JP2010089992A - Ink set for inkjet printing on glazed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set which is composed of water-soluble transition metal salt ink of four colors (CMYK) and a glass glaze component, enables inkjet printing on porcelain enamel wares or tiles having glass glaze layers formed on their surfaces and develops colors of high brightness and high saturation through chemical reaction between the ink and the glass glaze component when fired at a temperature equal to or higher than 500°C. <P>SOLUTION: The glass glaze component for porcelain enamel wares or tiles contains 0.1-10% of oxide of at least one chosen from titanium, antimony and niobium so that, when fired, it undergoes chemical reaction with the ink of four primary colors, i.e. cyan (C), magenta (M), yellow (Y) and black (K), each comprising an amine-neutralized aqueous solution of a transition metal salt, thereby increasing brightness and saturation of colors developed by the ink. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to the chemistry of the transition metal in the ink and the specific element component in the glaze when ink jet printed on the surface of a product having a glass glaze layer such as glaze or tile and baked at a high temperature of 500 ° C. or higher. The present invention relates to an ink set for ink jet printing that develops color by reaction.

  Currently, screen printing, roll printing, and transfer paper are used to decorate the surface of tiles and tiles. In the case of screen printing or roll printing, first, a screen or rubber plate having a pattern to be obtained, and a colored paste obtained by pulverizing glass and a colored inorganic pigment with water are prepared. After the colored paste is printed and transferred onto the surface of the glazed tile, it is baked at a high temperature of 700 ° C. to 1200 ° C. and the decoration is completed on the molten glaze layer. However, these methods are not suitable for forming a delicate pattern with high so-called resolution. This is because there is a limit to fine pulverization of glass and inorganic pigments, opening of screens and fine processing of rolls, even if precise lines and dots are to be formed.

In addition, when performing complex multicolor printing, it is necessary to have a pigment paste that is toned by the number of colors desired, and the desired intermediate colors can be instantly obtained by using basic primaries as in ink jet printing with an ink set. It cannot be created.

  It is known that an aqueous transition metal salt or complex develops color on a glass glaze. For example, Patent Document 1 describes a method for producing a fired circuit on a ceramic with an organometallic chelate compound ink. There are no reports on the ink components of the CMYK four primary colors that have only lightness and saturation with high print quality, and are related to single color and several color inks only.

  The glass glaze layer absorbs water easily and the water-based ink is easily fixed on the surface, but the ink penetrates into the glass glaze layer melted during firing, and is caused by chemical reaction with specific element components in the glaze. There is no recognition of the principle that the targeted hue appears, and that the brightness and saturation are determined by the type and amount of the specific element component in the glass glaze that affects the color development. Similarly, Patent Documents 2 and 3 show no knowledge about the concept of an ink set for printing on a ceramic substrate or color development due to a chemical reaction with a glass glaze. It is impossible to obtain satisfactory brightness and saturation with the inks described in these patents. Specifically, even if these inks are printed on a glass glaze and baked, only a very thin color can be obtained.

Ink-jet inks with industrial value are those that have high print quality CMYK4 primaries, and can produce high-quality intermediate colors that are expressed by their color mixture.
JP-A 63-283981 JP 2004-256319 A Japanese Patent No. 3789860

  In view of the above circumstances, the present invention supplies a high printing quality wrinkle and tile ink set by utilizing a chemical reaction between a specific component element of a glass glaze layer and a CMYK four-color aqueous metal salt ink.

  In the water-based ink set of the present invention, each ink is composed of water, a water-soluble organic solvent, a dye, a water-soluble transition metal salt or a water-soluble transition metal complex that decomposes upon firing at 500 ° C. or higher, neutralization stabilization, and pH adjustment. Of water-soluble amines. When this ink set is printed and fired on a glaze or tile glaze surface, satisfactory color development is obtained for CMK, but Y is very weak and only pale yellow is obtained, which is insufficient as an ink set. If the yellow color does not develop, especially the green color cannot be obtained.

  However, it has been found that a very strong yellow color can be obtained by including at least one oxide of titanium, antimony or niobium in the glass glaze. The amount is 0.1-10% of at least one oxide in the glaze component. If the content of the oxide is less than 0.1%, only insufficient yellow coloring can be obtained, and if it exceeds 10%, yellow, ocher or brown coloring with strong redness is obtained. At that time, the other CMK colors are also strongly influenced, the color becomes darker, and the basic four primary colors having high brightness and saturation cannot be obtained.

  The invention according to claim 1 is a glaze composition comprising 0.1 to 10% of at least one oxide of titanium, antimony and niobium in a glass glaze to be glazed.

  The invention according to claim 2 is a cyan (C) ink composition and a magenta (M) ink for performing inkjet printing on the surface of the glaze layer formed from the glass glaze composition according to claim 1 on the substrate. An ink set comprising a composition, a yellow (Y) ink composition, and a black (K) ink composition, wherein each ink composition decomposes upon firing at 500 ° C. or higher and chemistry with the element in the glass glaze An ink set for inkjet printing, comprising a water-soluble transition metal salt or water-soluble transition metal complex that forms a colored oxide by reaction, and an amine for neutralization stabilization and pH adjustment of the metal salt or metal complex is there.

  The invention according to claim 3 is a glaze composition comprising 0.1 to 10% of at least one oxide of titanium, antimony and niobium in the glass glaze to be glazed.

  The invention according to claim 4 is an ink set for ink-jet printing, wherein the cyan (C) ink composition according to claim 2 comprises a water-soluble cobalt salt or a water-soluble cobalt complex and amines.

The invention according to claim 5 is an ink set for ink jet printing, wherein the magenta (M) ink composition according to claim 2 comprises a water-soluble gold salt or a water-soluble gold complex and amines.

  The invention according to claim 6 is for inkjet printing, wherein the yellow (Y) ink composition according to claim 2 comprises a water-soluble chromium salt or water-soluble chromium complex, or a water-soluble nickel salt or water-soluble nickel complex and an amine. It is an ink set.

  The invention according to claim 7 is an ink set for ink jet printing, wherein the black (K) ink composition according to claim 2 comprises a water-soluble ruthenium salt or a water-soluble ruthenium complex and amines.

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

  Suitable water-soluble cobalt salts and complexes for cyan ink include cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt gluconate, and acetylacetonato cobalt. These can be used by mixing them according to the desired cyan color, or can be used in combination with other water-soluble transition metal salts or complexes.

  Gold chloride, sodium tetrachloroaurate, colloidal gold, and the like are suitable as the water-soluble gold salt or complex used as the magenta ink. These can be used by mixing them according to the desired azen color, or can be used in combination with other water-soluble transition metal salts or complexes.

  Examples of water-soluble chromium salts and complexes used as yellow ink include chromium chloride, chromium acetate, chromium sulfate, chromium nitrate, and acetylacetonatochrome. Water-soluble nickel salts and complexes include nickel chloride and nickel acetate. Nickel sulfate, nickel nitrate, acetylacetonato nickel and the like are suitable. Depending on the desired yellow color, these can be used in combination with the same metal, used together, or used in combination with other water-soluble transition metals or complexes such as vanadium or titanium.

  As the water-soluble ruthenium salt or complex used as the black ink, ruthenium chloride, nitrosyl ruthenium chloride, ruthenium red and the like are suitable. These can be used by mixing them according to the desired black color tone, or can be used in combination with other water-soluble transition metal salts or complexes. These water-soluble transition metal salts or transition metal complexes are used in the range of 5 to 70%, but the preferred hue is 5 to 30%.

  Water-soluble amines used to neutralize and stabilize these inks and adjust pH include primary amines such as methylamine and ethylamine, secondary amines such as dimethylamine and diethylamine, trimethylamine, It is selected from at least one tertiary amine such as triethylamine, triethanolamine or N, N-diisopropylethylamine. One or several of these may be used for all four colors or only for one ink. The amount of neutralizing agent added depends on the amount of metal salt or metal complex used, but is preferably in the range of 1.0 to 20%.

  In addition, each of these inks reacts with the glass glaze component only after being baked at a high temperature of 500 ° C. or higher, but the color of the aqueous ink solution is thin and greatly different from the color after baking. It is desirable to color each ink with a dye so that the colors after firing match. For this purpose, 0.5 to 2.0% of a dye of each color which is stable in an acidic solution is added.

  In order to adjust the viscosity and surface tension of the ink, and to prevent the ink from drying and solidifying at the nozzle part, alcohols, glycols and glycerin may be used alone or mixed to form 5-40% of the ink. Used in range. Typical examples include isopropyl alcohol, ethylene glycol, 1,3 propanediol, triethylene glycol and the like.

  Furthermore, surfactants, antifoaming agents, antifungal agents and the like for imparting wettability to the printer and ejection stability can be used in an amount of 1.0% or less.

  According to the present invention, at least one of titanium, antimony, or niobium oxide is contained in the glass glaze component of the glaze or tile in an amount of 0.1-10%. The transition metal complex is decomposed by baking at 500 ° C. or more, and a colored oxide is generated by a chemical reaction with the element in the glass glaze, so that the color of the ink is increased in brightness and saturation.

  Next, in order to specifically explain the present invention, some examples of the present invention and comparative examples for showing comparison with the examples will be given.

  A glass glaze for tiles and a glass glaze for glazes were prepared with the following composition, and a CMYK ink set was prepared. These are shown in Table 1, Table 2 and Table 3, respectively.

Glass glaze for tiles

        11-3870 and 12-3699 are transparent glazes for tiles made by Toago Material Technology.

        SGX-1135 is also an antimony glaze for tiles.

  The T1 and T6 glazes that do not contain any titanium oxide, antimony trioxide and niobium pentoxide are not corresponding to the present invention, but are shown for comparison.

Glass glaze for glaze

06-1603,06-1613 are antimony glazes for Tojo Material Technology.

02-1139 is also a titanium glaze for acupuncture.

  The glazes of H1, H3, and H5, which do not contain any titanium oxide and antimony trioxide, do not correspond to the present invention, but are shown for comparison.

CMYK ink set composition

Example 1 and Comparative Example 1
An inkjet ink set of IJ-1 was set in a printer, and four CMYK colors were solid-printed at a resolution of 720 × 720 DPI on each tile glazed with a glass glaze T1-T9 composition for tiles. They were baked with a roller hearth kiln at a maximum temperature of 1150 ° C. for 40 minutes. These colorimetric values are shown in Table 4.

As can be seen from Table 4, in Comparative Example 1 using the glazes of T1 and T6 containing no titanium oxide, antimony trioxide and niobium pentoxide, the yellow color was very thin and weak. On the other hand, in Example 1 using the glaze which mix | blended this element, yellow of high lightness saturation expressed.

Example 2 and Comparative Example 2
Printing was performed in the same manner as in Example 1 on each glazing plate coated with the glaze glass glaze H1-H6 composition using an inkjet ink set of IJ-1, and baked at 800 ° C. for 2 minutes. These colorimetric values are shown in Table 5.

As can be seen from Table 5, in Comparative Example 2 using glazes of H1, H3 and H5 which do not contain any titanium oxide and antimony trioxide, the yellow color is very thin and weak and does not function as one primary color of the ink set. On the other hand, in Example 2 using the glaze which mix | blended this element, yellow of high brightness saturation expressed.

Claims (7)

A glaze composition comprising 0.1 to 10% of at least one oxide of titanium, antimony and niobium in a glass glaze to be glazed. A cyan (C) ink composition, a magenta (M) ink composition, and a yellow (Y) ink for performing inkjet printing on the surface of the glaze layer formed from the glass glaze composition according to claim 1 on the substrate. An ink set comprising a composition and a black (K) ink composition, each ink composition being decomposed by baking at 500 ° C. or more, and generating a colored oxide by a chemical reaction with the element in the glass glaze An ink set for ink-jet printing comprising a water-soluble transition metal salt or a water-soluble transition metal complex, and amines for neutralization stabilization and pH adjustment of the metal salt or metal complex. An ink set for inkjet printing, wherein the amine according to claim 2 is at least one selected from a primary amine, a secondary amine and a tertiary amine. An ink set for inkjet printing, wherein the cyan (C) ink composition according to claim 2 comprises a water-soluble cobalt salt or a water-soluble cobalt complex and amines.
An ink set for inkjet printing, wherein the magenta (M) ink composition according to claim 2 comprises a water-soluble gold salt or a water-soluble gold complex and amines. An ink set for inkjet printing, wherein the yellow (Y) ink composition according to claim 2 comprises a water-soluble chromium salt or water-soluble chromium complex, or a water-soluble nickel salt or water-soluble nickel complex and an amine. An ink set for ink jet printing, wherein the black (K) ink composition according to claim 2 comprises a water-soluble ruthenium salt or a water-soluble ruthenium complex and an amine.