JP2004263176A - Ink set for inkjet recording, method for inkjet recording using the same, and recorded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for inkjet which uses inorganic pigments as coloring materials, is excellent in clarity, has no possibility of discoloration and color disappearance during calcination, and capable of obtaining an image expressing intermediate colors and having a wider color range, a method for inkjet recording using the same, and a recorded article. <P>SOLUTION: The ink set is furnished with two colors of inorganic pigments as red components, and with specified inorganic pigments selected as other colors. The ink set is excellent in clarity of the image, has the wider color range, is extremely excellent in gradation characteristics, has no possibility of discoloration and color disappearance after calcination, and capable of expressing intermediate colors. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to an inkjet ink set including an ink using an inorganic pigment as a coloring material, an inkjet recording method using the same, and a recorded matter. More specifically, an ink-jet ink set of an inorganic pigment, which is excellent in light resistance, sharpness, gradation, is capable of expressing a wide color gamut, and can be colored irrespective of a substrate, was used. The present invention relates to an inkjet recording method and a recorded matter.

  Conventionally, when coloring inorganic materials such as ceramics and metals, heat resistance, stability and light resistance have been emphasized. From these viewpoints, inorganic pigments have been mainly used as coloring materials, and are fixed by firing. Has been adopted.

  In recent years, in such fields, due to the sophistication of design trends, various studies have been made on color variations of inorganic pigments, and many intermediate colors with a wide color gamut (three primary colors (red, blue, yellow) and colors other than black) ) Has been proposed.

  These are proposed in principle not as a mixture of colors but as a color of the inorganic pigment itself. This is because the combination of inorganic pigments may cause decoloration or discoloration depending on conditions such as the firing temperature.

  It is considered that the cause of the decoloration and discoloration is that when a plurality of inorganic pigments are fired at once, the inorganic pigments cause an interaction and a change in crystal structure occurs.

  Therefore, when color materials having different firing temperatures are used, it is necessary to perform the firing process a plurality of times, which results in poor color reproducibility.

  As a method for solving the above-mentioned problem, in [Patent Document 1], in order to enhance color reproducibility, a specific inorganic pigment is colored in the order of cyan, yellow, magenta, and black so as to be fired at one time. It has been found that coloring that is excellent in color reproducibility can be performed.

  However, although this method is excellent in color reproducibility, if the coloring order is different, an expected intermediate color cannot be obtained, and there is a possibility that decoloring or discoloration may occur.

  Further, since there is no change in the method by handwriting, it is poor in industrial applicability, and special coloring such as gradation cannot be naturally performed.

  On the other hand, ink jet recording has attracted attention in the printing industry. This is because various expressions can be made with a small lot and a short delivery time, and industrial production is also possible.

  Therefore, there is a demand for a technique for applying an inorganic pigment by ink jet by applying these.

  However, when an inorganic pigment is used in an ink jet, various problems have arisen due to its specificity, and it has not yet been put to practical use.

  One of the main causes is that the intermediate colors in ink jet recording are expressed by mixing the ink on the base material, so it is necessary to bake in a state where the inorganic pigment is mixed, and as a result, decolorization and discoloration This is because a problem may occur.

  Also, in the expression of the red component, conventionally, even when used as a single product due to the characteristics of the inorganic pigment, the color expression is poor or not clear, especially when an image is formed, the red component is weak. Feeling, it is not possible to get a sense of luxury.

  On the other hand, as a prior art using an inorganic pigment for inkjet, [Patent Document 2] and [Patent Document 3] are mentioned. The former maintains the ejection stability of the inkjet method by adjusting the average particle diameter of the inorganic pigment and preventing sedimentation, and the latter uses a specific inorganic pigment with a dispersant, a solvent, a glass frit and an erasing agent. By adding a foaming agent, ejection stability, adhesiveness, etc. are improved.

  However, all of them are aimed at improving ejection stability, and there is no description about color expression peculiar to inkjet using an inorganic pigment. That is, it is difficult to express an intermediate color, and the advantages of an ink jet capable of expressing a design such as gradation and a wide color gamut cannot be effectively exhibited.

  As described above, a prior art for solving such a problem has not been established yet, and effective use of inorganic pigments for inkjet is required.

JP-A-60-234899 JP 2001-55530 A JP 2001-81363 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and in particular, an ink-jet ink set using an inorganic pigment as a coloring material, which has excellent clarity, does not discolor even during firing, and does not lose color. Another object of the present invention is to provide an ink-jet ink set capable of expressing an intermediate color and obtaining an image having a wider color gamut, an ink-jet recording method using the ink set, and a recorded matter.

  The present inventors have made intensive efforts to achieve the above object, and as a result, provided two colors of the inorganic pigment of the red component, and selected a specific inorganic pigment for the other colors and used it as an ink set, so that a clear image was obtained. It has been found that it has excellent characteristics, a wide color gamut, and very excellent gradation, and it is possible to express intermediate colors without discoloration or decoloration even after firing. The invention has been completed.

  That is, the present invention relates to an ink-jet ink set comprising an ink containing an inorganic pigment as a coloring material, wherein a red component of the ink set is at least two colors of a magenta ink composed of gold purple and a red ink composed of cadmium red. And an ink set for inkjet.

  Further, an inkjet ink set comprising an ink using an inorganic pigment as a coloring material, wherein the red component of the ink set is a magenta ink composed of gold purple and a red ink composed of cadmium red, and a yellow ink and a cyan ink. And at least four color inks.

  Preferably, the present invention resides in an ink set for ink jet, wherein the yellow ink is an ink composed of cadmium yellow and the cyan ink is an ink composed of cobalt aluminum chrome blue.

  Further, an ink-jet ink set comprising an ink using an inorganic pigment as a coloring material, wherein a red component of the ink set is a magenta ink composed of gold purple and a red ink composed of cadmium red, and a yellow ink composed of cadmium yellow , An ink set for ink jet, comprising at least five colors of ink including cyan ink composed of cobalt aluminum chrome blue and black ink.

  Preferably, the black ink is an ink composed of cobalt ferrite black.

  Also, preferably, there is provided an ink-jet recording method characterized by recording using an ink set and forming an image on a base material using the ink set, followed by baking.

  Also, preferably, the present invention resides in an ink jet recording method characterized in that the base material is made of an inorganic material and an ink receiving layer made of glass frit is formed on the surface of the base material before recording by the ink jet method.

  Further, preferably, there is provided an ink jet recording method characterized in that all inorganic pigments are simultaneously printed on the substrate by one firing after recording and forming an image on the substrate by an ink jet method.

  The present invention resides in a recorded matter obtained by the above method.

  As described above, the ink set for inkjet recording according to the present invention is excellent in clarity, capable of expressing a wide color gamut, and can be colored without choosing a base material, without discoloration or decoloration. . Furthermore, since high quality peculiar to inkjet, such as density and image quality, can be sufficiently expressed, it is possible to provide an inkjet printed matter using an inorganic pigment corresponding to recent improvement in design power.

Hereinafter, the present invention will be described in more detail.
The coloring material used in the present invention is an inorganic pigment, and specifically comprises a metal, a metal oxide or a metal salt. Although they are stable against heat and light, they have poor color expression due to their structure, and are easily decomposed by oxidation and reduction.

  Therefore, in the inkjet recording of inorganic pigments, generally, the color gamut is narrow, and particularly the red component is weak. Therefore, in the present invention, the color gamut of red is expanded by equipping the magenta ink and the red ink, and the expression of a so-called intermediate color is thereby performed. It is supported by making it possible.

  That is, the ink set needs to include at least two colors of magenta ink composed of gold purple and red ink composed of cadmium red.

  The cadmium red according to the present invention also includes zirconium cadmium inclusion red coated with zirconium silicate or the like.

Here, the red ink in the present invention means that the hue when the ink is baked is 0 ° on the a ^* axis (+) in the a ^* b ^* space coordinates of the CIEL ^* a ^* b ^* color matching space, and is counterclockwise. An ink around 10 ° to 50 °. Similarly, magenta ink refers to ink in the range from 0 ° to 10 ° and in the range from 330 ° to 360 °. However, as the saturation approaches the origin, the saturation decreases, and since the color approaches black, the object whose saturation from the origin is 10 or more is considered as the target.

  The reason for providing magenta ink and red ink is to expand the color gamut of red, which has a weak color expression, and to obtain an appropriate intermediate color when mixed with other colors (for example, yellow and cyan). is there.

  For example, to express orange, yellow ink and red ink can be expressed, and to express purple, magenta ink and cyan ink can be ejected and mixed on the base material to express a clear intermediate color. it can.

  Note that a clear orange cannot be obtained by mixing the yellow ink and the magenta ink, and a clear purple cannot be obtained by mixing the red ink and the cyan ink.

  The reason why gold purple is used as magenta and cadmium red is used as red is that it has excellent color clarity and density after firing and is suitable for an ink jet system. Furthermore, even if these two colors or any one of them and another inorganic pigment are baked in a state where ink dots are overlapped, it is a relatively stable property that does not easily cause an interaction.

  Further, it is preferable that the ink set includes a yellow ink and a cyan ink in addition to the magenta ink and the red ink.

  This is for expressing a color gamut suitable for an ink jet system for forming an image in full color. By including these four colors, any intermediate color can be expressed.

  Specifically, inorganic pigments that can be employed as yellow include lead antimony yellow, 10G lead, 5G yellow, 5G lead, yellow lead, cadmium yellow, yellow iron oxide, reinforced yellow iron oxide, ocher, titanium yellow, and titanium yellow. Barium nickel yellow, vanadium tin yellow, vanadium zirconium yellow, praseodymium yellow, chromium titanium yellow, antimony titanium chrome yellow, antimony titanium yellow, and the like are preferred, with cadmium yellow being preferred.

  Cadmium yellow in the present invention includes a complex salt of cadmium sulfide and zinc sulfide, a complex salt of cadmium sulfide and barium sulfate, a complex salt of cadmium sulfide and zinc sulfide and barium sulfate, and cadmium sulfide is zirconium silicate. And zirconium cadmium silicate inclusion yellow coated.

  Inorganic pigments that can be used as cyan include navy blue, cobalt blue, ultramarine, cerulean blue, and cobalt aluminum chrome blue, with cobalt aluminum chrome blue being preferred.

  Even when these inorganic pigments of the preferred form are mixed with the magenta gold purple or red cadmium red of the present invention and fired, they exhibit an intermediate color at the firing temperature without a problem of decoloration or discoloration. The reason is that the expression can be made wider and the color gamut can be wider than that of the related art.

  Further, it is more preferable that the ink set includes a black ink in addition to the magenta ink, the red ink, the yellow ink, and the cyan ink.

  Generally, black is obtained by mixing yellow, magenta, and cyan.However, since the hue changes due to a small difference in distribution, including black ink as a single color solves such a problem and obtains a stable colored material. This is because

  Inorganic pigments that can be employed as black include, specifically, lamp black, furnace black, charcoal black, ivory black, graphite, iron black, manganese ferrite black, cobalt ferrite black, copper chrome black, copper chrome manganese black, and the like. However, cobalt ferrite black is preferred. This is because there is no decoloration or discoloration even when baked with a mixture of other colors.

  In addition, it is also possible to include an ink composed of white, green, metallic, pearl, and the like in the ink set. This is because the more the number of colors, the more delicate the color difference can be adjusted, and a more delicate expression can be obtained. However, the ink preparation, the number of ink jet heads, the ink jet recording time, and the like are affected.

  Specific examples of inorganic pigments that can be used as white include lead white, zinc white, lithopone, titanium dioxide (anatase type), titanium dioxide (rutile type), zinc sulfide, antimony oxide, precipitated calcium carbonate, and heavy calcium carbonate. , Kaolin, mica, precipitated barium sulfate, barite powder, gloss white, alumina white, talc, silica, calcium silicate, cerium oxide and the like. Specific examples of the inorganic pigment that can be used as green include chrome green, chromium oxide, viridian, cobalt green, cobalt chrome green, and titanium cobalt green. Specific examples of inorganic pigments that can be employed as metallic include aluminum powder, copper powder, lead powder, tin powder, and zinc powder. Specific examples of the inorganic pigment that can be used as the pearl include titanium mica.

  In addition, glass frit can be added to the inorganic pigment ink for the purpose of imparting adhesiveness. The glass frit is mainly composed of silicon dioxide, and is used by adding an auxiliary agent according to the purpose of use. As auxiliary agents, lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, boric acid, zirconium oxide, titanium oxide Further, a mixture of natural products such as feldspar, quartzite, borax and kaolin can be added. These materials can be used alone or in a mixture.

  It should be noted that it is naturally possible to add and use glass frit from the stage of synthesizing the inorganic pigment instead of using a mixture of the inorganic pigment and the glass frit (hereinafter, referred to as an upper paint).

  The inorganic pigment in the ink composition used in the present invention, or the medium in which the inorganic pigment and the glass frit or the upper paint are dispersed include water, an organic solvent, a wax, or a mixture thereof, and is not particularly limited.

  Furthermore, when dispersing an inorganic pigment, or an inorganic pigment and a glass frit, or an overpaint in the ink, it is possible to arbitrarily use various surfactants alone or in a mixed form as a dispersant. .

  Specifically, as anionic surfactants, fatty acid soap, sodium alkylsuccinate, sodium alkylbenzenesulfonate, sodium sodium alkylnaphthalenesulfonate, sodium sodium alkylsulfate, sodium sodium polyoxyethylene alkyl ether sulfate, sodium dialkylate Cationic surfactant such as sodium sulfosuccinate, sodium alkyl phosphate, styrene maleic anhydride copolymer, olefin maleic anhydride copolymer, polyacrylamide partial hydrolyzate, acrylamide acrylate copolymer, sodium alginate Surfactants such as alkyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene. Polyoxyethylene alkyl allyl ethers, sorbitan fatty acid esters such as alkyl betaine amphoteric surfactant, an amide betaine. As the anionic surfactant, not only a sodium salt but also any metal salt or ammonium salt can be used.

  Also, if necessary, additives such as a surface tension adjuster, a viscosity adjuster, a specific resistance adjuster, a heat stabilizer, an antioxidant, an anti-reducing agent, a preservative, a pH adjuster, an antifoaming agent, a wetting agent, etc. Of course, it is possible to add.

  The inorganic pigment ink can be obtained by mixing the above materials, further dispersing the mixture using a dispersing machine such as a roll mill, a ball mill, a colloid mill, a jet mill, a bead mill, a sand mill, and then performing filtration.

  Further, if necessary, bleeding after ink ejection and landing can be suppressed by providing a material having a liquid absorbing property on the base material as the ink receiving layer.

  Preferably, by providing an ink receiving layer made of glass frit on the substrate, an image without bleeding is formed even after recording and after firing, and further, by using an unfired glass frit as the receiving layer, inorganic pigment and By melting and mixing the glass frit in the ink and the glass frit in the receiving layer, it becomes possible to form a glass film having excellent adhesion.

  Therefore, the glass frit used for the ink receiving layer is preferably the same as the glass frit that can be added to the above-described ink, or a glass frit having a different softening point or expansion coefficient even if different. If the difference is remarkably different, poor adhesion may occur.

The dry application amount of the glass frit is preferably 50 to 500 g / m ² . If it is less than 50 g / m ² , bleeding of the ink cannot be sufficiently suppressed, and if it exceeds 500 g / m ² , the glass frit layer after firing becomes too thick, and cracks and the like may occur. is there.

  The glass frit used as the ink receiving layer is preferably a glass frit containing about 2 to 10% of cadmium in its components.

  This is because the use of a cadmium-containing glass frit in the above ink combination significantly improves the color development of the inorganic pigment after firing.

  It should be noted that an adhesive can be added to the ink receiving layer made of the glass frit of the present invention as needed. This is because there is an effect of improving workability when applying the ink receiving layer. Specifically, natural polymers such as starch, natural gum, vegetable protein, seaweed, casein, and gelatin, and semi-synthetic polymers such as ether-type cellulose, ester-type cellulose, ether-type starch, ester-type starch, and processed natural gum , Polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyvinyl butyrate resin, polyvinyl acrylate resin, polyvinyl methyl resin, cross-linked polyacrylic acid, sodium polyacrylate, polyacrylate, polyacrylamide, sodium methacrylate, polybutadiene, polyurethane And synthetic polymers such as polyester, polylactic acid and the like.

  It is also possible to add additives such as a dispersant, an antioxidant, a reduction inhibitor, and a pH adjuster, if necessary.

  Examples of the substrate used in the present invention include, but are not particularly limited to, ceramic materials such as glass, porcelain, enamel, and tiles, and inorganic materials such as metals.

  Further, it is preferable to calcine all the inorganic pigments at one time. This is because if performed a plurality of times, there is a problem in terms of cost as well as color variation.

  In general, the firing temperature is 700 to 850 ° C. in the case of ceramics, in the case of inglaze, 1 to 1300 ° C. for 30 to 60 minutes, and in the case of glass, 500 to 650 ° C. for 30 to 60 minutes, and In the case of an enamel, it takes 1 to 2 minutes in a baking furnace preheated to 750 to 850 ° C., but in practice, the baking time and baking temperature are determined in consideration of the deformation of the base material to be used due to heat and the type of furnace. Is set.

  In the case of firing at a high temperature such as 1100 to 1300 ° C, it is desirable to use an inorganic pigment having excellent heat resistance. Specifically, gold magenta ink, zirconium cadmium silicate inclusion red as red ink, zirconium cadmium silicate inclusion yellow and praseodymium yellow as yellow ink, cobalt aluminum chrome blue as cyan ink, cobalt ferrite as black ink Black.

  On the other hand, for the glass frit used in such a case, a substance having an appropriate coefficient of thermal expansion and softening point is selected. If the thermal expansion coefficient and the softening point of the substrate and the glass frit are significantly different from each other, it is necessary to pay attention to the fact that the adhesion between the substrate and the glass frit may not be sufficiently performed, resulting in poor adhesion and cracking.

  For example, when the substrate is a glass having a softening point around 600 ° C., a softening point of a glass frit to be used is selected to be around 600 ° C. or lower than the softening point of the substrate, and a softening point around 800 ° C. In the case of tiles and ceramics, the softening point of the glass frit is selected to be around 800 ° C. or lower.

  Ink jet recording methods include a charge modulation method, a micro dot method, a charge injection control method, a continuous method such as an ink mist method, a stemme method, a pulse jet method, a bubble jet (registered trademark) method, and an electrostatic suction method. Any of the demand method and the like can be adopted.

  Next, the present invention will be described with reference to examples, but the present invention is not necessarily limited to these examples.

  An ink was blended for each inorganic pigment with the following formulation, and dispersed using a ball mill disperser. Thereafter, impurities were removed by filtration to produce a uniform inorganic pigment ink.

[Ink formulation]
Inorganic pigment x wt%
Frit: 12-3567 (lead transparent: manufactured by Nippon Fellow) 10% by weight
Dispersant: Cariblon B (polycarboxylic acid type activator: manufactured by Sanyo Chemical Co., Ltd.) 1% by weight
Wetting agent: polyethylene glycol 400 (manufactured by NOF Corporation) 10% by weight
Pure water remaining
100% by weight in total

《Inorganic pigment》
Y (yellow): Cadmium yellow 10% by weight
M (magenta): 2% by weight gold purple
C (cyan): 10% by weight of cobalt aluminum chrome blue
R (red): Cadmium red 10% by weight
K (black): 10% by weight of cobalt ferrite black

Next, an ink receiving layer was formed by the following method.
(Formulation of ink receiving layer)
Glass frit 32117
(Cadmium-containing glass flash, manufactured by Izawa Pigments) 65% by weight
Polyvinyl alcohol (adhesive: PVA-110, manufactured by Kuraray) 5% by weight
Pure water remaining
100% by weight in total

  Glass frit 32117 was dry-dispersed using a ball mill. Next, polyvinyl alcohol and pure water were added, and the mixture was kneaded in a mortar, coated on a tile (porcelain: glazed) using a screen, and then dried at 110 ° C. for 10 minutes to form an ink receiving layer on the substrate.

  The above ink was used for the tile on which the ink receiving layer was applied, and recording was performed using an ink jet printer under the following recording conditions. After the recording, baking was performed at 800 ° C. for 45 minutes using an electric furnace for pottery.

[Recording conditions]
B) Nozzle diameter: 70 (μm)
B) Applied voltage: 50 (V)
C) Pulse width: 20 (μs)
D) Driving frequency: 1 (kHz)
E) Resolution: 180 (dpi)
F) Evaluation pattern: 3cm x 3cm matrix

[Evaluation content]
The obtained recorded matter was evaluated as follows.
(1) Clarity The color of the recorded matter was visually judged.
：: Vivid expression without impairing the color of the pigment.
Δ: The color of the pigment is slightly dull and lacks in sharpness.
X: The color is extremely dull and not clear.
Evaluation ink (single color)
Recording ink: M, R (2 colors in total)
Ink application amount: 10 nl / mm ²
Table 1 shows the evaluation results.

(2) Discoloration The color of the recorded matter was visually judged.
：: No discoloration or decoloration was observed in the color of the evaluation pattern, and it was a faithful intermediate color.
Δ: The color of the evaluation pattern is slightly discolored or decolored.
×: The color of the evaluation pattern is clearly discolored or erased.
Evaluation ink (mixed color)
Recording ink: Y + R, Y + M, M + R, R + C, M + C (5 sets in total)
Ink application amount: 10 nl / mm ²
Table 2 shows the evaluation results.

(3) Expression of Intermediate Color The color of the recorded matter was visually judged to confirm whether an intermediate color such as orange, purple, or green was expressed.
：: An intermediate color is expressed with high density and high saturation.
Δ: An intermediate color is expressed, but the saturation is slightly low and the color is somewhat dull.
×: Inferior in color expression due to low saturation of intermediate colors and strong dullness of colors.
Evaluation ink (neutral color)
Orange recording ink: (for example, Y + R, Y + M)
Purple recording ink: (for example, R + C, M + C)
Green recording ink: (for example, Y + C, G)
Ink application amount: 5, 10, 20, 40 nl / mm ² (4 × 4 mode in total)
Table 2 shows the evaluation results.

(4) Pattern expression Pattern creation (JIS-X9201 N3 image)
Recording ink: Table 2 shows the evaluation results of all the inks described in the examples.

A recorded matter was prepared and evaluated in the same manner as in Example 1 except that Y of the ink used was changed to praseodymium yellow.
Y (yellow): Praseodymium yellow 10% by weight

Recorded matters were prepared and evaluated in the same manner as in Example 1 except that the inks used were six colors of Y, M, R, C, G (green), and K, and the following inorganic pigments were used for green.
G (green): titanium cobalt green 10% by weight

Comparative Example 1
A recorded matter was prepared and evaluated in the same manner as in Example 1 except that the red component of the inorganic pigment used was changed to only magenta ink.

Comparative Example 2
Chrome tin pink was used as magenta ink, and red iron ink was used as red ink. Other steps were the same as in Example 1.

  As is clear from Tables 1 and 2, the ink-jet recordings of Examples 1 to 3 prepared using the ink set for ink-jet recording of the present invention can express vivid colors, and exhibit discoloration even in the expression of intermediate colors. A recorded matter having a wide color gamut can be obtained without decoloring or the like. Furthermore, even when an image is formed, a high quality printed matter can be obtained. In particular, by specifying Y, M, R, and C as in Examples 1 and 3, it is possible to create an ink jet recorded matter having excellent saturation of intermediate colors.

Claims (9)

  An ink-jet ink set comprising an ink using an inorganic pigment as a coloring material, wherein the red component of the ink set includes at least two colors of ink, a magenta ink composed of gold purple and a red ink composed of cadmium red. Ink set for inkjet.   An inkjet ink set comprising an ink having an inorganic pigment as a coloring material, wherein a red component of the ink set is a magenta ink composed of gold purple and a red ink composed of cadmium red, and at least including a yellow ink and a cyan ink. An ink set for inkjet, comprising four colors of ink.   The ink set according to claim 2, wherein the yellow ink is cadmium yellow, and the cyan ink is an ink composed of cobalt aluminum chrome blue.   An ink-jet ink set comprising an ink containing an inorganic pigment as a coloring material, wherein the red component of the ink set is a magenta ink composed of gold purple and a red ink composed of cadmium red, and a yellow ink composed of cadmium yellow, cobalt An ink set for inkjet, comprising a cyan ink composed of aluminum chrome blue and at least five colors of ink including a black ink.   The ink set according to claim 4, wherein the black ink is an ink composed of cobalt ferrite black.   An ink jet recording method, comprising: using the ink set according to any one of claims 1 to 5, recording on a substrate by an ink jet method, forming an image on the substrate, and then firing.   7. The ink jet recording method according to claim 6, wherein the base material is made of an inorganic material, and an ink receiving layer made of glass frit is formed on the surface of the base material before recording by the ink jet recording method.   8. The ink jet recording method according to claim 6, wherein all the inorganic pigments are simultaneously baked on the substrate by one firing after recording and forming an image on the substrate by an ink jet method.   A recorded matter obtained by the method according to any one of claims 6 to 8.