JP3176139B2 - Ink jet recording medium for aqueous ink and ink jet recording method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink jet recording medium suitably used for ink jet recording and an ink jet recording method using the same.

[0002]

2. Description of the Related Art As a recording medium conventionally used for ink-jet recording, as described in Japanese Patent Publication No. 3-26665, a coating material containing fine powder silica and a water-soluble binder such as polyvinyl alcohol on a base paper. Recording paper provided with a layer, glossy paper in which a film containing a polyvinyl alcohol having a saponification degree of 50 to 90 mol% and a crosslinking agent is formed on cast-coated paper as described in JP-B-3-25352, As described in JP-B-3-13993, an overhead recording sheet or the like in which a hydrophilic film formed of a mixture of a water-soluble polyvinyl alcohol, a water-insoluble polyvinyl alcohol, and a water-dispersible polyester is provided on a polyester film. Has been used.

[0003]

In recent years, with the improvement of the performance of an ink jet recording apparatus such as high-speed recording and multi-color recording, higher and broader characteristics have been required for a recording medium for ink jet recording. I have. That is, (1) high absorption capacity of ink (large absorption capacity and quick absorption time) (2) high optical density of dots and no blur around the dots (3) dot shape is close to a perfect circle, (4) Changes in characteristics are small due to changes in temperature and humidity, and no curling occurs. (5) No blocking occurs. (6) Images are stable for long-term storage and do not deteriorate. It is required to satisfy the characteristics at the same time.

[0004] These properties are often in a trade-off relationship, and it has not been possible to satisfy them at the same time with the known techniques. For example, the recording medium of the prior art exemplified, the dot shape and blocking resistance are all moderate, but because of insufficient ink absorption capacity, a portion with high image density, that is, In a portion where the amount of ink applied is large, image smearing and density unevenness occur due to overflow of ink, and particularly in the case of color printing, color smearing occurs due to mixing of color boundaries at different colors.

[0005] As the recording speed is increased, the image density is increased, and the colorization is advanced, deterioration of image quality due to defective ink fixing has become a serious problem.

The recording sheet having an ink receiving layer mainly composed of polyvinylpyrrolidone described in JP-B-3-29596 has a relatively good ink absorption capacity at normal temperature and normal humidity, but has a high temperature absorption property. The ink dries very slowly under moisture and is likely to cause blocking. Further, it has a disadvantage that the mechanical strength of the recording surface is weak and the recording surface is easily scratched.

It is an object of the present invention to provide a water-based ink jet ink which satisfies the above-mentioned various properties at the same time in a well-balanced manner.
Tsu DOO recording medium and an inkjet recording method using the same is to provide.

[0008]

The above object is achieved by the present invention described below.

That is, the present invention provides

[Outside 5] Aqueous ink for applying a coating liquid containing a cyclic compound represented by formula (I) and a methylated product thereof to the surface of a substrate
It is a jet recording medium.

[0010]

[0011]

Further, the present invention provides

[Outside 6] In represented by cyclic compounds and their methylated derivatives, a water-based ink for ink-jet recording medium which comprises in the base material.

[0013]

[0014]

Further, the present invention is an ink jet recording method characterized in that recording is performed by discharging ink from an orifice of a recording head on a recording medium as described above in accordance with a recording signal.

[0016]

The present inventors have developed a recording paper suitable for ink-jet recording, a transparency film for an overhead projector, and the like. Extremely high ink absorption capacity, clear and sharp dots, excellent blocking resistance, small change in performance with changes in environmental conditions such as temperature and humidity, and stable recording media for long-term storage The present invention has been found.

That is, high practical performance is realized by the effect in the composition.

The above-mentioned composition, more specifically, a cyclic oligosaccharide (hereinafter referred to as CFR) in which 6 to 8 fructose molecules are bound by β2-1 frucside, and a cyclic compound composed of 6 fructose, a typical compound of which is Compound (CFR-
The structure and molecular formula of 6) are shown below.

[0019]

[Outside 13]

CFR and its methylated product are known as white crystalline compounds having functions such as inclusion of substances, trapping and separation of metals, similar to cyclodextrin and crown ether, which are compounds similar to CFR. I have. The feature of the cyclic compound (CFR) comprising 6 to 8 fructose molecules and the methylated form thereof used in the present invention is that the solubility in a solvent is extremely high. For example, the solubility of cyclodextrin in water is generally low (14
%, Β-form is almost insoluble), whereas CFR is 120%
(22 ° C). The methylated form of CFR is well dissolved in alcohols, ketones, esters, and organic solvents such as toluene and xylene.

The present inventors have been conducting research and development on a recording medium for receiving ink in a recording method of discharging ink as droplets to perform recording. The recording medium containing or containing the compound on the surface of the substrate has excellent ink absorption performance and image performance, and does not change under environmental conditions or long-term storage. Found to have. Although it is not clear why such an effect is obtained, cyclodextrin structurally has a bucket-shaped three-dimensional structure, whereas CFR is planar, so that the space inside the molecule is larger than that of cyclodextrin. It is estimated that CFR also has many hydroxyl groups,
It is estimated that there is a trapping effect that clings to other molecules. It is presumed that such properties of CFR may have some useful function in fixing non-volatile components (solvents and dyes) in the ink.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

The compound used in the present invention and which mainly characterizes the present invention is the aforementioned fructose (fructose) molecule 6 to
It is a cyclic compound consisting of eight.

CFR is efficiently produced in a bioreactor by the enzyme cycloinurooligofractanotransferase produced from Bacillus circulans using inulin, which is abundant in vegetable chicory, jerusalem artichoke and dahlia roots, as a raw material. Current methods produce 75% fructose, 20% fructose, and 5% fructose. These can be used as a mixture, or they can be separated and purified if necessary. A methylated form of CFR can be easily obtained by reacting a hydroxyl group in a CFR molecule with a known methylating agent.

In the present invention, the above-mentioned CFR can be used together with other materials, if necessary, as a coating liquid for coating the surface of the substrate, or can be used by being internally added to a substrate such as paper.

When the method of coating the surface of a base material by containing the above CFR in a coating liquid is used, the content of the cyclic compound of the present invention is 0.1 to the total weight of the coating liquid. -30% by weight, more preferably 0.5-10% by weight.

When the above-mentioned cyclic compound is used as a so-called internal additive or as a size press agent for mixing paper with pulp, filler and sizing agent, etc., the amount of the cyclic compound of the present invention is preferably The range of 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight is most preferably used, but is not limited to this range.

In the present invention, various binders and filler additives can be used together as long as the object of the present invention is not hindered. As an example of the binder, conventionally known starch, cationized starch, casein, acrylic resin, maleic anhydride resin, melamine resin, cellulose,
Examples include, but are not limited to, SBR latex, sodium alginate, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, and the like. Examples of fillers include silica, alumina, aluminum silicate, magnesium silicate, basic magnesium carbonate, talc, clay, haodotalcite, calcium carbonate, titanium oxide, zinc oxide, and polyethylene, polystyrene, polyacrylate, and the like. Examples include, but are not limited to, plastic pigments. Specific examples of additives include various surfactants, dye fixing agents (waterproofing agents),
Examples include an antifoaming agent, an antioxidant, an optical brightener, an ultraviolet absorber, a dispersant, a viscosity adjuster, a pH adjuster, a fungicide, and a plasticizer. These additives may be arbitrarily selected from conventionally known compounds according to the purpose.

The base material constituting the recording medium of the present invention includes paper such as high quality paper, medium quality paper, art paper, bond paper, recycled paper, baryta paper, cast coat paper, corrugated paper, polyethylene terephthalate, and the like. Film or plate made of plastic such as diacetate, triacetate, cellophane, celluloid, polycarbonate, polyimide, polyvinyl chloride, polyvinylidene chloride, polyacrylate, glass plate, or cotton,
Fabrics such as rayon, acrylic, nylon, silk, and polyester can be used. The substrate is appropriately selected from the above-mentioned substrates in accordance with various conditions such as the purpose of recording the recording medium, the use of the recorded image, or the adhesion to the composition coated or internally added on the recording medium.

As an example of the method for producing the recording medium of the present invention, a method for coating the surface of a base material by including the above-mentioned cyclic compound in a coating solution will be described below. Is not limited to the following.

For example, first, the above-mentioned cyclic compound is dissolved and dispersed in water, alcohol, or another appropriate organic solvent, if necessary, together with other additives, to prepare a coating solution. For example, coating is performed on the substrate surface by a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a bar coater method, a size press method, a spray coat method, a gravure coater method, a curtain coater method, or the like. Then, for example, a hot air drying oven,
Dry using a heat drum or the like. Further, if necessary, a super calender treatment or the like may be performed to smooth the coating liquid layer or increase the surface strength.

The coating amount of the coating liquid was 0.2 in total.
５０50 g / m ² , more preferably 0.2-20 g / m ²
Is within the range. When the coating amount is small, a part of the substrate may be exposed on the surface. The coating amount is 0.2 g / m
^{When the amount} is less than ² , there is no effect in terms of the coloring property of the dye as compared with the case where the coating is not applied, while on the other hand, when the coating exceeds 50 g / m ² , powder falling off of the coating layer occurs. Occurs undesirably. The coating amount when the coating amount is represented by the thickness is 0.5 to 1
A range having a thickness of 00 μm is preferable.

As the ink itself for performing ink jet recording on the recording medium described above, a known ink can be used without any problem. As the recording agent, a direct dye, an acid dye, a basic dye, a reactive dye, and a water-soluble dye represented by an edible dye can be used. I can do it. Such a water-soluble dye is generally used at a ratio of about 0.1 to 20% by weight in a conventional ink, and the same may be used in the present invention.

The solvent used in the water-based ink used in the present invention is water or a mixed solvent of water and a water-soluble organic solvent. Particularly preferred is a mixed solvent of water and a water-soluble organic solvent, It contains a polyhydric alcohol having an effect of preventing ink from drying as an organic solvent.

The method for performing recording by applying the above-mentioned ink to the recording medium is preferably an ink jet recording method. In this method, the ink is effectively separated from the nozzles, Any system may be used as long as it can apply ink to a certain recording medium.

In particular, according to the method described in Japanese Patent Application Laid-Open No. 54-59936, the ink that has been subjected to the action of thermal energy causes a sudden change in volume, and the ink is ejected from the nozzle by the action force resulting from this state change. The ink jet method used can be used effectively.

An example of an ink jet recording apparatus suitable for performing recording using the recording medium of the present invention will be described below. FIGS. 1 and 2 show examples of a head configuration which is a main part of the apparatus.
And FIG.

The head 13 includes a glass, ceramic or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for thermal recording (a head is shown in the figure, but is not limited to this). And obtained by bonding. The heating head 15 includes a protective film 16 made of silicon oxide or the like, and aluminum electrodes 17-1 and 17-.
2, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina.

The ink 21 has a discharge orifice (fine hole) 2
2, and the meniscus 23 is formed by the pressure P.

When an electric signal is applied to the electrodes 17-1 and 17-2, an area of the heating head 15 indicated by n rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area. The meniscus 23 protrudes due to the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the orifice 22, and flies toward the recording medium 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head includes a glass plate 27 having a multi-groove 26, and FIG.
The heat-generating head 28 similar to that described above is closely attached.

FIG. 1 shows a head 1 along an ink flow path.
3 is a sectional view, and FIG. 2 is a cross-sectional view taken along a line AB in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head.

In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is disposed at a position adjacent to a recording area of the recording head, and in this example, is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the direction in which the print head moves and comes into contact with the ejection port surface to perform capping. Reference numeral 63 denotes an ink absorber provided adjacent to the blade 61, which is held in a form protruding into the movement path of the recording head, similarly to the blade 61. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head which has discharge energy generating means and discharges ink on a recording medium facing the discharge port surface where discharge ports are arranged, and performs recording. 66 denotes a recording head on which the recording head 65 is mounted. Is a carriage for performing the movement. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area.

Reference numeral 51 denotes a paper feed unit for inserting a recording medium,
52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the discharge port surface of the recording head, and is discharged to a discharge section provided with discharge rollers 53 as the recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. I have. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement.

The above-described movement of the print head to the home position is performed not only at the end of printing or at the time of ejection recovery, but also at a home position adjacent to the printing area with a predetermined feeling while the printing head moves through the printing area for printing. Position, and the wiping is performed along with the movement.

[0049]

The present invention will be described in more detail with reference to the following examples. In the following description, parts or% are based on weight unless otherwise specified.

Example 1 and Comparative Example 1 Four parts (hereinafter all parts by weight) of six cyclic compounds of fructose were added and dissolved in 96 parts of water while stirring and mixing.
The obtained coating solution was applied to a high-quality paper (Silver Ring, manufactured by Sanyo Kokusaku Pulp) using a wire bar.
After drying for 0 minute and treating with a super calender, a recording medium of the present invention was obtained. Color recording was performed on the recording medium under the following conditions by using an ink jet recording apparatus in which the ink having the following composition was foamed by thermal energy to discharge the ink.

As a comparative example, high-quality paper (silver ring) to which no coating liquid was applied was used.

Ink composition (Formulation A) Dye 3 parts Diethylene glycol 15 parts Water 82 parts

Dye Y: C.I. I. Direct Yellow # 86 M: C.I. I. Acid Red # 35 C: C.I. I. Direct Blue # 199 Bk: C.I. I. Food Black # 2

Recording conditions Ejection frequency: 3 KHz Volume of ejected droplets: 30 pl Recording density: 400 DPI Maximum amount of single-color ink applied: 7.4 nl / mm ² Maximum number of superimposed colors: 3 colors The following items were obtained for the obtained color print samples. An evaluation was performed.

Evaluation item * 1 Ink absorption After recording three colors of yellow, cyan, and magenta in full dots, and then leaving the ink at room temperature (20 ° C., 65% RH) for 30 seconds, when touching the recorded image, The determination was made based on whether the ink was taken into the ink receiving layer and did not adhere to the finger.し な い indicates no attachment, X indicates attachment, and Δ indicates the middle.

* 2 Blocking resistance After recording three colors of yellow, cyan and magenta in full dots, warm air (100 ° C., wind speed 1 m / sec) was applied to the recording surface for 1 dot.
After exposure for 0 second, clear pocket (Lion, polypropylene film) at 40 g / cm ² pressure on the recorded image
Was determined based on whether or not this film could be easily peeled when laminated.場合 indicates that the film can be easily peeled, X indicates that the film requires considerable force, and 、 indicates the middle.

* 3 Image Density The black (Bk) image density of a solid printed image using the printer described above was measured using a Macbeth densitometer RD-918.
Was evaluated using

* 4 The storage stability of the recording media was determined by storing each recording medium in an environment of 35 ° C. and 90% RH for 7 days.
Stored in an environment of 23 ° C. and 55% RH for 1 day, and then
The evaluation was performed using the printer described above in an environment of 23 ° C. and 55% RH.

As compared with the recording medium before storage, ink overflow,
X indicates bleeding and thickening of the character and the image quality was remarkably inferior, ○ indicates no change, and Δ indicates a medium level. What was done was XX.

* 5 The unevenness of the image can be confirmed by observing the solid printed matter using the above-mentioned printer in which the unevenness of the density is not recognized, and visually observing the printed matter and the eye from a distance of 50 cm. The thing was x, and the medium thing was △.

* 6 Resolution A recorded image is projected on a screen by an OHP, and a clear and easy-to-view image with high contrast is obtained. ○, bleeding, etc., causing the boundary between two different colors to bleed or pitch width When a line of 1 mm and a thickness of 0.3 mm could not be clearly discriminated, it was evaluated as x, and the middle was evaluated as Δ.

[0062]

[Outside 14]

Example 2 and Comparative Example 2 As raw pulp, 80 parts of LBKP and 20 parts of NBKP were mixed and dissociated, beaten to a freeness of 350 ml, 7 parts of heavy calcium carbonate (Whiten SSB: Ishihara Sangyo), alkyl ketene dimer 0.2 parts of a sizing agent (Harcon 40: manufactured by Dick) and 0.3 parts of a paper strength enhancer (Polystron # 602: manufactured by Arakawa Chemical) were added, and 75% of a cyclic compound of 6 fructose and 7 parts of An aqueous solution prepared by dissolving 0.5 part of a mixture consisting of 20% of the cyclic compound and 5% of the eight cyclic compounds in 10 ml of water was added and mixed well, and the mixture was mixed well using a small fourdrinier paper machine to obtain a basis material of 75 g / m ² . Created paper. As a comparative example, paper was prepared in the same manner except that a mixture of 6 to 8 fructose cyclic compounds was removed from the above composition. Each was dried with a dryer at 60 ° C. to obtain a recording medium. In the recording medium,
Recording was performed using the same recording device as in Example 1, and the same evaluation was performed.

[0064]

[Outside 15]

Example 3 and Comparative Example 3 Freeness (CFS) 500 m as raw pulp
Using 1 part of LBKP, 10 parts of talc, rosin (Colopearl S-78L: manufactured by Seiko Chemical), 2 parts of sulfate band, and 0.5 part of cation resin (PAS-A120: manufactured by Nitto Bo)
A solution prepared by dissolving 1 part of a cyclic compound consisting of 6 fructose in 10 parts of water was added, and the basis weight was 85 g / m ² as in Example ^2.
Created a piece of paper. As a comparative example, paper was prepared in the same manner except that the cyclic compound consisting of six fructose was removed from the above composition,
A recorded matter was prepared and evaluated in the same manner as in Example 2.

[0066]

[Outside 16]

Example 4 and Comparative Example 4 1 part of a methylated form of a cyclic compound of 6 fructose, 5 parts of modified polyvinyl acetate (SMR-10H, manufactured by Shin-Etsu Chemical),
1 part of fine silica powder (Fine Seal X37 manufactured by Tokuyama Soda)
0.1 part of a surfactant (Ceramo P-16, manufactured by Daiichi Kogyo Seiyaku), 24 parts of water, and 70 parts of isopropyl alcohol were well dispersed using a ball mill to prepare a coating solution. This coating liquid was applied to a 100-μm-thick polyester film (manufactured by Toray Industries Inc.) so that the thickness became 10 μm. 60
After drying at 30 ° C. for 30 minutes, a recording medium was obtained. The recording was performed on the recording medium by using the same recording apparatus as in the first embodiment. The following items were evaluated with respect to the obtained recorded matter. As a comparative example, a similar recording medium was prepared using a coating liquid from which six cyclic compounds of fructose were removed.

Ink Composition (Formulation B) Dye 3 parts Diethylene glycol monomethyl ether 25 parts Urea 3 parts N-methylpyrrolidone 10 parts Water 59 parts

Dye Same as in Example 1.

Evaluation Items In addition to the evaluation items performed in Example 1, curl resistance and fingerprint resistance tests were performed.

* 7 Curl Resistance The printed film was placed on an overhead projector (Model 4000) manufactured by Sumitomo 3M, and the rise of the corner after 3 minutes was measured with a JIS first class metal scale. △, 10mm
The above was evaluated as x.

* 8 Fingerprint resistance When the right thumb was pressed firmly against the printed film and projected by OHP, a mark where the fingerprint was hardly visible was rated as ○, a mark that was seen faintly as Δ, and a sign that clearly appeared as X.

[0073]

[Outside 17]

Examples 5 to 14 and Comparative Examples 5 to 7 Various recording media were prepared in the same manner as in Examples 1 and 2, and color recording was performed. As a comparative example, the same recording was performed on a commercially available recording paper, a transparency film for inkjet, and the like. The contents of the recording medium and the evaluation results are shown below. In preparing the coating solution, a ball mill was used as necessary.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

As described above, according to the present invention, the ink absorption is high, the dots are clear, the blocking resistance is excellent, and the temperature and humidity are not changed. It is possible to supply a recording medium having ideal practical performance for inkjet recording, which is stable and excellent in storability, hardly curls, and hardly produces fingerprints.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head portion of an ink jet recording apparatus used in the method of the present invention.

FIG. 2 is a cross-sectional view of a head section of an ink jet recording apparatus used in the method of the present invention.

FIG. 3 is an external perspective view of a head obtained by multiplying the head shown in FIGS. 1 and 2.

FIG. 4 is a perspective view illustrating an example of an inkjet recording apparatus.

[Explanation of symbols]

 Reference Signs List 61 wiping member 62 cap 63 ink absorber 64 discharge recovery section 65 recording head 66 carriage

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tokuya Ota 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-63-230702 (JP, A) JP-A-60 -189482 (JP, A) JP-A-4-237496 (JP, A) JP-A-6-208188 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/00 D06P 5/00 111 D21H 17/24 CAPLUS (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] (1) Aqueous ink for applying a coating liquid containing a cyclic compound represented by formula (I) and a methylated product thereof to the surface of a substrate
Jet recording medium. (2) An ink-jet recording medium for water-based ink comprising a cyclic compound represented by the formula (1) and a methylated product thereof in a base material. 3. The water-based ink-jet recording medium according to claim 1, wherein the substrate is paper. 4. The ink jet recording medium according to claim 1, wherein the base material is a plastic film. 5. The method according to claim 1, wherein the base material is a cloth.
3. The ink jet recording medium for water-based ink according to 1.) . 6. The method according to claim 1, wherein the base material is paper. 3. The ink jet recording medium for water-based ink according to claim 2, wherein the cyclic compound represented by the formula (1) and a methylated product thereof are contained in an amount of 5 to 50% by weight based on the total weight of pulp as a main raw material of paper. 7. The coating solution according to claim 1, wherein The inkjet recording medium for water-based ink according to claim 1, wherein the cyclic compound represented by the formula (1) and a methylated product thereof are contained in an amount of 0.1 to 30% by weight based on the total weight of the coating solution. 8. The aqueous inn according to claim 1,
An ink jet recording method, comprising: performing recording by discharging ink from an orifice of a recording head in accordance with a recording signal on an ink jet recording medium for printing . 9. An ink jet recording method according to claim 8, wherein the liquid medium component of the ink according to claim 8 is mainly composed of water and a water-miscible glycol or glycol ether. 10. A color inkjet recording method, wherein the ink according to claim 8 is cyan, magenta, yellow, and black inks. 11. The ink jet recording method according to claim 8, wherein the ink is ejected by thermal energy.