Ink composition

Abstract

The present invention provides an ink composition that can be used to decorate a glass substrate and can produce an ink layer that has excellent adhesion to the glass surface and resistance to drop impact. [Solution] An ink composition for decorating a glass substrate, comprising glass frit, a solvent, and an auxiliary agent, wherein the glass frit includes crystallized glass frit.

Description

[Technical Field]

[0001] The present invention relates to an ink composition. More specifically, the present invention relates to an ink composition that can be used to decorate a glass substrate and can produce an ink layer having excellent adhesion and drop impact resistance to the glass surface. [Background technology]

[0002] Conventionally, technologies have been developed to produce printed materials by applying inkjet ink to various substrates using an inkjet method. Patent Document 1 discloses an inkjet printing method for decorating ceramics, glass, etc., by applying an ink containing glass frit to an inorganic substrate and firing it. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2003-410214 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, the ink described in Patent Document 1 has poor adhesion between the resulting ink layer and the glass substrate. Furthermore, the resulting ink layer has poor resistance to drop impact.

[0005] The present invention was made to solve these problems, and aims to provide an ink composition that can be used to decorate a glass substrate and can produce an ink layer that has excellent adhesion to the glass surface and drop impact resistance. [Means for solving the problem]

[0006] The ink composition of the present invention, which solves the above problems, mainly comprises the following components.

[0007] (1) An ink composition for decorating a glass substrate, comprising a glass frit, a solvent, and an auxiliary agent, wherein the glass frit includes a crystallized glass frit.

[0008] According to such a configuration, the ink composition can decorate the glass substrate. The obtained ink layer exhibits excellent adhesion and drop impact resistance to the glass surface.

[0009] (2) The ink composition according to (1), wherein the glass substrate is a crystallized glass substrate.

[0010] According to such a configuration, the obtained ink layer exhibits better adhesion and drop impact resistance to the glass surface.

[0011] (3) The ink composition according to (1) or (2), wherein the expansion coefficient of the crystallized glass frit is 0×10 -7 ~15×10 -7 ( / °C).

[0012] According to such a configuration, the obtained ink layer exhibits better adhesion and drop impact resistance to the glass surface.

[0013] (4) The ink composition according to any one of (1) to (3), wherein the glass frit contains a pigment, and the ratio (mass ratio) of the pigment to the crystallized glass frit is 1:9 to 5:5.

[0014] According to such a configuration, the obtained ink layer exhibits better adhesion to the glass surface. Also, the ink composition is likely to obtain an ink layer with an appropriate concentration.

[0015] (5) The ink composition according to (4), wherein the pigment comprises at least one selected from the group consisting of yellow pigment, magenta pigment, cyan pigment, black pigment and white pigment, the yellow pigment comprises at least one selected from the group consisting of lead antimony yellow, antimony titanium chromium yellow, antimony titanium yellow, antimony titanium nickel yellow and zircon praseodymium yellow, the magenta pigment comprises at least one selected from the group consisting of iron oxide, gold purple and tin chromium maroon, the cyan pigment comprises at least one selected from the group consisting of cobalt blue, cobalt aluminum blue and cobalt aluminum chromium blue, the black pigment comprises at least one selected from the group consisting of manganese ferrite black, cobalt ferrite black and cobalt manganese ferrite black and the white pigment comprises a titanium oxide-based pigment.

[0016] With this configuration, the resulting ink layer is less prone to fading over time.

[0017] (6) The ink composition according to any one of (1) to (5), wherein the softening point of the glass frit is 500 to 800°C.

[0018] With this configuration, the ink composition has good compatibility with the crystallized glass substrate and has the effect of improving the adhesion between the decorative ink and the substrate. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide an ink composition that can be used to decorate a glass substrate and can produce an ink layer having excellent adhesion to the glass surface and drop impact resistance. [Modes for carrying out the invention]

[0020] <Ink composition> An ink composition according to one embodiment of the present invention is an ink composition for decorating a glass substrate. The ink composition comprises glass frit, a solvent, and an auxiliary agent. The glass frit includes crystallized glass frit. Each of these will be described below.

[0021] (Glass substrate) The glass substrate to be decorated using the ink composition of this embodiment is not particularly limited. For example, the glass substrate may be borosilicate glass, crystallized glass, soda glass, etc. Among these, the glass substrate is preferably a crystallized glass substrate. As a result, the resulting ink layer exhibits better adhesion and drop impact resistance to the glass surface.

[0022] The thermal expansion coefficient of the glass substrate is not particularly limited. For example, it is preferable that the thermal expansion coefficient of the glass substrate is close to that of the glass frit contained in the ink composition. Specifically, the thermal expansion coefficient of the glass substrate is 0 × 10⁻⁶. -7 It is preferable that the temperature is above ( / °C). Also, the coefficient of thermal expansion of the glass substrate is 20 × 10 -7 It is preferable that the temperature is below ( / °C), and 10 × 10 -7 It is more preferable that the temperature is below ( / ℃), 5 × 10 -7 It is even more preferable that the temperature is below ( / °C). When the thermal expansion coefficient of the glass substrate is within the above range, the resulting ink layer exhibits better adhesion and drop impact resistance to the glass surface. In this embodiment, the thermal expansion coefficient of the glass substrate can be measured by the compressive load method using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, manufactured by Rigaku Corporation).

[0023] The thickness of the glass substrate is not particularly limited. For example, the thickness of the glass substrate is preferably 3.0 μm or more, and more preferably 3.5 μm or more. Furthermore, the thickness of the glass substrate is preferably 10.0 μm or less, and more preferably 8.0 μm or less. When the thickness of the glass substrate is within the above range, the resulting printed material has excellent handling and processability.

[0024] (Glass frit) The glass frit includes crystallized glass frit. Crystallized glass frit is an amorphous glass during glass production, but partially crystallizes when the glass is heated. The crystallized glass frit in this embodiment contains SiO2 and further contains Zr (zirconia), Al (aluminum), or Li (lithium).

[0025] SiO2 is the main component of crystallized glass frit and is the main component that forms the network structure of glass. The SiO2 content in crystallized glass frit is not particularly limited. For example, the SiO2 content is preferably 40% by mass or more, and more preferably 45% by mass or more, in the crystallized glass frit. Furthermore, the SiO2 content is preferably 80% by mass or less, and more preferably 70% by mass or less, in the crystallized glass frit. Crystallized glass frit containing SiO2 within the above range has a low coefficient of thermal expansion and therefore has excellent impact resistance.

[0026] Zr is present in crystalline glass frit in the form of ZrO2.

[0027] In crystalline glass frit, Ti is present in the form of TiO2.

[0028] In crystalline glass frit, Mg is present in the form of MgO.

[0029] Na is present in crystalline glass frit in the form of Na2O.

[0030] Al is present in crystalline glass frit in the form of Al2O3.

[0031] Li is present in crystalline glass frit in the form of Li2O.

[0032] B is contained in the form of B2O3 in the crystallized glass frit.

[0033] The expansion coefficient of the crystallized glass frit is preferably 0 × 10 -7 ( / °C) or more. Further, the expansion coefficient of the crystallized glass frit is preferably 20 × 10 -7 ( / °C) or less, and more preferably 5 × 10 -7 ( / °C) or less. When the expansion coefficient of the crystallized glass frit is within the above range, the obtained ink layer exhibits better adhesion and drop impact resistance to the glass surface. In this embodiment, the expansion coefficient can be measured by the compression load method using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, manufactured by Rigaku Corporation).

[0034] In the ink composition of this embodiment, the expansion coefficient of the crystallized glass frit is close to that of the base material (for example, a crystallized glass base material). Thereby, the ink composition can exhibit excellent adhesion to the base material (when the base material is a crystallized glass base material, the glass surface). Further, the ink composition can exhibit excellent drop impact resistance.

[0035] The content of ZrO2 in the crystallized glass frit is not particularly limited. For example, the content of ZrO2 is preferably 1% by mass or more, and more preferably 5% by mass or more in the crystallized glass frit. Further, the content of ZrO2 is preferably 20% by mass or less, and more preferably 15% by mass or less in the crystallized glass frit.

[0036] The content of Al2O3 in the crystallized glass frit is not particularly limited. For example, the content of Al2O3 is preferably 5% by mass or more, and more preferably 10% by mass or more in the crystallized glass frit. Further, the content of Al2O3 is preferably 40% by mass or less, and more preferably 30% by mass or less in the crystallized glass frit.

[0037] The Li2O content in the crystallized glass frit is not particularly limited. For example, the Li2O content is preferably 1% by mass or more, and more preferably 5% by mass or more, in the crystallized glass frit. Furthermore, the Li2O content is preferably 20% by mass or less, and more preferably 15% by mass or less, in the crystallized glass frit.

[0038] Crystallized glass frit containing the above-mentioned components has a low coefficient of thermal expansion, resulting in excellent impact resistance.

[0039] In addition to the above, the crystalline glass frit may optionally contain ZnO, monovalent alkali metal oxides (Na2O, K2O, etc.), F2, etc.

[0040] Furthermore, fermenting agents may be added to the crystallized glass frit depending on its intended use. The fermenting agents are not particularly limited. For example, fermenting agents include 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, and even natural products such as feldspar, silica, borax, and kaolin.

[0041] The content of crystallized glass frit is not particularly limited. For example, the content of crystallized glass frit in the ink composition is preferably 20% by mass or more, and more preferably 30% by mass or more. Furthermore, the content of crystallized glass frit in the ink composition is preferably 60% by mass or less, and more preferably 50% by mass or less. When the content of crystallized glass frit is within the above range, the ink composition has excellent storage stability as an ink and adhesion to the substrate.

[0042] Returning to the general explanation of glass frit, the softening point of glass frit is not particularly limited. For example, the softening point is preferably 500°C or higher, and more preferably 550°C or higher. Furthermore, the softening point is preferably 700°C or lower, and more preferably 650°C or lower. Having the softening point within the above range allows the ink composition to have excellent adhesion to the substrate and drop impact resistance after decoration.

[0043] If the glass frit contains other glass frits besides crystallized glass frit, the content of the other glass frits is not particularly limited. For example, it is preferable that the content of the other glass frits be 10% by mass or less in the ink composition. It is presumed that the ink composition will not be significantly affected in terms of adhesion and drop impact resistance as long as the content of the other glass frits is within the above range.

[0044] (solvent) The solvent is not particularly limited. For example, solvents include water, glycol ether solvents, acetate solvents, alcohol solvents, ketone solvents, ester solvents, hydrocarbon solvents, fatty acid ester solvents, aromatic solvents, etc.

[0045] In this embodiment, the solvent preferably contains at least one of either a glycol ether-based solvent or an acetate-based solvent. Both glycol ether-based and acetate-based solvents have low viscosity and relatively high boiling points. Therefore, inks containing these as solvents have improved drying properties and superior ejection stability during inkjet printing.

[0046] Glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono(iso)propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol Examples include mono-n-propyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, and tripropylene glycol dimethyl ether.

[0047] Acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec-butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, and propylene glycol mono-sec-butyl ether acetate. Examples include alkylene glycol monoalkyl ether acetates such as propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-ethoxybutyl acetate, 3-methyl-3-propoxybutyl acetate, 3-methyl-3-isopropoxybutyl acetate, 3-methyl-3-n-butoxyethyl acetate, 3-methyl-3-isobutoxybutyl acetate, 3-methyl-3-sec-butoxybutyl acetate, and 3-methyl-3-tert-butoxybutyl acetate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, and tripropylene glycol diacetate.

[0048] The solvent in this embodiment preferably has a boiling point of 150°C or higher, and more preferably 180°C or higher. Furthermore, the solvent preferably has a boiling point of 300°C or lower, and more preferably 280°C or lower. When the boiling point is within the above range, the resulting ink exhibits improved drying properties and superior ejection stability during inkjet printing. Additionally, the ink tends to produce sharp prints with less bleeding. If the solvent's boiling point is below 150°C, the ink tends to dry more easily near the print head nozzle, reducing ejection stability. On the other hand, if the solvent's boiling point exceeds 300°C, the ink becomes more difficult to dry, and the drying process during print formation tends to take longer. Furthermore, the resulting prints tend to have smudged images.

[0049] The solvent content is not particularly limited. For example, the solvent content in the ink composition is preferably 30% by mass or more, and more preferably 35% by mass or more. Furthermore, the solvent content is preferably 60% by mass or less, and more preferably 55% by mass or less. When the solvent content is within the above range, the ink composition is easily adjusted to an appropriate viscosity and exhibits excellent ejection stability during inkjet printing. In addition, the ink composition makes it easy to incorporate the desired amount of pigment and binder resin, making it easy to obtain the desired color development and performance.

[0050] (Auxiliary agent) Additives are added to improve the storage stability of the ink composition. Additives are not particularly limited. For example, additives include various additives such as surface tension modifiers, viscosity modifiers, resistivity modifiers, heat stabilizers, antioxidants, reduction inhibitors, preservatives, pH adjusters, defoamers, and wetting agents. Among these, dispersants are preferably polymer-type dispersants, and more preferably have acidic or basic adsorption groups at their ends, due to their suitability for glass.

[0051] (Dispersant) Dispersants are added to prevent pigment re-aggregation and improve ink stability. Examples of polymeric dispersants include polyester-based, polyether-based, acrylic-based, and aliphatic-based dispersants. These are appropriately selected considering their compatibility with the solvent used. Examples of dispersants with acidic or basic adsorbent groups at their terminals include those containing phosphate groups, carboxyl groups, tertiary amino groups, amide groups, or their salts as pigment adsorbent groups within the molecule. These are appropriately selected considering the pigment used.

[0052] The content of the additive is not particularly limited. For example, the content of the additive is preferably 2% by mass or more, and more preferably 4% by mass or more, in the ink composition. Furthermore, the content of the additive is preferably 20% by mass or less, and more preferably 10% by mass or less, in the ink composition. By having the content of the additive within the above range, the ink composition has excellent storage stability.

[0053] (optional ingredient) • Synthetic resin The ink composition of this embodiment may optionally contain a synthetic resin. The viscosity of the ink composition can be adjusted by adding a synthetic resin. The synthetic resin is not particularly limited. For example, synthetic resins include acrylic resins, urethane resins, polyester resins, vinyl acetate resins, and the like.

[0054] The weight-average molecular weight of the synthetic resin is preferably between 10,000 and 200,000. Having the molecular weight of the synthetic resin within this range makes it easier to appropriately adjust the viscosity of the ink composition.

[0055] • Pigments (colorants) The ink composition of this embodiment may contain various pigments (colorants). The pigments are not particularly limited. For example, the pigments may be yellow pigment, magenta pigment, cyan pigment, black pigment, white pigment, etc.

[0056] Yellow pigments are not particularly limited. For example, yellow pigments include lead antimony yellow, antimony titanium chromium yellow, antimony titanium yellow, antimony titanium nickel yellow, and zirconpraseodymium yellow.

[0057] The magenta pigment is not particularly limited. Examples of magenta pigments include iron oxide, gold purple, and tin-chromium maroon.

[0058] The cyan pigment is not particularly limited. For example, cyan pigments include cobalt blue, cobalt aluminum blue, and cobalt aluminum chromium blue.

[0059] The black pigment is not particularly limited. For example, black pigments include manganese ferrite black, cobalt ferrite black, and cobalt manganese ferrite black.

[0060] White pigments are not particularly limited. For example, white pigments include titanium dioxide-based pigments.

[0061] By selecting pigments from the above options, the resulting ink layer is less prone to fading over time.

[0062] When a pigment is included, the ratio (mass ratio) of the pigment to the crystalline glass frit is preferably 1:9 to 5:5, and more preferably 2:8 to 4:6. By having the ratio (mass ratio) of pigment to crystalline glass frit within the above range, the resulting ink layer exhibits superior adhesion to the glass surface. Furthermore, the ink composition makes it easier to obtain an ink layer of appropriate concentration.

[0063] ·others The ink composition of this embodiment may also contain various additives as needed, such as surface tension modifiers, viscosity modifiers, resistivity modifiers, heat stabilizers, antioxidants, reduction inhibitors, preservatives, pH adjusters, defoamers, and wetting agents.

[0064] In the ink composition of this embodiment, when a pigment is included, the expansion coefficient of the mixture of the glass frit and pigment described above is 0 × 10 -7 It is preferable that the temperature is above ( / °C). Also, the expansion coefficient of the mixture is 30 × 10 -7 It is preferable that the temperature is below ( / °C), and 10 × 10 -7 It is more preferable that the temperature is below ( / °C). When the expansion coefficient of the mixture is within the above range, the resulting ink layer exhibits better adhesion and drop impact resistance to the glass surface.

[0065] The method for preparing the ink composition of this embodiment is not particularly limited. For example, the ink composition may be prepared by mixing the materials to be used, further dispersing the mixture using a disperser such as a roll mill, ball mill, colloid mill, jet mill, or bead mill, and then filtering it.

[0066] As described above, the ink compositions used in this demonstration can be used to decorate glass substrates. The resulting ink layer exhibits excellent adhesion and drop impact resistance to the glass surface.

[0067] <Printed materials and methods for manufacturing printed materials> A printed material according to one embodiment of the present invention comprises a glass substrate and an ink layer. The ink layer is a layer on the glass substrate to which the above-described ink composition is applied. Each of these will be described below.

[0068] (Glass substrate) The glass substrate is the same as that described above in relation to the embodiment of the ink composition. The printed material of this embodiment exhibits particularly excellent adhesion between the ink layer and the glass surface when the glass substrate is a crystallized glass substrate.

[0069] (Ink layer) The ink layer is a layer on a glass substrate to which an ink composition has been applied.

[0070] The method for forming the ink layer on the glass substrate is not particularly limited. For example, the ink layer may be formed by a step of applying an ink composition to the glass substrate using an inkjet recording method (ink application step), and a step of drying the applied ink composition (drying step).

[0071] In the ink application process, the method of applying inkjet ink to the glass substrate using an inkjet recording method is not particularly limited. Examples of such methods include continuous methods such as charge modulation methods, microdot methods, charged jet control methods, and ink mist methods, as well as on-demand methods such as piezo methods, pulse jet methods, bubble jet (registered trademark) methods, and electrostatic attraction methods.

[0072] The amount of ink applied by the ink composition is not particularly limited. For example, the amount of ink applied is 1 g / m² relative to the glass substrate. 2 Preferably, it is 2 g / m 2 It is more preferable that the amount is greater than or equal to the above. In addition, the amount of ink applied should be 150 g / m² relative to the glass substrate. 2 Preferably, it is 50 g / m 2 The following is more preferable: When the amount of ink applied is within the above range, the resulting print is more likely to achieve the desired image density.

[0073] In the drying process, the drying conditions for the ink composition are not particularly limited. For example, the drying process may be carried out under conditions of a drying temperature of 620-680°C and a drying time of 8-10 minutes.

[0074] As described above, the printed material of this embodiment can be used to decorate a glass substrate because the ink composition described above is used. The resulting ink layer exhibits excellent adhesion and drop impact resistance to the glass surface. [Examples]

[0075] The present invention will be described more specifically below with reference to examples. The present invention is not limited in any way to these examples.

[0076] The raw materials used are listed below. <glass frit> Crystallized glass frit 1: Manufactured by Okuno Pharmaceutical Co., Ltd., ProGlass LE-0565, softening point 607°C, coefficient of thermal expansion 1 × 10⁻⁶ -7 ( / ℃) Crystallized glass frit 2: Manufactured by Okuno Pharmaceutical Co., Ltd., ProGlass LE-1064, softening point 584°C, coefficient of thermal expansion 10 × 10⁻⁶ -7 ( / ℃) The thermal expansion coefficient of glass frit was measured using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, manufactured by Rigaku Corporation) by the compressive load method. <Solvent> Glycol ether-based solvent: Manufactured by Nippon Emulsifier Co., Ltd., DEDG <Auxiliary agent> Dispersant: SOLSPERSE J981, manufactured by Lubrizol Japan Co., Ltd. Dispersant: SOLSPERSE 9000, manufactured by Lubrizol Japan Co., Ltd., basic dispersant Alkyl ether type nonionic surfactant: LUCRAMUL WT100, manufactured by Tanatex Chemicals Japan Co., Ltd. <Pigments> Yellow pigment: Manufactured by Nikken Co., Ltd., GS-77 YELLOW, zirconpraseodium composite oxide system Magenta pigment: Manufactured by Nikken Co., Ltd., HS-76 MAROON, tin-chromium composite oxide system Cyan pigment: Manufactured by Nikken Co., Ltd., NF-2800 BLUE, cobalt-aluminum composite oxide system Black pigment: GC-90 BLACK, manufactured by Nikken Co., Ltd., cobalt manganese ferrite composite oxide system. White pigment: Manufactured by Teika Co., Ltd., JR-805, titanium dioxide-based.

[0077] <Example 1> The materials were formulated according to ink formulations 1-4 below and dispersed using a bead mill disperser. Impurities were then removed by filtration to prepare the ink of Example 1. The expansion coefficient of the mixture was measured using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, Rigaku Corporation) by the compression load method (the same method was used hereafter).

[0078] <Ink Formula 1> • Yellow pigment: GS-77 YELLOW (Manufactured by Nikken Co., Ltd., Zirconpraseodium Yellow) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-0565 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 1 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 11 × 10⁻⁶. -7 It was ( / ℃).

[0079] <Ink Formula 2> • Magenta pigment: HS-76 MAROON (Manufactured by Nikken Co., Ltd., tin-chromium marron) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-0565 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 1 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 9 × 10 -7 It was ( / ℃).

[0080] <Ink Formula 3> • Blue pigment: NF-2800 BLUE (Manufactured by Nikken Co., Ltd., Cobalt Aluminum Blue) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-0565 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 1 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 12 × 10⁻⁶. -7 It was ( / ℃).

[0081] <Ink Formula 4> • Black pigment: GC-90 BLACK (Manufactured by Nikken Co., Ltd., Cobalt Manganese Ferrite Black) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-0565 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 1 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 10 × 10 -7 It was ( / ℃).

[0082] <Ink Formula 5> • White pigment: JR-805 (Manufactured by Teika Co., Ltd., Titanium Oxide) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-0565 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 1 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 10 × 10 -7 It was ( / ℃).

[0083] <Example 2> The materials were formulated according to ink formulations 6-10 below and dispersed using a bead mill disperser. Impurities were then removed by filtration to prepare the ink of Example 2. The expansion coefficient of the mixture was measured using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, Rigaku Corporation) by the compression load method (the same method was used hereafter).

[0084] <Ink Formula 6> • Yellow pigment: GS-77 YELLOW (Manufactured by Nikken Co., Ltd., Zirconpraseodium Yellow) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 20 × 10⁻⁶. -7 It was ( / ℃).

[0085] <Ink Formula 7> • Magenta pigment: HS-76 MAROON (Manufactured by Nikken Co., Ltd., tin-chromium marron) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 19 × 10⁻⁶. -7 It was ( / ℃).

[0086] <Ink Formula 8> • Blue pigment: NF-2800 BLUE (Manufactured by Nikken Co., Ltd., Cobalt Aluminum Blue) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 17 × 10⁻⁶. -7 It was ( / ℃).

[0087] <Ink Formula 9> • Black pigment: GC-90 BLACK (Manufactured by Nikken Co., Ltd., Cobalt Manganese Ferrite Black) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 18 × 10⁻⁶. -7 It was ( / ℃).

[0088] <Ink Formula 10> • White pigment: JR-805 (Manufactured by Teika Co., Ltd., Titanium Oxide) 10% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 39% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 21 × 10⁻⁶. -7 It was ( / ℃).

[0089] <Example 3> The materials were formulated according to ink formulations 11-15 below and dispersed using a bead mill disperser. Impurities were then removed by filtration to prepare the ink of Example 3. The expansion coefficient of the mixture was measured using a thermomechanical analyzer (Thermo plus EVO2 TMA8311, Rigaku Corporation) by the compression load method (the same method was used hereafter).

[0090] <Ink Formula 11> • Yellow pigment: GS-77 YELLOW (Manufactured by Nikken Co., Ltd., Zirconpraseodium Yellow) 29% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 20% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 25 × 10⁻⁶. -7 It was ( / ℃).

[0091] <Ink Formula 12> • Magenta pigment: HS-76 MAROON (Manufactured by Nikken Co., Ltd., tin-chromium marron) 29% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 20% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 29 × 10⁻⁶. -7 It was ( / ℃).

[0092] <Ink Formula 13> • Blue pigment: NF-2800 BLUE (Manufactured by Nikken Co., Ltd., Cobalt Aluminum Blue) 29% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 20% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 28 × 10⁻⁶. -7 It was ( / ℃).

[0093] <Ink Formula 14> • Black pigment: GC-90 BLACK (Manufactured by Nikken Co., Ltd., Cobalt Manganese Ferrite Black) 29% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 20% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 24 × 10⁻⁶. -7 It was ( / ℃).

[0094] <Ink Formula 15> • White pigment: JR-805 (Manufactured by Teika Co., Ltd., Titanium Oxide) 29% by mass • Dispersant: SOLSPERSE J981 (Manufactured by Lubrizol Japan Co., Ltd., basic polymer dispersant) 4% by mass Glycol ether-based solvent: DEDG (Manufactured by Nippon Emulsifier Co., Ltd.) 45% by mass • Crystallized glass frit: ProGlass LE-1064 (Manufactured by Okuno Pharmaceutical Co., Ltd., expansion coefficient 10 x 10) -7 ( / ℃)) 20% by mass • Alkyl ether type nonionic surfactant: LUCRAMUL WT100 (Manufactured by Tanatex Chemicals Japan Co., Ltd., alkyl alkoxylate) 2% by mass Total 100% by mass The coefficient of expansion of the mixture of pigment and glass frit is 25 × 10⁻⁶. -7 It was ( / ℃).

[0095] <Comparative Example 1> Ink formulations 11 to 15 were prepared in the same manner as above, except that crystallized glass frit 1 used in ink formulations 1 to 5 was replaced with the borosilicate glass frit described below. • Borosilicate glass frit: BS-1, manufactured by Okamoto Glass Co., Ltd., coefficient of thermal expansion 52 × 10 -7 ( / ℃) The coefficient of expansion of the mixture of pigment and glass frit is approximately 60 × 10⁻⁶. -7 It was ( / ℃).

[0096] • Printing Using the obtained ink composition, a crystallized glass substrate (NEPHERAM N-0, manufactured by Nippon Electric Glass Co., Ltd., expansion coefficient: 1.0 × 10) was subjected to the following inkjet conditions. -7 Inkjet printing was performed on a material with a low coefficient of thermal expansion ( / °C), excellent heat resistance, and thermal shock resistance, and the ink composition was dried under the following conditions to produce printed materials.

[0097] • Inkjet conditions for ink compositions Inkjet recording device: Piezoelectric type Nozzle diameter: 40 μm Operating voltage: 100V Frequency: 8kHz Resolution: 600 x 600 dpi Base material temperature: 40~70℃ (room temperature) <Drying conditions> Bake at 650℃ for 10 minutes.

[0098] The ink compositions (ink sets) and printed materials obtained in Examples 1-3 and Comparative Example 1 were evaluated for adhesion to the substrate and drop impact resistance based on the following evaluation methods and criteria. The results are shown in Table 1.

[0099] [Table 1]

[0100] <Adhesion> A cross-cut test (JIS K 5400-8.5) was conducted and evaluated according to the following evaluation criteria. (Evaluation Criteria) ○: The result classification according to the JIS standard was 0. △: The result classification according to the JIS standard was 1 to 3. ×: The result classification according to the JIS standard was 4-5.

[0101] <Drop Impact Resistance> A 250mm x 250mm sample (glass substrate thickness 3.5-4.5mm) was suspended from the ground using a 3cm jig, and a 530g steel ball was dropped from a specified height to check for shattering. The following evaluation criteria were used for evaluation. (Evaluation Criteria) ○: No cracks occurred when a steel ball was dropped from a height of 70 cm. △: The steel ball cracked when dropped from a height of 70 cm, but did not crack when dropped from a height of 40 cm. ×: The steel ball will crack if dropped from a height of 40 cm.

[0102] As shown in Table 1, the ink layers obtained from the ink compositions of Examples 1 to 3 of the present invention exhibited excellent adhesion to glass surfaces, and the printed materials showed excellent drop impact resistance.

Claims

1. This is an ink composition for decorating a glass substrate. It contains glass frit, a solvent, and an auxiliary agent. The glass frit is an ink composition containing crystallized glass frit.

2. The ink composition according to claim 1, wherein the glass substrate is a crystallized glass substrate.

3. The coefficient of thermal expansion of the aforementioned crystallized glass frit is 0 × 10 -7 ~15 x 10 -7 The ink composition according to claim 1 or 2, wherein the temperature is ( / °C).

4. The glass frit contains a pigment, The ink composition according to claim 1 or 2, wherein the ratio (mass ratio) of the pigment to the crystallized glass frit is 1:9 to 5:

5.

5. The aforementioned pigment includes at least one selected from the group consisting of yellow pigment, magenta pigment, cyan pigment, black pigment, and white pigment. The aforementioned yellow pigment includes at least one selected from the group consisting of lead antimony yellow, antimony titanium chromium yellow, antimony titanium yellow, antimony titanium nickel yellow, and zirconpraseodymium yellow. The magenta pigment comprises at least one selected from the group consisting of iron oxide, gold purple, and tin chromium maroon. The cyan pigment comprises at least one selected from the group consisting of cobalt blue, cobalt aluminum blue, and cobalt aluminum chromium blue. The aforementioned black pigment includes at least one selected from the group consisting of manganese ferrite black, cobalt ferrite black, and cobalt manganese ferrite black. The ink composition according to claim 4, wherein the white pigment comprises a titanium dioxide-based pigment.

6. The ink composition according to claim 1 or 2, wherein the softening point of the glass frit is 500 to 800°C.

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