having a 50% distillation point of 300 ° C. or higher are used, the organic solvent having a 50% distillation point of less than 300 ° C. is contained at least 10% by mass or more with respect to the total amount of the first liquid. It is preferable.

  When the first liquid contains an organic solvent having a 50% distillation point of 300 ° C. or higher, volatilization of the entire organic solvent is easily suppressed, and odor and the like are less likely to be generated. Further, when the first liquid contains an organic solvent having a 50% distillation point of 300 ° C. or higher, volatilization of the entire organic solvent is easily suppressed, and clogging of the nozzles of the ink jet recording apparatus can be suppressed.

1.3. Other components The first liquid of this embodiment includes dyes, surfactants, water-soluble organic solvents, dispersants (resins), preservatives, dissolution aids, antioxidants, antifungal agents, and other ordinary inkjet inks. One or a plurality of additives that may be contained in the resin may be included.

2. Step of attaching the second liquid The second liquid used in the step of attaching the second liquid contains at least one of a cellulose derivative and a urethane resin.

The amount of the second liquid adhered to the recording medium in this step is 2 mg / inch ² (2 mg / in ² ) or more and 20 mg / inch ² or less, preferably 3 mg / inch ² or more and 15 mg / inch ² , more preferably 3 mg / inch ² . Inch ² or more and 10 mg / inch ² . If the amount of the second liquid adhering to the recording medium is within this range, the pigment of the first liquid can be captured by at least one of the cellulose derivative and the urethane resin, and the effect of keeping the pigment on the surface side of the recording medium. Can be obtained. Moreover, if it is this range, the glossiness of the image obtained can be made favorable.

  After the first liquid is attached to the recording medium, the time interval until the second liquid is attached by this process is such that the second liquid is attached before the attached first liquid is dried. Is preferred. In this way, the penetration of at least one of the cellulose derivative and the urethane resin in the recording medium can easily catch up with the penetration of the pigment, and the pigment can be more easily fixed on the recording medium.

  The second liquid may be an aqueous liquid whose main solvent is water, or a non-aqueous (oil-based) liquid whose main solvent is an organic solvent. The second liquid contains at least one of a cellulose derivative and a urethane resin. Depending on the type, the second liquid may be aqueous or non-aqueous, and the second liquid may be aqueous or non-aqueous. According to another, a water-soluble or oil-soluble cellulose derivative and a urethane resin may be selected.

2.1. Cellulose Derivative The type of cellulose derivative that can be contained in the second liquid of the present embodiment is not particularly limited. Examples of the cellulose derivative include cellulose ether, cellulose ester, alkali metal salts such as sodium and potassium, and ammonium salts thereof.

  Specific examples of the cellulose ether include carboxymethylcellulose (CMC), carboxyethylcellulose, carboxymethylethylcellulose, and sodium and potassium salts thereof, hydroxymethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose, methylcellulose, and ethylcellulose. , Methoxymethyl cellulose, benzyl cellulose, and one or more selected from mixtures and copolymers thereof.

  Examples of the cellulose ester include one or more selected from cellulose nitrate (nitrocellulose), cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, and other higher fatty acid cellulose.

  Note that sodium carboxymethylcellulose, which is a sodium salt of carboxymethylcellulose, is obtained by, for example, converting natural pulp as a raw material into alkali cellulose with sodium hydroxide and etherifying with monochloroacetic acid. Production methods include a solvent method and a water medium method. In addition, for example, commercially available CMC can be used from Daiichi Kogyo Seiyaku Co., Ltd., and cellulose nitrate is available from Inabata Sangyo Co., Ltd., grade names: DHX4-6, DHX5-10, DHX8-13, Commercially available products such as DHX11-16, DHX30-50, and DHX40-70 can be used.

  These cellulose derivatives have hydrophilicity, and part or all of the molecules are dissolved in water contained when the second liquid is an aqueous system. Furthermore, since the cellulose derivative has a cellulose skeleton (a structure linked by β-glucose (glucopyranose) 1,4-bond), it has an affinity for cellulose fibers contained in recording media such as paper, fabrics including cotton, and the like. High nature. Therefore, it can be favorably bound to cellulose fibers. In addition, since the cellulose derivative has a surface active action and also has an affinity for the pigment, the pigment of the first liquid can be satisfactorily fixed to the cellulose fiber when the second liquid is adhered. Further, when the second liquid is an emulsion, the dispersion state of the emulsion can be stabilized by the surface active action of the cellulose derivative.

  Among these cellulose derivatives, at least one selected from carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylcellulose, methylcellulose, and cellulose nitrate is preferable in that better pigment fixing and gloss can be obtained. It is more preferable that

  The content of the cellulose derivative in the second liquid is 0.5% by mass or more and 20.0% by mass or less, preferably 2.0% by mass or more and 15.0% by mass or less, more preferably with respect to the entire second liquid. Is 5.0 mass% or more and 10.0 mass% or less. When the content of the cellulose derivative is within this range, the viscosity of the second liquid can be easily adjusted to a range suitable for inkjet recording, and the ejection stability in inkjet recording can be improved.

  In addition, if the content of the cellulose derivative is within this range, the pigment contained in the first liquid is easily captured and retained by the cellulose derivative, which makes it difficult for the pigment to move toward the back surface of the recording medium. It can be satisfactorily fixed on the medium. Thereby, the color development is better and the set-off can be further reduced.

The properties of cellulose ether vary depending on the degree of polymerization and the degree of etherification in units of anhydrous glycol. The degree of etherification (the degree of substitution per glucose unit) of cellulose ether (the whole when plural kinds are contained) is preferably 0.01 or more and 4 or less from the viewpoint of further suppressing the set-off of the pigment. Preferably it is 0.1-2.8, More preferably, it is 0.6-1.6. The degree of etherification is the average value of the total number of cellulose ethers per number of glucose ether ether units. In addition, in the case of sodium carboxymethylcellulose, for example, the degree of etherification is a value obtained according to the CMC industry association analysis method (ashing method). Specifically, for the degree of etherification, 1 g of sodium carboxymethylcellulose is precisely weighed, put into a magnetic crucible and incinerated at 600 ° C., and sodium oxide produced by incineration is titrated with N / 10 sulfuric acid and phenolphthalein as an indicator. In addition, the titration amount YmL per 1 g of sodium carboxymethylcellulose can be calculated and put into the following equation.
Degree of etherification = (162 × Y) / (10,000-80 × Y)

  The number average molecular weight of the cellulose derivative is 1,000 to 5,000,000, preferably 3,000 to 1,000,000, more preferably when measured by GPC (gel permeation chromatography) using polyethylene oxide as a standard. It is 5,000 to 500,000, more preferably 10,000 to 150,000. From the viewpoint of ejection stability in the second liquid ink jet recording, the number average molecular weight of the cellulose derivative (or the whole when plural kinds are included) is more preferably 10,000 or more and 140,000 or less.

Since the degree of water-solubility and oil-solubility (non-water-solubility) of the cellulose derivative varies depending on the type and amount of substituents, a soluble one is selected according to the distinction between the aqueous and non-aqueous liquids of the second liquid. In general, CMC is water-soluble, so it is suitable when the second liquid is aqueous, and cellulose nitrate is oil-soluble, so it is suitable when the second liquid is non-aqueous. Even when the second liquid is an amphiphilic mixed solvent system or an emulsion, a cellulose derivative that can be dissolved in the system can be selected.

2.2. Urethane resin The kind of urethane resin which can be contained in the 2nd liquid of this embodiment is not specifically limited. Examples of the urethane resin include urethane polymers (homopolymers or copolymers) that are insoluble in water at room temperature and normal pressure, or a mixture of plural kinds thereof. The urethane copolymer may be a linear, block, branched, graft, comb or star copolymer.

  The content of the urethane resin in the second liquid is 1.0% by mass or more and 20.0% by mass or less, preferably 2.0% by mass or more and 15.0% by mass or less, more preferably 5.0% by mass as a solid content. The content is 10.0% by mass or less.

  The urethane resin is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyether type urethane resin having an ether bond in the main chain, and a polyester type urethane having an ester bond in the main chain. Resin, polycarbonate-type urethane resin containing a carbonate bond in the main chain, and the like can also be used. More specifically, the urethane resin may be selected from aromatic polyether polyurethane, aliphatic polyether polyurethane, aromatic polyester polyurethane, aliphatic polyester polyurethane, aromatic polycaprolactam polyurethane and aliphatic polycaprolactam polyurethane. preferable. More preferred urethane resins are aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes and aliphatic polyester polyurethanes.

  Specific examples of urethane resins include Suncure 2710 (trade name) and / or Avalua UR445 (trade name) [these are polypropylene having the international nomenclature cosmetic ingredient name “PPG-17 / PPG-34 / IPDI / DMPA copolymer”. Glycol, isophorone diisocyanate and 2,2-dimethylolpropionic acid]], Sancure 878 (trade name), Sancure 815 (trade name), Sancure 1301 (trade name), Sancure 2715 (trade name), Sancure 1828 (Product Name), Sancure 2026 (Product Name), Sancure 1818 (Product Name), Sancure 853 (Product Name), Sancure 830 (Product Name), Sancure 825 (Product Name), Sancure 776 (Product Name), Sancure 850 ( Product name), Sun Cure 12140 (trade name), Sancure 12619 (trade name), Sancure 835 (trade name), Sancure 843 (trade name), Sancure 898 (trade name), Sancure 899 (trade name), Sancure 1511 (trade name), Sancure 1514 (trade name), Sancure 1517 (trade name), Sancure 1591 (trade name), Sancure 2255 (trade name), Sancure 2260 (trade name), Sancure 2310 (trade name), Sancure 2725 (trade name) and Sancure 12471 (trade name) (all are commercially available from BF Goodrich, Cleveland, OH), Bayhydrol DLN, Bayhydrol LS-2033, Bayhydrol 123, Bayhydrol PU402A, Bayhydrol 110 (these are commercially available from BayerCorp., McMurray, PA). Has been ), Witcobond W-320, Witcobond W-242, Witcobond W-160, Witcobond W-612, Witcobond W-506 (commercially available from WitcoPerformanceChemicals), Neoletz R-940, Neoletz R-960, Neolets R-962, Neolets R-966, Neolets R-967, Neolets R-972, Neolets R-9409, Neolets R-9537, Neolets R-9649, and Neolets R-9679 (these are commercially available from ZenecaResins) Etc.

  The urethane resin may be blended in the form of an emulsion. For example, as a commercially available urethane resin emulsion, Sancure 2710 (manufactured by Nippon Lubrizol Co., Ltd.), Permarin UA-150 (manufactured by Sanyo Chemical Industries Ltd.), Superflex 150 420, 460, 470, 610, 700 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), NeoRez R-9660, R-9637, R-940 (above, manufactured by Enomoto Kasei Co., Ltd.), Adekabon titer HUX-380 290K (above, manufactured by ADEKA Corporation), Takerak (R) W-605, W-635, WS-6021 (above, manufactured by Mitsui Chemicals, Inc.), and the like.

  When a urethane resin is blended with the second liquid, it is preferable that an organic solvent is blended with the second liquid. The organic solvent will be described later. Even in this case, the second liquid may contain water. The water content in this case is, for example, 4% by mass or more and 85% by mass or less of the second liquid, preferably 10% by mass or more and 80% by mass or less, and more preferably 25% by mass or more and 80% by mass or less. It may be a solvent. When the second liquid contains about 10% by weight or more and about 40% by weight of an organic solvent, the second liquid optionally contains about 20% by weight or less monohydric alcohol, or two or three types. It is preferable to contain more than one organic solvent. Moreover, when selecting an aliphatic polyurethane as a urethane resin, it is preferable not to contain substantially the hardening | curing agent as described in US Patent 5,681,550.

  Here, in the present specification, the composition does not substantially contain a specific substance means that the composition is less than about 1% by mass of the composition, more preferably less than about 0.75% by mass, and even more preferably about Including the case of containing less than 0.50% by mass, most preferably less than about 0.25% by mass, for example, meaning that the composition does not intentionally contain the substance.

  Since the degree of water-solubility and oil-solubility (non-water-solubility) of the urethane resin varies depending on the type and amount of substituents, a soluble resin is selected according to the distinction between the aqueous and non-aqueous liquids of the second liquid. Also, when the second liquid is an amphiphilic mixed solvent system or an emulsion, a urethane resin that can be dissolved in the system can be selected.

2.3. Water The second liquid of the present embodiment may contain water. When water is about 40% or more of the liquid components in the second liquid, the second liquid can be said to be an aqueous liquid. As water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. The content of water in the second liquid can be 20% by mass to 90% by mass when the total mass of the second liquid is 100% by mass. Here, the water content is not limited to the amount of water added, but also includes water contained in the pigment dispersion when supplying water or pigment in other additives as the dispersion.

2.4. Organic solvent An organic solvent may be contained in the 2nd liquid of this embodiment. When the organic solvent is about 40% or more of the liquid components in the second liquid, the second liquid can be referred to as a non-aqueous (oil-based) liquid.

  As the organic solvent, for example, an organic solvent having a 50% distillation point exceeding 280 ° C. described in the section of the first liquid can be used. Moreover, you may use what has a boiling point of 50 to 140 degreeC at atmospheric pressure, Preferably it is 56 to 125 degreeC, More preferably, it is 56 to 98 degreeC. Furthermore, the organic solvent may be a mixed solvent or water miscible. Specific examples of such an organic solvent include alcohols, esters, ketones, aromatic hydrocarbons, aliphatic hydrocarbons and ethers having 1 to 15 carbon atoms. Further preferred organic solvents are selected from alcohols and esters having 1 to 10 carbon atoms.

  A preferred alcohol is a monohydric alcohol. Preferred monohydric alcohols are selected from ethanol, isopropanol and n-propanol. Preferred esters are selected from ethyl acetate (ethyl acetate) and butyl acetate (butyl acetate). Examples of other organic solvents include benzyl alcohol, amyl acetate, propyl acetate, acetone, heptane, isobutyl acetate, isopropyl acetate, toluene, methyl acetate, isobutanol, n-amyl alcohol, n-butyl alcohol, hexane and methyl ethyl ketone. Can be mentioned. Among these, it is more preferable to select from isopropanol, n-propanol, ethanol, ethyl acetate, butyl acetate and acetone.

  The content of the organic solvent in the second liquid can be 20.0 mass% or more and 90.0 mass% or less when the total mass of the second liquid is 100 mass%. Here, the content of the organic solvent is not limited to the amount to which the organic solvent is added, but also includes the organic solvent in other additives.

2.5. Other components In the second liquid of the present embodiment, surfactants, water-soluble organic solvents, other resins, preservatives, pH adjusters, dissolution aids, antioxidants, antifungal agents, etc. One or a plurality of additives that may be contained in the resin may be included.

3. Components that can be blended in the first liquid and the second liquid The first liquid and the second liquid used in the ink jet recording method according to the present embodiment can include the following components, respectively.

3.1. Surfactant At least one of the first liquid and the second liquid according to the present embodiment may include a surfactant. As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and these may be used in combination. By including the surfactant, wettability when the second liquid adheres to the recording medium can be improved, and at least one penetration rate of the cellulose derivative and the urethane resin can be improved. Further, foaming and foaming when the second liquid is discharged from the nozzle of the ink jet recording head can be suppressed.

  As the nonionic surfactant, at least one of acetylene glycol surfactant, acetylene alcohol surfactant, fluorosurfactant, and polysiloxane surfactant is preferable.

Examples of the acetylene glycol surfactant and the acetylene alcohol surfactant include, but are not limited to, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7. , 9-tetramethyl-5-decyne-4,7-diol alkylene oxide adduct, and 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol, Selected from alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol, 2,4-dimethyl-5-hexyn-3-ol One or more types can be exemplified. Commercially available acetylene glycol surfactants and acetylene alcohol surfactants can also be used. Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all are trade names, manufactured by Air Products and Chemicals, Inc.), Olphin B, Y, P, A STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, S
K-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.

  As the fluorosurfactant, commercially available ones may be used, and examples thereof include Megafac F-479 (manufactured by DIC Corporation), BYK-340 (manufactured by Big Chemie Japan), and the like.

  As the polyorganosiloxane-based surfactant, commercially available ones can be used. For example, Olfine PD-501, Olfine PD-502, Olfine PD-570 (all manufactured by Nissin Chemical Industry Co., Ltd.), BYK-347, BYK-348 (both are manufactured by Big Chemie Co., Ltd.) and the like.

  Furthermore, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl glucoside, polyoxyalkylene glycol alkyl ether, polyoxyalkylene glycol, polyoxyalkylene glycol alkyl phenyl ether, and sugar fatty acid. Ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene acetylene glycol, polyoxyalkylene glycol alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine oxide, fatty acid alkanolamide, alkyl Roll amide, polyoxyethylene polyoxypropylene block polymer It may be used mer and the like.

  Examples of the anionic surfactant include higher fatty acid salt, soap, α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, monoalkyl phosphate ester salt, α -Olefin sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyalkylene glycol alkyl ether phosphate ester, etc. Is mentioned.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts as quaternary ammonium series, and N-methylbishydroxyethylamine fatty acid ester hydrochloride as amine salt series.

  Examples of amphoteric surfactants include alkylamino fatty acid salts as amino acids, alkylcarboxyl betaines as betaines, and alkylamine oxides as amine oxides. The amphoteric surfactant is not limited to these.

  When the surfactant is added to the first liquid or the second liquid, the total content of the surfactant is 0.1 to 3 when the total mass of the first liquid or the second liquid is 100% by mass. It is preferable to make it 0.0 mass%.

3.2. Water-soluble organic solvent At least one of the first liquid and the second liquid according to the present embodiment may contain a water-soluble organic solvent. Preferred examples of such water-soluble organic solvents include polyhydric alcohol alkyl ethers (glycol ethers) and 1,2-alkanediols. Examples of the glycol ethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl. Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, and alkylene glycol monoalkyl ethers such as dipropylene glycol monobutyl ether. The 1,2-alkyldiol is not limited to the following, and examples thereof include 1,2-pentanediol and 1,2-hexanediol. Besides these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and the like Mention may also be made of chain hydrocarbon diols.

  Specific examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3- Hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, trimethylolpropane, polyethylene glycol having a number average molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol, Examples also include pentaerythritol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone.

  A water-soluble organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. If the first liquid or the second liquid contains a water-soluble organic solvent, for example, even if the first liquid or the second liquid is left in contact with air, it can be made more difficult to dry. The water-soluble organic solvent preferably has a standard boiling point of 180 ° C. or higher, more preferably 200 ° C. or higher. When the standard boiling point is within this range, good water retention and wettability can be imparted to the first liquid or the second liquid, and the storage stability may be improved.

  When a water-soluble organic solvent is blended with the first liquid or the second liquid, the content of the water-soluble organic solvent is preferably 0 when the total mass of the first liquid or the second liquid is 100% by mass. 0.1 to 50.0 mass%, more preferably 0.5 to 40.0 mass%. When the water-soluble organic solvent is contained in the first liquid or the second liquid, the surface tension becomes low, so that the wettability to media such as paper becomes high.

3.3. Other resins At least one of the first liquid and the second liquid may contain a resin in addition to the above-described cellulose derivative and urethane resin as a polymer component. The resin may be supplied in the form of a resin emulsion. The resin may be added for the purpose of enhancing the fixability of the pigment contained in the first liquid and enhancing the fastness of printing.

  Such resins include, but are not limited to, styrene resins, styrene acrylic resins, acrylic resins, and the like.

Examples of commercially available styrene acrylic resins and acrylic resins include Mobile Vinyl 966A, Mobile Vinyl 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.), Microgel E-1002, Microgel E-5002 (manufactured by Nippon Paint Co., Ltd.), Bon Coat 4001 Boncoat 5454 (above, manufactured by DIC Corporation), SAE1014 (manufactured by Zeon Corporation), Cybinol SK-200 (manufactured by Seiden Chemical Co., Ltd.), Jonkrill 7100, Jonkrill 390, Jonkrill 711, Jonkrill 511, John Krill 7001, John Krill 632, John Krill 741, John Krill 450, John Krill 840, John Krill 74J, John Krill HRC-1645J, John Krill 734, John Krill 852, John Krill 7600 John Crill 775, John Crill 537J, John Crill 1535, John Crill PDX-7630A, John Crill 352J, John Crill 352D, John Crill PDX-7145, John Crill 538J, John Crill 7640, John Crill 7641, John Crill 631, John Crill 790, Jonkrill 780, Jonkrill 7610 (above, manufactured by BASF), NK binder R-5HN (made by Shin-Nakamura Chemical Co., Ltd.), and the like.

  When these other resins are contained in the first liquid or the second liquid, the content of the resin in the first liquid or the second liquid in terms of solid content is the total mass of the first liquid or the second liquid. Is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 5.0% by mass.

4). Arrangement of the first liquid and the second liquid in the recording medium The first liquid and the second liquid are attached to the recording medium, but it is sufficient if the second liquid is attached to the region where the first liquid is attached. Can be obtained. Since the ink jet recording method of the present embodiment is performed using an ink jet recording apparatus, control of the attachment position and timing can be easily achieved. It is more preferable that the second liquid is attached only to the region where the first liquid is attached. In this way, the amount of cellulose derivative and urethane resin used can be suppressed, and such a region should not be formed when only the second liquid is attached to the recording medium and a glossy region is not required. Can do.

5. Deformation of the second liquid The second liquid described above may be an emulsion or a dispersion. That is, the second liquid may be a liquid containing an aqueous phase and an oil phase. In this way, when it is desired to contain at least one of the cellulose derivative and the urethane resin in the second liquid in a high concentration, the viscosity of the phase is increased by containing at least one of the cellulose derivative and the urethane resin in one phase. Even if the other phase contains a low-viscosity solvent, an increase in the viscosity of the entire second liquid can be suppressed. The phase separation structure when the second liquid of the present embodiment is an emulsion or a dispersion is not particularly limited, and examples thereof include a water-in-oil structure (W / O) and an oil-in-water structure (O / W). can do. In addition, the phase separation structure can be regarded as a hierarchical phase separation structure such as a so-called composite emulsion such as an oil-in-water structure (O / W / O) or a matrix in which both the water phase and the oil phase are a matrix. In addition, a so-called common (mutual) continuous structure may be included.

  When the second liquid is an emulsion or a dispersion, the content of at least one of the cellulose derivative and the urethane resin may be increased. The oil phase when the second liquid is used as an emulsion or dispersion may be the same as the component obtained by removing the pigment from the first liquid described above. Whether or not the second liquid is in the form of an emulsion or a dispersion can be confirmed by visual observation, for example.

6). According to the ink jet recording method of the present embodiment, the surface of the recording medium is captured by capturing the pigment attached to the recording medium by the first liquid by at least one of the cellulose derivative and the urethane resin contained in the second liquid. It can stay in the vicinity. Accordingly, the pigment is difficult to move toward the back surface of the recording medium, and the pigment is fixed to the recording medium by at least one of the cellulose derivative and the urethane resin. Therefore, according to the ink jet recording method of the present embodiment, it is possible to perform recording with good color development and reduced offset.

7). Ink Set The ink set of the present embodiment is an ink set for ink jet recording, and includes the above-described first liquid and the above-described second liquid. In addition, the ink set of the present embodiment can appropriately include inks of respective colors. The second liquid contained in the ink set may be any of water, oil, mixed solvent, and emulsion.

  According to the ink set of the present embodiment, the pigment contained in the first liquid is attached to the recording medium, and then the second liquid is attached, thereby at least one of the cellulose derivative and the urethane resin contained in the second liquid. Thus, the pigment can be captured and fastened. Accordingly, the pigment is difficult to move toward the back surface of the recording medium, and is fixed to the recording medium by at least one of a cellulose derivative and a urethane resin. Therefore, according to the ink set of this application example, it is possible to perform recording with good color development and reduced offset.

8). Examples and Comparative Examples Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

8.1. Preparation of the first liquid: Soybean oil methyl 13% by weight, soybean oil isobutyl 20% by weight, ethyl oleate 10% by weight, oleyl alcohol 10% by weight, naphthenic solvent (AF-4 manufactured by Nisseki Chemical Co., Ltd.) 17% by weight, naphthene 15% by mass of an organic solvent (manufactured by Nisseki Chemical Co., Ltd.), 5% by mass of Solsperse 13940 (manufactured by Abyssia) as a dispersant, and 10% by mass of carbon black (MA-8) were further dissolved. Added and premixed. Thereafter, the mixture was dispersed in a bead mill with a residence time of about 20 minutes to prepare a first liquid.

8.2. Preparation of 2nd liquid 17 types of 2nd liquids (1-17) were prepared as follows.

  Each component was put into a container so as to have the composition shown in Table 1, mixed and stirred with a magnetic stirrer for 2 hours, and then filtered through a membrane filter having a pore size of 5 μm to prepare a second liquid. In addition, the numerical value in Table 1 shows the mass%.

  In Table 1, the components described by the compound names were obtained as reagents. As the cellulose derivative, sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd.) was used. Urethane resins include aromatic polyether urethane (Mitsubishi Chemical Co., Ltd .: Maximol), aliphatic polyether urethane (Mitsui Chemicals Co., Ltd .: CN963A80), aromatic polyester urethane (Hitachi Chemical Co., Ltd .: Phantor). Aliphatic polyester urethane (manufactured by Sartomer: CN964B85) was used. In addition, polystyrene (Arakawa Chemical Industries, Ltd .: 700) and acrylic resin (Arakawa Chemical Industries, Ltd .: Polymeron 1383) were used as other resins in the comparative example.

  Moreover, each brand name is as follows. DHX4-6 (Inabata Sangyo Co., Ltd .: Nitrocellulose), DHX11-16 (Inabata Sangyo Co., Ltd .: Nitrocellulose), Olphin E1010 (Nisshin Chemical Industry Co., Ltd., acetylene glycol surfactant), Surfynol 104 (Air Products and Chemicals, Inc., acetylene alcohol-based surfactant), AF-4 (naphthenic solvent (manufactured by Nisseki Chemical Co., Ltd. (JX Nippon Oil & Energy Corporation))).

8.3. Evaluation Test Each Example and Comparative Example shown in Table 2 was evaluated as follows. In addition, the comparative example 1 is an example which does not use the 2nd liquid, and the 2nd liquid is not made to adhere in each evaluation of this example.

≪OD value≫
The prepared first liquid and second liquid are respectively introduced into a cartridge of an ink jet printer (Seiko Epson Corporation, model PX-B700), and the first liquid is sequentially attached from a plurality of nozzles communicating with the cartridge. Later, it was confirmed that the second liquid was discharged so as to adhere to the region, and a solid pattern was printed on one sheet of A4 paper (plain paper: Xerox P paper (manufactured by Fuji Xerox Co., Ltd.). Was 13 mg / inch ² and the coating amount of the second liquid was 7 mg / inch ² .

Then, the OD value of the pattern was measured with a Gretag densitometer (manufactured by Gretag Macbeth). The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ・ ・ ・ OD value 1.4 or more ○ ・ ・ ・ OD value 1.2 or more and less than 1.4 △ ・ ・ ・ OD value less than 1.2

≪Glossy≫
The gloss (60 °) of the printed matter was measured using a handy gloss meter PG-II / IIM. The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ・ ・ ・ 3 or more ○ ・ ・ ・ 1.5 or more and less than 3 △ ・ ・ ・ less than 1.5

≪Back-to-back≫
The OD value of the back surface of the A4 paper from which the OD value was measured was measured in the same manner. The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ・ ・ ・ OD value less than 0.2 ○ ・ ・ ・ OD value 0.2 or more and less than 0.3 △ ・ ・ ・ OD value 0.3 or more

≪Dryness≫
Immediately after printing, the printed surface was rubbed with Ben cotton applied with a load of 200 g, and the OD value of the rubbed Ben cotton was measured. The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ... OD value less than 0.1 ○ ... OD value 0.1 or more and less than 0.2 △ ・ ・ ・ OD value 0.3 or more

≪Fixability≫
A line was drawn on the A4 paper on which the OD value was measured by applying a load of 220 g to the printed portion using a fluorescent pen. The evaluation was performed visually and used as the following evaluation criteria.
◎ ・ ・ ・ No blurring ○ ・ ・ ・ Slightly blurring △ ・ ・ ・ Hardening the tail of characters

≪Curl≫
The prepared first liquid and second liquid are respectively introduced into a cartridge of an ink jet printer (Seiko Epson Corporation, model PX-B700), and after the first liquid is sequentially attached from a plurality of nozzles communicating with the cartridge. After confirming that the second liquid adheres to the area, print a solid pattern on one A4 sheet (plain paper: Xerox P paper (Fuji Xerox Co., Ltd.)), and the sheet is discharged. The curl height (maximum height (separation distance) of the paper from the paper conveyance surface) was measured.The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ・ ・ ・ less than 5mm ○ ・ ・ ・ 5mm or more and less than 10mm △ ・ ・ ・ 10mm or more

≪Dischargeability≫
The prepared first liquid and second liquid are introduced into a cartridge of an ink jet printer (Seiko Epson Corporation, model PX-B700), and are confirmed to be discharged from a plurality of nozzles communicating with the cartridge. Then, a test pattern was printed on 30 sheets of A4 paper, a nozzle check was performed after printing 30 sheets, and the ejection characteristics were evaluated according to the following criteria. The evaluation results are shown in Table 2.
◎ ... No nozzle missing ○ ... No more than 5 missing nozzles, recovered with one cleaning △ ・ ・ ・ No more than 10 missing nozzles, recovered with 2 or more cleanings

≪Storage stability≫
The prepared first and second liquids were allowed to stand in a 60 ° C. environment for 24 hours, and after returning to room temperature, the absorbance was measured. The evaluation criteria are as follows, and the results are shown in Table 2.
◎ ... Deviation from initial is within 3% ○ ... Deviation from initial is within 10% △ ... Deviation from initial is more than 10%

8.4. Evaluation results As shown in the evaluation results of Table 2, in the examples, the OD value (color development) and the back-through (back-off) were all good with respect to the comparative example.

This result shows that at least one of the cellulose derivative and the urethane resin contained in the second liquid caused the trapping of the pigment contained in the first liquid, and the movement of the pigment accompanying the penetration of the first liquid into the paper was suppressed. Is considered to be a cause. That is, it is considered that one reason is that the pigment of the first liquid is kept near the surface of the recording medium by at least one of the cellulose derivative and the urethane resin of the second liquid, and the pigment is difficult to flow.

  In addition, in the examples, in addition to this, the overall balance of gloss, drying properties, fixing properties, curling, ejection properties, and storage stability was good. Furthermore, when an Example is seen, in Example 1-6 which used the 2nd liquid as the water system, when content of carboxymethylcellulose (CMC) is large, it turns out that curl is a little inferior. This is considered to be due to the fact that the CMC has an action of retaining moisture, so that moisture tends to stay on the recording medium. Further, when the second liquid was non-aqueous, no moisture was imparted to the recording medium, and the curl was very good.

  The reason why the gloss is improved is considered that at least one of the cellulose derivative and the urethane resin is dried, and a smooth film is formed on the surface of the recording medium. It has been found that the fixability is better when a resin of a kind that can capture the pigment is used. That is, it was found that when the molecular weight is large or the degree of etherification is high, there is a tendency to improve. Further, the fixing property is better as the amount of the resin is larger, and this is considered to be due to the fact that the resin solidifies in a state of capturing the pigment to form a film.

  Regarding the drying property, in the case of an aqueous system, it is considered that the amount of the humectant is small and the drying property of the resin is good to improve the drying property. From Tables 1 and 2, it can be seen that the larger the molecular weight of the aqueous cellulose derivative, the easier it is to form a film, and the greater the degree of etherification, the easier it is to form a film. Further, curl depends on the amount of water, and when the amount of water increases, the curl characteristics tend to deteriorate.

  With respect to the ejection property, it is considered that the resin type having a structural viscosity is deteriorated. For example, it is considered that the resin has a structural viscosity when the molecular weight is large or the viscosity is high. Regarding the storage stability, it is considered that there is a tendency to deteriorate in the case of a resin type that is easily crosslinked or a resin that is easily aggregated.

The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (8)

Attaching the first liquid to the recording medium with an inkjet recording apparatus;
Attaching a second liquid to an area of the recording medium to which the first liquid is attached by an ink jet recording apparatus;
Including
The first liquid includes a pigment and an organic solvent having a 50% distillation point of 280 ° C. or lower,
The ink jet recording method, wherein the second liquid contains at least one of a cellulose derivative and a urethane resin. In claim 1,
The ink jet recording method, wherein the second liquid contains at least one of the cellulose derivative and the urethane resin in an amount of 1% by mass to 15% by mass with respect to the entire second liquid. In claim 1 or claim 2,
The inkjet recording method, wherein the cellulose derivative is at least one selected from carboxymethylcellulose and a salt thereof, and nitrocellulose and a salt thereof. In claim 3,
The inkjet recording method whose mass mean molecular weights of the said cellulose derivative are 1000 or more and 50000 or less. In claim 3 or claim 4,
The inkjet recording method whose etherification degree of the said cellulose derivative is 0.5-1.5. In claim 1 or claim 2,
The said urethane resin is an inkjet recording method which is a polyether type or a polyester type. In any one of Claims 1 thru | or 6,
An ink jet recording method, wherein a step of attaching the second liquid is performed after the step of attaching the first liquid and before the first liquid is dried. It is used for the inkjet recording method according to any one of claims 1 to 7,
A first liquid containing a pigment and an organic solvent having a 50% distillation point of 280 ° C. or lower;
A second liquid containing at least one of a cellulose derivative and a urethane resin;
Including ink set.