JP5590827B2 - Inkjet recording material and inkjet recording method - Google Patents

Description

  The present invention relates to an ink jet recording material excellent in color stability and color developability and an ink jet recording method excellent in color stability and color developability.

  With the widespread use of digital cameras, digital photography has become familiar, and inkjet printers equipped with water-soluble ink suitable for outputting digital photo images have become widespread. Non-absorptive property represented by polyolefin resin-coated paper (laminated at least one side of the base paper with polyolefin resin such as polyethylene) as a recording material with glossiness and image quality suitable for such photo image output 2. Related Art Inkjet recording paper is known in which an ink receiving layer mainly composed of fine inorganic fine particles is provided on a support.

  Combining the above inkjet recording material and an inkjet printer equipped with water-soluble ink has improved printing speed, improved image quality, and improved weather resistance over a long period of time, but stabilizes the hue of the printed area. There was a problem that it took several hours or more to complete and it took a lot of time to confirm the image quality (hereinafter referred to as color stability).

  The water-soluble ink includes dye ink and pigment ink. Compared with pigment inks, dye inks can express fine hues, have transparency and glossy printed matter, and have good ink aging stability, and clogging in the heads of inkjet printers. There were features that were difficult to wake up. JP-A-2008-81693 (Patent Document 1) and JP-A-2005-105135 (Patent Document 2) disclose dye inks capable of recording good images. Conventionally, development has been progressed mainly on long-term color stability (ozone resistance and light resistance) of dye inks. On the other hand, regarding short-term color stability in a short time after recording ink on a recording material. Has not been fully studied.

  As a technique for improving color stability from an ink jet recording material, JP-A-2003-291488 (Patent Document 3) contains a silica-alumina composite xerogel having an average pore radius of 12 nm or more on at least one surface of a substrate. An ink jet recording medium having an ink receiving layer containing a silica alumina composite xerogel having an average pore radius of 6 to 10 nm has been disclosed, but it was not satisfactory.

  On the other hand, in an ink jet recording material mainly containing fine particle silica on a support for the purpose of improving color developability, bronzing, bleeding in a high humidity environment, etc., the ink receiving layer has a water-soluble zirconium compound having a pH of less than 8 and pH 8 An ink jet recording material containing the above water-soluble zirconium compound is disclosed in Japanese Patent Application Laid-Open No. 2006-224573 (Patent Document 4), and the ink receiving layer separated from the support contains the water-soluble zirconium compound. JP-A-2006-110771 (Patent Document 5) discloses an ink-jet recording material that is contained and has a non-uniform distribution of the water-soluble aluminum compound in the entire ink-receiving layer and is distributed more in the portion close to the support. ing. However, the color stability was not satisfactory.

  Japanese Patent Application Laid-Open No. 2006-264231 (Patent Document 6) discloses an ink containing colloidal silica and a polyaluminum hydroxide compound as an ink jet recording material for improving color stability resulting from fluctuations in the production lot of colloidal silica. Inkjet recording materials provided with a receiving layer are known.

JP 2008-81693 A JP-A-2005-105135 JP 2003-291488 A JP 2006-224573 A JP 2006-110771 A JP 2006-264231 A

  An object of the present invention is to provide an ink jet recording material excellent in color stability and color developability and an ink jet recording method excellent in color stability and color developability.

The above object of the present invention has been achieved by the following invention.
1) An inkjet recording material for recording an image using a water-soluble ink comprising at least a dye, water, a water-soluble organic solvent, an acetylene glycol surfactant, and a glycol ether compound. An ink receiving layer containing a basic polyaluminum hydroxide compound mainly containing gas phase method silica on the recording material on at least one surface of the polyolefin resin-coated support from the side close to the polyolefin resin-coated support; An ink jet recording material comprising an ink receiving layer mainly containing a phase method silica and containing a water-soluble zirconium compound, and a layer containing colloidal silica and containing a basic polyaluminum hydroxide compound in this order.
2) An ink jet recording method for recording an image on an ink jet recording material by discharging a water soluble ink from a recording head of an ink jet recording apparatus, wherein the water soluble ink comprises a dye, water, a water soluble organic solvent, and acetylene. An ink comprising at least a glycol-based surfactant and a glycol ether compound, wherein the ink jet recording material is a gas phase method from at least one surface of the polyolefin resin-coated support, close to the polyolefin resin-coated support. An ink receiving layer mainly containing silica and containing a basic polyaluminum hydroxide compound, an ink receiving layer mainly containing gas phase method silica and containing a water-soluble zirconium compound, and a basic polyhydroxide containing colloidal silica. Ink jet recording material having an aluminum compound-containing layer in this order An ink jet recording method characterized in that there.

  According to the present invention, an ink jet recording material excellent in color stability and color developability and an ink jet recording method excellent in color stability and color developability can be provided.

FIG. 6 is a diagram showing the color stability evaluation results recorded with the dye ink set 1 in Example 1. It is a figure which shows the color stability evaluation result recorded with the dye ink set 2 in Example 1. FIG. It is a figure which shows the color stability evaluation result recorded on Example 1 with the pigment ink set. It is a figure which shows the color stability evaluation result recorded with the dye ink set 1 in the comparative example 4. It is a figure which shows the color stability evaluation result recorded by the dye ink set 2 in the comparative example 4. FIG. It is a figure which shows the color stability evaluation result recorded on the comparative example 4 by the pigment ink set.

  Hereinafter, embodiments of the present invention will be described in detail.

  The ink jet recording material as this embodiment will be described. The ink jet recording material of the present embodiment is an ink containing a basic polyaluminum hydroxide compound mainly containing gas phase method silica on at least one surface of a polyolefin resin-coated support from the side close to the polyolefin resin-coated support. A receiving layer, an ink receiving layer mainly containing vapor phase method silica and containing a water-soluble zirconium compound, and a layer containing colloidal silica and containing a basic polyaluminum hydroxide compound are sequentially provided.

  The ink jet recording material of the present embodiment has an ink receiving layer mainly containing vapor phase silica. The fact that the ink-receiving layer mainly contains vapor-phase method silica means that the gas-phase method silica is contained in an amount of 50% by mass or more, preferably 60% by mass or more, based on the total solid content constituting the ink-receiving layer. That is.

  Vapor phase silica is made by flame hydrolysis. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane are also used alone or mixed with silicon tetrachloride instead of silicon tetrachloride. Can be used in the state. Vapor phase silica is commercially available as Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd., and can be obtained.

  The average secondary particle size of the vapor phase silica contained in the ink receiving layer is preferably 500 nm or less. In order to obtain higher ink absorbency, the average secondary particle size is preferably 30 nm to 300 nm, and the average primary particle size is preferably 3 to 10 nm from the viewpoint of obtaining high film transparency. The average primary particle diameter in the present embodiment is a diameter of a circle equal to the projected area of each of 100 particles existing in a certain area by electron microscope observation of particles dispersed to such an extent that the primary particle diameter can be discriminated. It is the average particle size obtained as the primary particle size of the particles. The average secondary particle size is a value obtained by measuring a dilute dispersion with a laser diffraction / scattering particle size distribution analyzer.

  In order to obtain the gas phase method silica having the above average secondary particle size, the gas phase method silica and the dispersion medium are preliminarily dispersed by ordinary propeller stirring, turbine stirring, homomixer type stirring, etc., and then ball mill, bead mill, It is preferable to perform dispersion using a media mill such as a sand grinder, a pressure disperser such as a high pressure homogenizer, an ultra high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, or the like.

  The content of the basic polyaluminum hydroxide in the ink receiving layer mainly containing vapor phase method silica and containing the basic polyaluminum hydroxide compound is 1 to 5% by mass based on the vapor phase method silica. Is preferable, and it is more preferable to contain 2-4 mass%. Further, the content of the basic polyaluminum hydroxide compound in the layer containing colloidal silica and containing the basic polyaluminum hydroxide compound is preferably 50 to 200% by mass, more preferably 100 to 150% by mass with respect to the colloidal silica. preferable.

The basic polyaluminum hydroxide compound has a main component represented by the following general formula 1, 2, or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , It is a water-soluble polyaluminum hydroxide containing a basic and high-molecular polynuclear condensed ion stably such as [Al ₁₃ (OH) ₃₄ ] ⁵⁺ , [Al ₂₁ (OH) ₆₀ ] ³⁺ , etc. .

[Al ₂ (OH) _n Cl _6-n ] _m General formula 1
[Al (OH) ₃ ] _n AlCl ₃ general formula 2
Al _n (OH) _m Cl _(3n-m) 0 <m <3n General formula 3

  These are water treatment agents from Taki Chemical Co., Ltd. under the name of polyaluminum chloride (PAC), from Asada Chemical Co., Ltd. under the name of polyaluminum hydroxide (Paho), and from Riken Green Co., Ltd. It is marketed under the name of Purachem WT and from other manufacturers for the same purpose, and various grades can be easily obtained.

  The water-soluble zirconium compound of the ink receiving layer mainly containing vapor-phase method silica and containing a water-soluble zirconium compound may be any one of inorganic salts, organic salts, single salts, double salts, metal complexes, and the like. Zirconium (zirconyl acetate), zirconium nitrate, zirconium sulfate, zirconium fluoride, zirconium chloride, zirconium chloride octahydrate, zirconium oxychloride, hydroxy zirconium chloride, basic zirconium carbonate, zirconium hydroxide, ammonium zirconium carbonate, potassium zirconium carbonate Zirconium acetate (zirconyl acetate) and zirconyl oxychloride are preferable. Examples of commercially available products of zirconium acetate (zirconyl acetate) and zirconyl oxychloride include Zircosol (registered trademark) ZA-30 and ZC-2 manufactured by Daiichi Rare Element Chemical Co., Ltd.

  The content of the water-soluble zirconium compound in the ink receiving layer mainly containing vapor-phase method silica and containing the water-soluble zirconium compound is preferably 0.5 to 2.5% by mass with respect to the vapor-phase method silica. 2 mass% is more preferable.

The ink-receiving layer solid coating amount of containing fumed silica mainly is preferably ^{15~35g / m 2, 20~30g / m} 2 is more preferable. Further, the solid content coating ratio of the ink receiving layer mainly containing gas phase method silica and containing a basic polyaluminum hydroxide compound and the ink receiving layer mainly containing gas phase method silica and containing a water-soluble zirconium compound is It is preferably 10: 1 to 1: 1, and more preferably 5: 1 to 3: 1.

The solid coating amount of the layer containing containing colloidal silica basic poly aluminum hydroxide compound is preferably 0.05~0.35g / m ^2, more preferably 0.1 to 0.3 g / m ^2.

  Colloidal silica used for layers containing colloidal silica and containing basic polyaluminum hydroxide compound is colloidal silicon dioxide obtained by heating and aging silica sol obtained through metathesis with sodium silicate acid or ion exchange resin layer. In water. The colloidal silica used in the present embodiment preferably has an average primary particle size of 20 nm to 80 nm, more preferably 20 to 60 nm, from the viewpoint of glossiness of the blank paper portion and ink absorbability.

  Colloidal silica is PL-10A, PL-3L, PL-1, etc. from Fuso Chemical Co., Ltd., Snowtex (registered trademark) ST-20, ST-30, ST-40 from Nissan Chemical Industries, Ltd. ST-C, ST-N, ST-20L, ST-O, ST-OL, ST-S, ST-XS, ST-XL, ST-YL, ST-ZL, ST-OZL, ST-UP, ST It is commercially available as -OUP, ST-PS-MO, etc., and can be obtained.

  In addition to the basic polyaluminum hydroxide compound, known agents such as a resin binder, a surfactant, and a pH adjuster can be used for the ink receiving layer mainly containing colloidal silica. When using a resin binder, it is preferable to use the same ink-receiving layer that mainly contains vapor-phase process silica, preferably 5% by mass or less based on colloidal silica. The content is preferably 1% by mass or less, and is preferably not added.

  It is preferable to select and use a resin binder for the ink receiving layer mainly containing vapor phase method silica from the viewpoint of high transparency and high ink permeability. In using the resin binder, it is important that the resin binder does not swell at the initial permeation of the ink and block the voids. From this viewpoint, a resin binder having a relatively low swellability around room temperature is preferably used. Preferred resin binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

  The cation-modified polyvinyl alcohol is, for example, a polyvinyl alcohol having a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of polyvinyl alcohol as described in JP-A-61-110483. It is.

  Among the polyvinyl alcohols, those partially saponified or completely saponified with a saponification degree of 80% or more are preferable. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferred. Polyvinyl alcohol having an average degree of polymerization of 3000 to 4000 is preferable from the viewpoint of the coating property of the ink receiving layer and the ink absorbability.

  The ratio of the resin binder to the vapor phase silica in the ink receiving layer mainly containing the vapor phase silica is preferably in the range of 10 to 30% by mass, and more preferably in the range of 15 to 25% by mass.

  The ink receiving layer mainly containing vapor-phase process silica preferably contains a boron-containing compound as a hardener together with the resin binder. Examples of boron-containing compounds include boric acid, borates, and borax, and these can be used alone or in combination. Examples of borates include orthoborate, metaborate, diborate, tetraborate, and pentaborate.

  In addition to hardeners, basic polyaluminum hydroxide compounds, and water-soluble zirconium compounds, surfactants, UV absorbers, antioxidants, and pigment dispersions are used in ink-receiving layers mainly containing vapor-phase process silica. Various known additives such as an agent, an antifoaming agent, a leveling agent, a preservative, a viscosity stabilizer, and a pH adjuster can also be added.

  The polyolefin resin-coated support used in this embodiment is a polyolefin resin-coated paper or the like in which a polyolefin resin layer is coated on both sides of a base paper, and the thickness of the support is 150 to 350 μm, preferably 200 to 300 μm. preferable.

  The moisture content of the polyolefin resin-coated paper is not particularly limited, but is preferably in the range of 5 to 9% by mass, more preferably in the range of 6 to 9% by mass. The moisture content of the polyolefin resin-coated paper can be measured using any moisture measuring method. For example, an infrared moisture meter, an absolute dry weight method, a dielectric constant method, a Karl Fischer method, or the like can be used.

  The base paper constituting the polyolefin resin-coated paper is not particularly limited, and commonly used paper can be used. More preferably, for example, a smooth base paper used for a photographic support is preferable. As the pulp constituting the base paper, natural pulp, regenerated pulp, synthetic pulp or the like is used alone or in combination. This base paper is blended with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, and dye generally used in papermaking. Further, a surface sizing agent, surface paper strengthening agent, fluorescent brightening agent, antistatic agent, dye, anchor agent and the like may be applied on the surface.

Although there is no restriction | limiting in particular regarding the thickness of a base paper, The thing with good surface smoothness which applied the pressure with the calendar | calender etc. during papermaking or after papermaking is preferable, and the basic weight is 100-250 g / m. ² is preferred.

  Examples of the polyolefin resin that coats the base paper include olefin homopolymers such as low density polyethylene, high density polyethylene, polypropylene, polybutene, and polypentene, or copolymers composed of two or more olefins such as ethylene-propylene copolymer, and the like. Of various densities and melt viscosity indices (melt index) can be used alone or as a mixture thereof.

  In the resin of the polyolefin resin-coated support, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, stearin Fatty acid metal salts such as magnesium acid, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet, manganese purple, fluorescent brighteners, UV absorbers It is preferable to add various additives such as

In the polyolefin resin layer on the side where the ink receiving layer is provided, it is preferable to use a low density polyethylene resin having a density of 0.930 g / m ³ or less of 90% by mass or more, further 100% by mass of the total resin. In the polyolefin resin layer opposite to the ink absorbing layer, it is preferable to use a high density polyethylene resin having a density of 0.950 g / m ³ or more of 30% by mass or more, more preferably 50% by mass or more of the total resin. The upper limit is about 95% by mass.

  The main production method of the polyolefin resin-coated support is produced by a so-called extrusion coating method in which a polyolefin resin is cast on a traveling base paper in a heated and melted state, and both surfaces of the base paper are covered with the resin. Further, before the resin is coated on the base paper, the base paper is preferably subjected to an activation treatment such as corona discharge treatment or flame treatment. The thickness of the resin coating layer is suitably 5 to 50 μm.

An undercoat layer is preferably provided on the side of the polyolefin resin-coated support on which the ink receiving layer is to be applied. This undercoat layer is preferably applied and dried in advance on the surface of the polyolefin resin-coated support before the ink receiving layer is applied. This undercoat layer mainly contains a water-soluble polymer or polymer latex that can form a film. Preferred are water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble cellulose, and particularly preferred is gelatin. 10-500 mg / m < ² > is preferable and the adhesion amount of these water-soluble polymers has more preferable 20-300 mg / m < ² >. Furthermore, it is preferable that the undercoat layer contains a surfactant and a hardener. By providing the undercoat layer on the support, it effectively works to prevent cracking when the ink receiving layer is applied, and a uniform coated surface is obtained.

  Hereinafter, although the ink jet recording material of the present invention will be described in detail by way of examples, the contents regarding the ink jet recording material of the present invention are not limited to the following examples. In addition, a part represents the mass part of solid content or a substantial component.

<Preparation of polyolefin resin-coated support 1>
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and hardwood bleached sulfite pulp (LBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. The sizing agent and alkyl ketene dimer were 0.5% by mass of pulp, 1% by mass of polyacrylamide as a strengthening agent, 1% by mass of cationized starch, 2% by mass of pulp, and polyamide epichlorohydrin resin by 0.1% of pulp. 5% by mass was added and diluted with water to make a 0.2% slurry. This slurry was made with a long paper machine to a basis weight of 190 g / m ² , dried and conditioned to obtain a base paper for the support. 10% by mass of anatase-type titanium and 0.06 part of fluorescent whitening agent with respect to 100% by mass of low-density polyethylene having a density of 0.918 g / cm ³ on the side of the coated base paper where the ink-receiving layer is applied The resin on the ink-receiving layer coating surface side is melted at 320 ° C., extruded to a thickness of 40 μm at 200 m / min, and cooled with a fine-roughened cooling roll. A coating layer was provided. On the opposite side to melt at similarly 320 ° C. The blend resin composition of the low density polyethylene resin 30 parts of a density 0.962 g / cm 70 parts high density polyethylene resin of ³ and a density 0.918 g / cm ^3, a thickness The resin coating layer was provided while cooling with a cooling roll so as to be 35 μm.

The polyolefin resin-coated support 1 was subjected to high-frequency corona discharge treatment on the ink-receiving layer-coated surface side, and then an undercoat layer having the following composition was coated and dried so that the gelatin content was 50 mg / m ² .

<Underlayer>
Lime-processed gelatin 100 parts Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome alum 10 parts

From the side closer to the polyolefin resin-coated paper support 1 provided with the undercoat layer, the ink receiving layer A-1 having the following composition is dried at 20 g / m ² in dry solid content, and the ink receiving layer B-1 having the following composition is dried. The ink-jet recording material of Example 1 was prepared by coating and drying the layer C-1 having a solid content coating amount of 5 g / m ² and colloidal silica having the following composition so as to be 0.2 g / m ² .

<Ink receiving layer A-1>
Gas phase method silica 100 parts (average secondary particle size 100 nm, average primary particle size 7 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P, molecular weight 9000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
3 parts of basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

<Ink receiving layer B-1>
Gas phase method silica 100 parts (average secondary particle size 100 nm, average primary particle size 7 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P, molecular weight 9000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
Water-soluble zirconium compound 1.5 parts (Zircosol (registered trademark) ZA-30 manufactured by Daiichi Rare Element Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

<Layer C-1 having colloidal silica>
100 parts of PL-3L (Fuso Chemical Co., Ltd. colloidal silica, average primary particle size 32 nm)
125 parts of basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.)
It adjusted with water so that solid content concentration might be 1 mass%.

(Comparative Example 1)
An inkjet recording material of Comparative Example 1 was produced in the same manner as in Example 1 except that the layer C-1 having colloidal silica of Example 1 was not provided.

(Comparative Example 2)
From the side closer to the polyolefin resin-coated paper support 1, the ink receiving layer A-2 having the following composition is applied in a dry solid content of 20 g / m ² , and the ink receiving layer B-2 having the above composition is applied in a dry solid content. An inkjet recording material of Comparative Example 2 was produced in the same manner as in Example 1 except that coating and drying were sequentially performed so as to be 5 g / m ² .

<Ink receiving layer A-2>
Gas phase method silica 100 parts (average secondary particle size 100 nm, average primary particle size 7 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P, molecular weight 9000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
3 parts of water-soluble zirconium compound (Zircosol (registered trademark) ZA-30 manufactured by Daiichi Rare Element Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

<Ink receiving layer B-2>
Gas phase method silica 100 parts (average secondary particle size 100 nm, average primary particle size 7 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P, molecular weight 9000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
1.5 parts of basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

(Comparative Example 3)
From the side closer to the polyolefin resin-coated support 1, the ink receiving layer A-3 having the following composition was applied in a solid content of 20 g / m ² , and the ink receiving layer B-3 having the following composition was applied in a dry solid content of 5 g / m. ² An inkjet recording material of Comparative Example 3 was produced in the same manner as in Example 1 except that coating and drying were performed in order.

<Ink receiving layer A-3>
Wet process silica 100 parts (average secondary particle size 100 nm, average primary particle size 15 nm)
4 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P manufactured by Daiichi Kogyo Seiyaku Co., Ltd., molecular weight 9000)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
3 parts of basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

<Ink receiving layer B-3>
Wet process silica 100 parts (average secondary particle size 100 nm, average primary particle size 15 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol (registered trademark) DC902P, molecular weight 9000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
Water-soluble zirconium compound 1.5 parts (Zircosol (registered trademark) ZA-30 manufactured by Daiichi Rare Element Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

(Comparative Example 4)
From the side close to the polyolefin resin-coated support 1, the ink receiving layer A-1 having the above composition is 25 g / m ^{2 in} terms of solid content, and the ink receiving layer C-1 having the above composition is 0.2 g in dry solid content. The ink jet recording material of Comparative Example 4 was prepared by coating and drying in order so as to be / m ² .

  Next, the water-soluble ink used for evaluation of the recording material of this example will be described. As the water-soluble ink to be used, among the water-soluble inks, a dye ink can be used to obtain a recorded material with good image quality, which is preferable in terms of ejection stability from the head of an ink jet printer. Various dyes can be used as the dye used in the dye ink. The ink (ink composition) contains at least water, a water-soluble organic solvent, an acetylene glycol surfactant, and a glycol ether compound. The water-soluble ink is preferably from the viewpoint of improving the ejection stability by adjusting the viscosity and surface tension of the ink when recording from an ink jet printer, and the stability of the ink over time in the head. Water, a water-soluble organic solvent, an acetylene glycol surfactant, and a glycol ether compound will be described later.

  The dye contained in the ink composition will be described. As the dye, various existing dyes such as organic dyes and inorganic dyes can be used. In particular, when performing color printing, it is configured as a color ink set composed of a plurality of ink compositions, and the ink composition constituting the ink set includes an ink composition containing a magenta dye, an ink composition containing a cyan dye, It is preferable to provide an ink composition containing a yellow dye. In particular, an ink composition containing the following dye is suitable.

  The ink composition is preferably an ink composition containing a cyan dye which is a compound represented by the following formula (C-1).

で表されるフタロシアニン化合物及びその塩からなる群から選ばれる化合物。

A compound selected from the group consisting of a phthalocyanine compound represented by the formula:

Here, in formula _{(C-1), X 1} , X 2, X 3 and X ₄ independently represents any of -SO-Z and -SO ₂ -Z. Here, each Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group. Or a substituted or unsubstituted heterocyclic group.
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, or ionic Represents a hydrophilic group, each group is further substituted It may have a group.
a ₁ ~a ₄ and b ₁ ~b ₄ each represent the number of substituents of X ₁ to X ₄ and Y ₁ to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all of them are not 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4.
M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group. As a group possessed as

In this example, in the above formula (C-1), a ₁ , a ₂ , a ₃ and a ₄ are 0 or 1, and two or more of a ₁ , a ₂ , a ₃ and a ₄ Is 1, and b ₁ , b ₂ , b ₃ and b ₄ are each preferably an integer such that the sum of a ₁ , a ₂ , a ₃ and a ₄ is 4, respectively.

As described above, in the formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ each independently represent either —SO—Z or —SO ₂ —Z, and Z is further substituted. The substituent which Z can have is a halogen atom (for example, a chlorine atom or a bromine atom); a linear or branched alkyl group having 1 to 12 carbon atoms, carbon 7 to 18 aralkyl groups, 2 to 12 alkenyl groups, 2 to 12 linear or branched alkynyl groups, and 3 to 12 carbon cycloalkyls optionally having side chains A C3-C12 cycloalkenyl group optionally having a side chain (for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl) , Trifluoromethyl, Cyclopentyl); aryl groups (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl); heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2 -Pyrimidinyl, 2-benzothiazolyl); alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); acylamino group (eg, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide); alkylamino group ( For example, methyl amino Anilino group (eg, phenylamino, 2-chloroanilino; ureido group (eg, phenylureido, methylureido, N, N-dibutylureido)); sulfamoylamino group (eg, butylamino, diethylamino, methylbutylamino); N, N-dipropylsulfamoylamino); alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio); arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenyl) Thio); alkyloxycarbonylamino group (eg methoxycarbonylamino); sulfonamide group (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane); carbamoyl group (eg N-ethylcarbamoyl, N, N-dibutylcarbamoyl); sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl groups (eg, methane) Sulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy) An azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); an acyloxy group (eg, acetoxy); a carbamoyloxy group (eg, N -Methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy groups (eg trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino groups (eg phenoxycarbonylamino); imide groups (eg N-succinimide, N- Phthalimi); heterocyclic thio groups (eg 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio); sulfinyl groups (eg 3-phenoxy) Propylsulfinyl); phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg phenoxycarbonyl); acyl group (eg acetyl, 3-phenylpropanoyl, Nzoiru); ionic hydrophilic group (e.g., carboxyl group, sulfo group, and a quaternary ammonium group), cyano groups, hydroxy groups, nitro groups, and amino group.

  In addition, the ionic hydrophilic group in the formula (C-1) includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and specific examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion, lithium ion) and an organic cation (eg, tetra Methyl guanidinium ion).

Among the compounds represented by the formula (C-1), M in the formula (C-1) is a copper atom, X _{1 to} X ₄ are represented by —SO ₂ Z, and the Z is R ⁵ ( R ⁵ is, - (CH ₂₎ represents a ₃ SO ₃ M ^2, wherein M ² represents an alkali metal atom) and / or R ⁶ (R ⁶ _{is, - (CH 2). 3} SO 2 NHCH 2 CH (OH) represents CH _3. ), And a compound in which M ² is Li is more preferable. In particular, the compound represented by the formula (C-1) is preferably a mixture of a tetrasulfonic acid body, a trisulfonic acid body, and a disulfonic acid body in which R ⁵ / R ⁶ (molar ratio) = 3/1. This tetrasulfonic acid body, trisulfonic acid body, and disulfonic acid body each have three of a _{1 to} a ₄ when all _four of a _{1 to} a ₄ are 1 in the formula (C-1). This corresponds to the case where 1 is 1 and 0, and 2 out of a _{1 to} a ₄ are 1 and 2 are 0.

In particular, in the compound represented by the formula (C-1) as the cyan dye, M is a copper atom, X ₁ , X ₂ , X ₃ and X ₄ are —SO ₂ Z, and Z represents R ⁵ (wherein R ⁵ represents — (CH ₂ ) ₃ SO ₃ M ² , where M ² represents an alkali metal atom) and / or R ⁶ (wherein R ⁶ represents — (CH _{2 3} SO ₂ NHCH ₂ CH (OH) CH ₃ ), Y ₁ , Y ₂ , Y ₃ and Y ₄ are hydrogen atoms, and a ₁ , a ₂ , a ₃ and a ₄ are 0 or 1 and two or more of a ₁ , a ₂ , a ₃ and a ₄ are 1, and b ₁ , b ₂ , b ₃ and b ₄ are a ₁ , a ₂ , a ₃ , respectively. and if the sum of the a ₄ is an integer which is a 4, it is possible to ensure the color material of good hue (including saturation), particularly preferable because it can ensure water-soluble. In this case, it is even more preferable that M ² is Li, since the water-solubility of the coloring material can be secured and bronze can be avoided.

In this case, Z is a mixture of a tetrasulfonic acid body, a trisulfonic acid body, and a disulfonic acid body independently selected from R ⁵ or R ⁶ , and is included in the cyan dye as a whole. the molar ratio of R ⁵ and the R ⁶ is R ⁵ / R ⁶ = 3/1 is preferred because of the compatibility of a higher dimension of ozone resistance and bronzing suppression.

  A method for synthesizing the compound represented by the formula (C-1) is shown below.

In the above reaction formula, the phthalocyanine compound represented by the general formula II is an embodiment of the compound represented by the formula (C-1), and can be used in this example. The phthalocyanine compound represented by the general formula II is represented by, for example, a phthalonitrile compound represented by the general formula III and / or a diiminoisoindoline derivative represented by the general formula IV and M- (Y) d. It can be synthesized by reacting a metal derivative. In General Formula II, General Formula III, and General Formula IV, Z and Z _{1 to} Z ₄ are synonymous with Z in Formula (C-1), and M is M in Formula (C-1). It is synonymous with. Here, Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate, or oxygen, and d is an integer of 1 to 4. Examples of the metal derivative represented by M- (Y) d include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, and Pb. And halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, and complexes. Specific examples of this metal derivative include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, iodine. Zinc chloride, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, and tin chloride Etc.

The compound represented by the general formula II thus obtained is usually (SO ₂ -Z ₁ ), (SO ₂ -Z ₂ ), (SO ₂ -Z ₃ ) in the general formula II, and (SO ₂ —Z ₄ ) (these groups also correspond to R ₁ , R ₂ , R ₃ , and R ₄ in the formula (1)), which is an isomer of the following general formula (a) It is a mixture of the compounds represented by -1 to (a) -4.

In the present embodiment, the content of the cyan-based dye contained in the cyan ink composition is the type of X ₁ to X ₄ and Y ₁ to Y ₄ in formula (C-1), and for producing an ink composition In this embodiment, the total amount of the cyan dye represented by the formula (C-1) (the dye of the formula (C-1)) is determined by the cyan ink composition. The content is preferably 1 to 10% by weight, more preferably 2 to 6% by weight, based on the total weight of the cyan ink composition. When the total amount of the dye of the formula (C-1) contained in the cyan ink composition is 1% by weight or more, the color developability of the ink on the recording medium when printed can be improved and is required. Image density can be secured. Further, by making the total amount of the dye of the formula (C-1) contained in the cyan ink composition 10% by weight or less, the discharge property of the cyan ink composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  As described above, in the cyan ink composition in the ink set of the present embodiment, other cyan dyes are used in combination so as not to greatly impair ozone resistance, light resistance, and moisture resistance for adjusting the color tone of the ink. be able to.

  Examples of other cyan dyes that can be used in this example include C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251 252, 264, 270, 280, 288, 289, 291, C.I. I. Acid Blue 9,25,40,41,62,72,76,78,80,82,92,106,112,113,120,127: 1,129,138,143,175,181,205,207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, etc. Not.

  Next, the ink composition contains, as a magenta dye, at least one compound represented by the following formula (M-1) and at least one compound represented by the following formula (M-2). Is preferred.

ここで、前記式（Ｍ−１）中、Ａは、５員複素環ジアゾ成分Ａ−ＮＨ２の残基を表す。Ｂ１およびＢ２は、各々−ＣＲ１＝、−ＣＲ２＝を表すか、あるいはいずれか一方が窒素原子，他方が−ＣＲ１＝または−ＣＲ２＝を表す。Ｒ５，Ｒ６は、各々独立に、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基を表わす。各基は更に置換基を有していてもよい。Ｇ、Ｒ1、Ｒ2は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキル基またはアリール基または複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルフアモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルおよびアリールスルホニルアミノ基、アリールオキシカルボニルアミノ基、ニトロ基、アルキルおよびアリールチオ基、アルキルおよびアリールスルホニル基、アルキルおよびアリールスルフィニル基、スルファモイル基、スルホ基、またはヘテロ環チオ基を表す。各基は更に置換されていてもよい。また、Ｒ１とＲ５、あるいはＲ１とＲ５が結合して５〜６員環を形成してもよい。

Here, in the formula (M-1), A represents a residue of a 5-membered heterocyclic diazo component A-NH2. B1 and B2 each represent -CR1 = and -CR2 =, or one of them represents a nitrogen atom and the other represents -CR1 = or -CR2 =. R5 and R6 are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group. Represents. Each group may further have a substituent. G, R 1 and R 2 are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group Substituted with hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and arylthio group, Kill or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted. R1 and R5, or R1 and R5 may be bonded to form a 5- to 6-membered ring.

ここで、前記式（Ｍ−２）中、Ｍは水素原子、アンモニウム基、又はアルカリ金属原子、Ｘはジアミノアルキレン基を表し、ｎは１又は２である。

Here, in the formula (M-2), M represents a hydrogen atom, an ammonium group, or an alkali metal atom, X represents a diaminoalkylene group, and n is 1 or 2.

  The magenta ink composition used in the ink of this example is at least one compound represented by the formula (M-1) as a colorant in water or an aqueous medium composed of water and a water-soluble organic solvent. And at least one compound represented by the formula (M-2), and further contains a surfactant and a glycol ether compound. If necessary, a moisturizing agent, a viscosity adjusting agent, a pH adjusting agent and other additives may be further contained. By using the compound represented by the formula (M-1) and the compound represented by the formula (M-2) in combination, it has excellent light resistance, ozone resistance and moisture resistance, and is well balanced. An ink composition having the above characteristics can be provided.

  As the compound (magenta dye) represented by the formula (M-1) used in this example, one kind may be used alone, or a plurality kinds may be mixed and used.

  Among the compounds represented by the formula (M-1), a compound represented by the following formula (M-3) is preferable.

式（Ｍ−３）において、Ｒ₁〜Ｒ₅は、水素原子、アルキル基、スルホ基又はその塩を表す。式（Ｍ−３）において、Ｒ₁，Ｒ₅はそれぞれ独立に、共にアルキル基の時はそのアルキル基を構成する炭素数の合計が３以上であってそれらに置換基を有していてもよい。Ｘは水素原子、脂肪族基、芳香族基、または複素環基を表し、Ｙ及びＺは各々独立に、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基を表す。各基は更に置換基を有していてもよい。また、Ｒ₁〜Ｒ₅にスルホ基が含まれる場合には−ＳＯ₃Ｍの形となっている。その場合、Ｍとしては、アルカリ金属原子が好ましく、より好ましくはＬｉ又はＮａである。

In formula (M-3), R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, a sulfo group, or a salt thereof. In formula (M-3), when R ₁ and R ₅ are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may have a substituent. Good. X represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y and Z each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, An aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group is represented. Each group may further have a substituent. When R _{1 to} R ₅ contain a sulfo group, it is in the form of —SO ₃ M. In that case, M is preferably an alkali metal atom, more preferably Li or Na.

  Among the compounds represented by the formula (M-3), a compound represented by the following formula (M-4) is particularly preferable because of having excellent light resistance and ozone resistance.

前記式Ｍ−４中、Ｒ₁〜Ｒ₁₀は水素原子、アルキル基、スルホ基又はその塩を表し、（Ｒ₁，Ｒ₅）及び（Ｒ₆，Ｒ₁₀）は、それぞれ独立に、共にアルキル基を構成する炭素数の合計が３以上であってそれらに置換基を有していてもよい。また、Ｍは水素原子又はアルカリ金属原子を表す。

In the formula M-4, R _{1 to} R ₁₀ represent a hydrogen atom, an alkyl group, a sulfo group or a salt thereof, and (R ₁ , R ₅ ) and (R ₆ , R ₁₀ ) are each independently alkyl. The total number of carbon atoms constituting the group is 3 or more, and they may have a substituent. M represents a hydrogen atom or an alkali metal atom.

  In the compound (magenta dye) represented by the formula (M-2) used in combination with the compound represented by the formula (M-1) as a colorant in the magenta ink composition, M forms a hydrogen atom and a salt. Represents an ammonium group or an alkali metal atom, X represents a diaminoalkylene group, and n is 1 or 2.

  Addition of the compound represented by formula (M-2) has an effect of improving moisture resistance. The compound represented by general formula (M-2) may be used individually by 1 type, or may use multiple types together. Among the compounds represented by the general formula (M-2), a compound having a structure where n is 2 has particularly good moisture resistance and is particularly preferable.

  In addition, the magenta ink composition may be used in combination with other magenta dyes within a range that does not significantly impair each characteristic such as light resistance, in order to adjust the color tone. Examples of magenta dyes other than the compounds represented by formula (M-1) and formula (M-2) include C.I. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Reactive violet 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34, C.I. I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I. Basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, etc. can be mentioned.

  In the magenta ink composition, the content of the compound represented by the formula (M-1) is preferably 0.2 to 2.5 wt%, more preferably the total weight with respect to the total weight of the ink composition. 0.3 to 2.0 wt%. Light resistance and ozone resistance can be improved by setting it as 0.2 wt% or more, and a fall in moisture resistance can be prevented by setting it as 2.5 wt% or less.

Further, the content of the compound represented by the formula (M-2) is preferably 0.4 to 7.0 wt%, more preferably 0.6 to 7% by total weight with respect to the total weight of the ink composition. 6 wt%. When the content is 0.4 wt% or more, moisture resistance can be improved, and when the content is 7.0 wt% or less, a decrease in light resistance can be prevented.
In the examples,% by weight is the same as% by mass.

  In the magenta ink composition, the content ratio of the compound represented by the formula (M-1) and the compound represented by the formula (M-2) is 2: 1 to 1: 8 by weight. And is more preferably in the range of 1: 1 to 1: 6. By containing both compounds in such a ratio, light resistance, ozone resistance and moisture resistance can be satisfied at a high level.

  In the magenta ink composition, the total colorant solid content (dye solid content) is preferably in the range of 0.6 to 8.0 wt% with respect to the total weight of the ink composition. When the amount is 0.6 wt% or more, the required color developability (maximum density) can be obtained, and when the amount is 8.0 wt% or less, clogging when used in an ink set or the like can be prevented.

  The magenta ink composition is represented by the following formula (2) in addition to the ink composition containing the compound represented by the formula (M-1) and the compound represented by the formula (M-2). An ink composition containing the compound represented may be used.

  An ink composition comprising at least one compound selected from the group consisting of a compound represented by the following formula (2) and a salt thereof.

Ａは、アルキレン基、フェニレン基を含有するアルキレン基で表される基、又は下記式（３）で表される基を表し、さらにＸは、ＮＨ₂、ＯＨ、及びＣｌからなる群から選ばれる基を表す。

A represents an alkylene group, a group represented by an alkylene group containing a phenylene group, or a group represented by the following formula (3), and X is selected from the group consisting of NH ₂ , OH, and Cl. Represents a group.

Ｒは、水素又はアルキル基を意味する。

R means hydrogen or an alkyl group.

The compound of the formula (2) may be produced by any method, but as an example, it can be produced by the following method.
1) 1-methylamino-4-bromoanthraquinone is reacted with benzoylacetic acid ethyl ester in a solvent to give 1-benzoyl-6-bromo-2,7-dihydro-3-methyl-2,7-dioxo-3H-dibenzo [F, ij] Isoquinoline is obtained.
2) Next, the compound obtained in 1) above and metaaminoacetanilide are reacted in a solvent to produce 3 ′-[1-benzoyl-2,7-dihydro-3-methyl-2,7-dioxo-3H-dibenzo. [F, ij] isoquinolin-6-ylamino] -acetanilide is obtained.
3) Next, the compound obtained in 2) above was reacted in fuming sulfuric acid, and trisodium-6-amino-4- [2,7-dihydro-3-methyl-1- (3-sulfonatobenzoyl)- 2,7-Dioxo-3H-dibenzo [f, ij] isoquinolin-6-ylamino] -benzene-1,3-disulfonate is obtained.
4) Next, the compound obtained in 3) above and cyanuric chloride are reacted in water to obtain a primary condensate, which is further reacted with a diamine having a linking group A represented by formula (2) to obtain a secondary product. A condensate is obtained.
5) Next, the compound obtained in 4) above is directly or hydrolyzed or reacted with ammonia to form a tertiary condensate to obtain the target compound represented by the formula (2).

  In addition, what is necessary is just at least 1 type of the compound represented by the said Formula (2), and its salt, and the total content in those ink compositions can be suitably defined based on the color value of the dye. However, it is preferable to contain 2.0 to 10 weight% in total amount. By setting the dye concentration to 2.0% by weight or more, sufficient color developability can be secured as an ink. Further, by setting the dye concentration to 10% by weight or less, the ink composition used in the ink jet recording method can be ejected from a nozzle. It is easy to ensure the property and prevent nozzle clogging.

  Next, the ink composition is preferably an ink composition containing at least one compound represented by the following formula (Y-1) as a yellow dye.

（上記式（Ｙ−１）中、Ｘ₁、Ｘ₂、Ｙ₁、及びＹ₂は水素原子、又はシアノ基を表し、Ｚ₁及びＺ₂は芳香環を有する置換基を表し、Ｒ₁及びＲ₂はアルキル基を表し、Ｍは金属原子を表す。）

(In the above formula (Y-1), X ₁ , X ₂ , Y ₁ , and Y ₂ represent a hydrogen atom or a cyano group, Z ₁ and Z ₂ represent a substituent having an aromatic ring, R ₁ and R ₂ represents an alkyl group, and M represents a metal atom.)

  In particular, the compound represented by the formula (Y-1) is preferably a compound represented by the following formula (Y-2) from the viewpoint of improving light resistance and ozone resistance.

（上記式（Ｙ−２）中、Ｘ₁、Ｘ₂、Ｙ₁、及びＹ₂は水素原子、又はシアノ基を表し、Ｗ₁〜Ｗ₅及びＷ₁₁〜Ｗ₁₅は、それぞれ水素原子、カルボキシル基又はその塩を表し、Ｍは金属原子を表し、ｔ−Ｂｕはターシャリーブチル基を表す。）

(In the formula _{(Y-2), X 1} , X 2, Y 1, and Y ₂ represents a hydrogen atom, or a cyano group, W ₁ to _W-5 and W ₁₁ to _W-15 are each a hydrogen atom, a carboxyl A group or a salt thereof, M represents a metal atom, and t-Bu represents a tertiary butyl group.)

  Furthermore, in this embodiment, in order to adjust the color tone of the yellow ink composition, other yellow dyes can be used in combination as long as the ozone resistance, light resistance, and moisture resistance are not significantly impaired.

  In this embodiment, the concentration of the colorant contained in the yellow ink composition can be appropriately determined according to the color value of the compound (dye) used as the colorant, but the total amount of the colorant is determined according to the yellow ink composition. It is preferable that 1.0 to 7.0% by weight is contained in the product with respect to the total weight of the yellow ink composition. By setting the concentration of the total amount of the colorant contained in the yellow ink composition to 1.0% by weight or more, good color developability can be obtained, and the concentration of the total amount of the colorant is set to 7.0. By setting it to not more than% by weight, it is possible to improve the characteristics such as ejection properties from the nozzles required as an ink composition for use in the ink jet recording method, and to prevent clogging of the ink nozzles.

In addition to the ink composition containing the compound represented by the above formula (Y-1), the yellow ink composition is represented by the compound represented by the following formula (5) and the following formula (6). An ink composition containing a compound may be used.
The compound represented by following formula (5).

及び、下記の式（６）で表される化合物。

And a compound represented by the following formula (6).

（前記式（５）及び（６）中、Ｒ₅、Ｒ₅’、Ｒ₆、及びＲ₆’、は独立して、ＣＨ₃、ＯＣＨ₃を表し、Ｚ及びＺ’は、独立して、

(In the above formulas (5) and (6), R ₅ , R ₅ ′, R ₆ , and R ₆ ′ independently represent CH ₃ , OCH ₃ , and Z and Z ′ are independently

のいずれかの構造を有するものであり、互いに同一であっても異なっていても良い。ここで、Ｍは、Ｈ、Ｌｉ、Ｎａ、Ｋ、アンモニウム、又は有機アミン類を表し、ｎは１又は２の整数である。）
上記式（５）で表される化合物からなる群から選ばれる少なくとも一種と上記式（６）で表される化合物からなる群から選ばれる少なくとも一種含むインク組成物である。

These structures may be the same as or different from each other. Here, M represents H, Li, Na, K, ammonium, or organic amines, and n is an integer of 1 or 2. )
An ink composition comprising at least one selected from the group consisting of compounds represented by the above formula (5) and at least one selected from the group consisting of compounds represented by the above formula (6).

  The total amount contained in at least one ink composition selected from the group consisting of at least one selected from the group consisting of the compound represented by the above formula (5) and from the group consisting of the compound represented by the above formula (6), Although it can be appropriately determined according to the color value of the compound used as the colorant, generally, the total amount is 1.0 to 6.0% by weight with respect to the total weight of the ink composition. preferable. By making the concentration of the total amount of the colorant contained in the ink composition 1.0% by weight or more, good color development can be obtained, and the concentration of the total amount of the colorant is 6.0% by weight. By setting the ratio to less than or equal to%, it is possible to improve the properties such as ejection properties from the nozzles required as an ink composition for use in the ink jet recording method, and to prevent clogging of the ink nozzles.

  The colorant used in the ink composition used for the evaluation of the recording material of the present embodiment and the content of the colorant in the ink composition have been described above. Hereinafter, other components included in each ink composition will be described. .

  Each ink composition can be obtained by dissolving the above-described colorant (dye) in an appropriate solvent. As a solvent for dissolving the colorant in each ink composition, water or a mixed liquid of water and a water-soluble organic solvent is preferably used as a main solvent. As water, ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or the like can be used. From the viewpoint of long-term storage, it is preferable to use water that has been subjected to various chemical sterilization treatments such as ultraviolet irradiation and addition of hydrogen peroxide. The water content in each ink composition constituting the ink set of this example is preferably 40 to 90% by weight, more preferably 50 to 80% by weight of the ink composition.

  As described above, each ink composition can use a water-soluble organic solvent as a solvent together with water. As the water-soluble organic solvent, those having the ability to dissolve the dye are preferable, and those having a vapor pressure smaller than that of pure water are preferable.

  Examples of the water-soluble organic solvent to be used include ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2,6. -Polyhydric alcohols such as hexanetriol, diethylene glycol, triethylene glycol, dipropylene glycol, ketones such as acetonylacetone, esters such as γ-butyrolactone, triethyl phosphate, furfuryl alcohol, tetrahydrofurfuryl alcohol, thio Although diglycol etc. are preferable, it is not limited to these. By using a water-soluble organic solvent together with water as the solvent of the ink composition, the ejection stability of the ink composition from the ink head can be improved, and the viscosity of the ink composition can be lowered with almost no other change. Etc. can be easily adjusted.

  The ink composition further contains a nonionic surfactant. By adding a nonionic surfactant, the penetrability of the ink composition into the recording medium is improved, and the ink composition can be quickly fixed on the recording medium during printing. Further, it is preferable that one dot recorded by the ink composition on the recording medium is as close to a perfect circle as possible. However, by containing a nonionic surfactant in the ink composition, an image formed by one dot It is possible to increase the roundness and improve the image quality of the obtained image.

  As the nonionic surfactant that can be used, an acetylene glycol surfactant is particularly preferable. As the acetylene glycol surfactant used in the ink composition of this embodiment, it is particularly preferable to use a compound represented by the following formula (a-1).

式（ａ-１）中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴はそれぞれ独立して、Ｃ１〜Ｃ６の直鎖、環式又は分枝アルキル鎖を表し、さらにＡ¹Ｏ及びＡ²Ｏはそれぞれ独立してＣ２〜Ｃ３のオキシアルキレン鎖、例えばオキシエチレン若しくはオキシプロピレン、又はＣ２〜Ｃ３のアルキレンオキサイドが重合又は共重合して得られるポリオキシアルキレン鎖、例えばポリオキシエチレン鎖、ポリオキシプロピレン鎖、若しくはポリオキシエチレンプロピレン鎖を表す。また式中、ｎ及びｍはＡ¹Ｏ又はＡ²Ｏ単位、すなわちオキシアルキレンの繰り返し数を表し、０≦ｎ＜３０、０≦ｍ＜３０、及び０≦ｎ＋ｍ＜５０を満たす数である。

In the formula (a-1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a C1-C6 linear, cyclic, or branched alkyl chain, and A ¹ O and A ² O is each independently a C2-C3 oxyalkylene chain, such as oxyethylene or oxypropylene, or a polyoxyalkylene chain obtained by polymerization or copolymerization of C2-C3 alkylene oxide, such as a polyoxyethylene chain, polyoxy A propylene chain or a polyoxyethylene propylene chain is represented. In the formula, n and m represent A ¹ O or A ² O units, that is, the number of oxyalkylene repeats, and are numbers satisfying 0 ≦ n <30, 0 ≦ m <30, and 0 ≦ n + m <50.

  Examples of the acetylene glycol surfactants include Surfinol 465, Surfinol 104 (produced by Air Products and Chemicals Inc.), Olphine PD001, Olphine E1010 (named above, trade name, manufactured by Nissin Chemical Industry Co., Ltd.). It is preferable to add at least one selected from these to the ink composition constituting the ink set of this embodiment.

  The nonionic surfactant is added to the ink composition so that the nonionic surfactant is preferably contained in the ink composition in an amount of 0.1 to 5% by weight, more preferably 0.5 to 2% by weight. Is good. By including 0.1% by weight or more of a nonionic surfactant in the ink composition, the penetrability of each ink composition with respect to the recording medium can be increased. Further, by making the content of the nonionic surfactant in the ink composition 5% by weight or less, an effect that an image formed with the ink composition on the recording medium is difficult to blur can be obtained.

  Further, by adding a glycol ether compound as a penetration accelerator to the ink composition, the permeability of the ink composition to the recording medium is improved, and at the boundary between adjacent color inks when color printing is performed, Ink bleeding (bleeding) is reduced, and a very clear image can be obtained.

  Examples of the glycol ether compound used in this example as a penetration enhancer include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol Propylene glycol monobutyl ether, triethylene glycol monobutyl ether and the like are preferable, but are not limited thereto. These glycol ether compounds are preferably contained in the ink composition in an amount of 3 to 30% by weight, more preferably 5 to 15% by weight. By making the addition amount of the glycol ether compound 3% by weight or more, bleeding (bleeding) between adjacent inks during color printing can be effectively prevented, and by making this addition amount 30% by weight or less, image It becomes easy to prevent the occurrence of bleeding, and the storage stability of the ink can be improved.

  Other additives may be added to the ink composition as necessary. This will be described below. At least one moisturizing agent selected from saccharides can be contained in each ink composition of this embodiment. By including a moisturizing agent in the ink composition, when the ink composition is used in the ink jet recording method, it is possible to suppress moisture evaporation from the ink and moisturize the ink. As the saccharide used in this example, maltitol, sorbitol, gluconolactone, maltose and the like are preferable. In addition, the water-soluble organic solvent mentioned above may work as a moisturizer.

  The water-soluble organic solvent and / or humectant can be contained in the ink composition in a total amount of 5 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 5 to 20% by weight. By making these contents 5% by weight or more, good ink moisture retention can be obtained, and by making it 50% by weight or less, the viscosity of the ink composition is adjusted to a preferred viscosity for use in the ink jet recording method. can do.

  In addition, the ink composition includes pH adjusters such as triethanolamine and alkali metal hydroxides, water-soluble polymers such as sodium alginate, water-soluble resins, fluorosurfactants, antiseptics, fungicides, and rust-proofs. A material selected from an agent, a dissolution aid, an antioxidant, an ultraviolet absorber, and the like can be added as desired. These components can be used alone or in combination of two or more. Moreover, it is not necessary to add, if it is not necessary to add. Those skilled in the art can use the preferable additive selected in a preferable amount as long as the effects of the present invention are not impaired. The dissolution aid is an additive for dissolving the insoluble matter and keeping the ink composition in a uniform solution when the insoluble matter is precipitated from the ink composition.

  Examples of the solubilizer include pyrrolidones such as N-methyl-2-pyrrolidone and 2-pyrrolidone, ureas such as urea, thiourea and tetramethylurea, allophanates such as allohanate and methyl allophanate, biuret and dimethylbiuret. And biurets such as tetramethylbiuret can be mentioned, but the invention is not limited to these. Moreover, as an example of the said antioxidant, although L-ascorbic acid and its salt etc. can be illustrated, it is not limited to these.

  Examples of the antiseptic or antifungal agent include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazoline-3. -ON (Alexia CRL, Proxel BDN, Proxel GXL, Proxel XL-2, and Proxel TN (trade name)) can be exemplified, but is not limited thereto. Examples of the rust inhibitor include benzotriazole, but are not limited thereto. Furthermore, a chelating agent can be added as necessary. Examples of the chelating agent include, but are not limited to, EDTA (ethylenediaminetetraacetic acid).

  Examples of the pH adjuster include amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and modified products thereof, metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, Examples thereof include ammonium salts such as quaternary ammonium hydroxide (tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates, but are not limited thereto.

  The ink composition is prepared by including components appropriately selected from the components described above, and the viscosity of the obtained ink composition is preferably less than 10 mPa · s at 20 ° C. Further, in this embodiment, the surface tension of the ink composition is preferably 45 mN / m or less at 20 ° C., and particularly preferably in the range of 25 to 45 mN / m. By adjusting the viscosity and the surface tension in this way, an ink composition having desirable characteristics for use in the ink jet recording method can be obtained. The adjustment of the viscosity and the surface tension can be performed by appropriately adjusting and selecting the addition amount of the solvent and various additives to be contained in the ink composition, the kind thereof, and the like.

  The ink composition preferably has a pH of 7.0 to 10.5 at 20 ° C., more preferably 7.5 to 10.0. By making the pH of the ink composition at 20 ° C. 7.0 or more, it is possible to prevent the eutectoid plating of the ink jet head from being peeled off, and to stabilize the ejection characteristics of the ink composition from the ink jet head. Can do. In addition, by setting the pH of the ink composition to 10.5 or less at 20 ° C., it is possible to prevent deterioration of various members that come into contact with the ink composition, for example, members constituting an ink cartridge or an inkjet head. .

  As a method for preparing the ink composition, for example, various components contained in the ink composition were sufficiently mixed and dissolved as uniformly as possible, followed by pressure filtration with a membrane filter having a pore diameter of 0.8 μm, and further obtained. Although the method of preparing by deaeration-processing a solution using a vacuum pump can be illustrated, it is not limited to this.

  Although it is desirable to use an ink composition containing each of the above dyes, each dye can also be contained in a separate ink composition, and can be contained in a single ink composition. An intermediate color ink composition may be used. Moreover, you may use as an ink set provided with the dark and light ink composition which varied the content containing the dye of the same color. Furthermore, in addition to the ink composition containing the above dye, the ink set may include an ink composition containing a color material other than the above dye. For example, an image having a good contrast can be formed on a recording medium by including a black ink composition containing a black color material such as a black dye. The components other than the color material of the ink composition containing another color material may be composed of the same composition as the ink composition containing the dye described above.

[Ink Example]
Hereinafter, the ink examples will be described more specifically, but the ink composition is not limited to the following ink examples.

[Preparation of each ink composition]
Based on the composition shown in Table 1 below, each component was mixed and stirred at room temperature for 30 minutes, and then the resulting solution was filtered using a membrane filter having a mesh size of 1.0 μm to obtain each ink composition. Obtained. In Table 1, the numerical value of each component indicates the weight percent of each component when the mass of the ink composition is 100%, and the “residue” indicating the amount of water is combined with the components other than water. The amount is 100% in total.

  In Table 1, “C−” represents a cyan ink composition, “M−” represents a magenta ink composition, and “Y−” represents a yellow ink composition.

  In Table 1, Cyan (cyan) dye 1 is an example of a compound represented by the formula (C-1), and has the following formula (A):

Z1 to Z4 in Cyan dye 1 (formula (A)) are those shown in Table 2 below.

  In Table 1, Magenta (magenta) dye 1 is an example of a compound represented by the formula (M-2), and is a compound represented by the following formula (B).

In the formula (B), M represents NH ₄ or Na, and NH ₄ : Na = 1: 1 (molar ratio).

Further, the Magenta (magenta) dye 2 is an example of a compound represented by the formula (M-1), is a compound represented by the following formula (C), and R _{1 to} R in the Magenta dye 2 ₄ is a group shown below, respectively.

  In Table 1, Magenta (magenta) dye 3 is a compound represented by the above formula (2), and is a compound represented by the following formula (D).

なお、式（Ｄ）中、ＭはＮＨ₄又はＮａを表し、ＮＨ₄：Ｎａ＝１：１（モル比）である。

In formula (D), M represents NH ₄ or Na, and NH ₄ : Na = 1: 1 (molar ratio).

  In Table 1, Yellow (yellow) dye 1 is an example of a compound represented by the formula (Y-2), and is a compound represented by the following formula (F).

  In Table 1, Yellow dye 2 is C.I. as a dye represented by the formula (4). I. Direct Yellow 173 (C.I. Direct Yellow 173), and in Table 1, Yellow dye 3 is C.I. as a dye represented by the formula (5). I. Direct Yellow 86 (C.I. Direct Yellow 86) was used.

  Next, dye ink sets 1 and 2 were prepared with the combinations shown in Table 4 using the prepared ink compositions.

The pigment ink set in Table 4 was prepared as an ink set composed of the following ink compositions.
(Magenta ink M-21)
Pigment (PR202) 1.5% by weight
Styrene-acrylic copolymer resin (solid content conversion)
0.5% by weight
Olfine E1010 0.5% by weight
Glycerin 20% by weight
20% ethylene glycol
1,2-hexanediol 5.0% by weight
2-pyrrolidone 2.0% by weight
TEA (triethanolamine) 1.0% by weight
Water remaining Total 100% by weight
(Yellow ink Y-21)
Pigment (PY74) 3.0% by weight
Styrene-acrylic copolymer resin (solid content conversion)
1.0% by weight
Olfine E1010 0.5% by weight
Glycerin 20% by weight
20% ethylene glycol
1,2-hexanediol 5.0% by weight
2-pyrrolidone 2.0% by weight
TEA (triethanolamine) 1.0% by weight
Water remaining Total 100% by weight
(Cyan ink C-21)
Pigment (PB15: 3) 1.5% by weight
Styrene-acrylic copolymer resin (solid content conversion)
0.5% by weight
Olfine E1010 0.5% by weight
Glycerin 20% by weight
20% ethylene glycol
1,2-hexanediol 5.0% by weight
2-pyrrolidone 2.0% by weight
TEA (triethanolamine) 1.0% by weight
Water remaining Total 100% by weight

  Next, a method for recording the ink composition on the ink jet recording material will be described. The ink composition described above can be contained in an ink cartridge and supplied to an ink jet printer. When the ink composition is used as an ink set, it can be an ink cartridge that accommodates the ink set integrally or independently.

  The ink composition of this example is particularly preferably used in an ink jet recording method, and includes any recording method in which the ink composition is ejected as droplets from a thin nozzle and the droplets are attached to a recording medium. Specific examples of the ink jet recording method in which the ink composition of the present invention can be used include a method called an electrostatic suction method, a method in which pressure is applied to an ink by an electromechanical conversion element such as a piezoelectric element, and the ink is ejected from a nozzle, For example, a method of heating and foaming ink and discharging from a nozzle can be used.

  Hereinafter, the following evaluation was performed on the ink jet recording material produced as described above.

[Inkjet recording]
Using an inkjet printer PM-G860 (trade name, Seiko Epson Corporation), each ink set consisting of yellow ink, magenta ink, and cyan ink is sequentially filled, and each ink jet recording material has a density of each color. A recorded matter was created by solid printing each color pattern in increments of 100% to 10% (10 density patterns). Each color pattern is recorded in a mixed color or a single color by the ink of each ink set. The following tests were performed on the obtained recorded matter.

[Short-term color stability test method]
The OD value of each color recorded on each recorded matter using a densitometer (SPECTROLINO (registered trademark) (manufactured by Gretag Macbeth)) at every elapse of a certain time immediately after printing under conditions of 23 ° C. and 50% RH. The color stability evaluation is evaluated as an average value (AVE) of each density pattern of ΔE (color difference) at each previous measurement with respect to 1 W (after one week) for each density pattern for each color. The results are summarized in Table 5, and details of Nos. 1 to 6 in Table 5 are shown in Fig. 1 to 6. In Fig. 1 to Fig. 6, the Black series is a black pattern, the Yellow series is a yellow pattern, The Magenta series is a magenta pattern, the Cyan series is a cyan pattern, the Red series is a red pattern, and the Green series is a green pattern.
[Criteria]
○: ΔE after 1 week and 15 minutes is 2 or less.
Δ: ΔE after 1 week and 15 minutes is 3 or less.
X: ΔE after 1 week and 15 minutes is more than 3.
(ΔE average value of each color pattern was used)

  The evaluation results are summarized in Table 5 below.

[Color development test method]
After the recorded material was dried all day and night, the OD values of the 100% cyan, 100% magenta, 100% yellow, and 100% black printing portions recorded on each recorded material were measured and integrated. The results are shown in Table 6 and summarized in Table 5.
[Criteria]
○: higher than 8.50
(Triangle | delta): 7.70-8.50.
X: Lower than 7.70.

  The color development test results are summarized in Table 6 below.

  1 to 6 and Table 5, when the recording material of Example 1 was evaluated using each dye ink set, a recording material having excellent color stability and color developability was obtained, and color stability and color developability were excellent. It can be seen that this is an ink jet recording method. On the other hand, when the recording material of Comparative Example 4 was evaluated using each dye ink set, the color stability and color developability were inferior to those of Example 1. The evaluation result using the pigment ink set for the recording material of Example 1 was excellent in color stability but poor in color development. Further, since it is a pigment ink set, it is more disadvantageous than a dye ink set in terms of the image quality of the recorded matter, ejection stability, and ink aging stability. Further, Comparative Example 1 in which the layer having colloidal silica was not provided had considerably poor color stability and poor color development. Further, Comparative Example 2 which does not have an ink receiving layer containing a basic polyaluminum hydroxide compound and an ink receiving layer containing a water-soluble zirconium compound in this order from the side closer to the support is also inferior in color stability. there were. Further, Comparative Example 3 in which an ink receiving layer mainly containing vapor-phase method silica was not provided had considerably poor color development.

[Summary]
According to the ink jet recording material and the ink jet recording method using the ink jet recording material of the present invention, it is possible to achieve excellent short-term color stability and color developability. Excellent short-term color stability is particularly suitable for use in proof (color proofing) printing applications.

Claims (4)

An inkjet recording material for recording an image using a water-soluble ink comprising at least a dye, water, a water-soluble organic solvent, an acetylene glycol surfactant, and a glycol ether compound, the inkjet recording material An ink receiving layer mainly containing vapor phase silica and containing a basic polyaluminum hydroxide compound on at least one surface of the polyolefin resin coated support from the side close to the polyolefin resin coated support; an ink receiving layer containing containing silica mainly water-soluble zirconium compound, 50 to the content of the contained colloidal silica basic polyaluminum hydroxide compound unrealized basic polyaluminum hydroxide compounds against colloidal silica a layer is 200% by mass, the ink jet characterized by having in this order Recorded material. The solid content coating amount of the layer containing the colloidal silica and containing the basic polyaluminum hydroxide compound is 0.05 to 0.35 g / m. ² The inkjet recording material according to claim 1, wherein An ink jet recording method for recording an image on an ink jet recording material by discharging water soluble ink from a recording head of an ink jet recording apparatus, wherein the water soluble ink comprises a dye, water, a water soluble organic solvent, and an acetylene glycol type. An ink comprising at least a surfactant and a glycol ether compound, wherein the inkjet recording material has a gas phase process silica on at least one surface of the polyolefin resin-coated support from the side close to the polyolefin resin-coated support. An ink receiving layer containing mainly a basic polyaluminum hydroxide compound, an ink receiving layer mainly containing gas phase method silica and containing a water-soluble zirconium compound, and a basic polyaluminum hydroxide compound containing colloidal silica Koh content of unrealized basic polyaluminum hydroxide compound is The ink jet recording method, characterized in that the layer is 50 to 200 wt% with respect to Idarushirika, which is the ink jet recording material having in this order. The solid content coating amount of the layer containing the colloidal silica and containing the basic polyaluminum hydroxide compound is 0.05 to 0.35 g / m. ² The inkjet recording method according to claim 1, wherein

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