JP2004231491A - Coloring agent and method of manufacturing colored glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring agent for glass capable of brightly and deeply coloring using gold and silver as coloring sources and a method of manufacturing a colored glass having a colored coating film formed by using the coloring agent. <P>SOLUTION: The coloring agent comprising (A) gold microparticles, (B) an organic silver compound, (C) an organic compound having amino group, (D) a film forming compound, (E) a binder resin, and (F) an organic solvent is painted on the surface of a glass substrate, dried, and then baked at 400-800°C to form the colored coating film. The film forming compound (D) comprises an organic metal compound containing ≥1 kinds of metals selected from titanium, zirconia, tin, iron, and nickel and ≥1 kinds of organic silicon compounds. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００３９】
得られた着色ガラス板の透過スペクトルを図１に示す。結果、有機銀化合物を配合しない比較例１では、吸収ピークの極大値は非常に小さく、また吸収ピークの形状も幅広なものとなっている。これは、着色ガラスの色が薄く、鈍い色調を呈していることを示している。またアミノ基を有する化合物を配合していない比較例２では、比較例１に比べて、吸収ピークの極大値が大きく、吸収ピークの形状もシャープになっており、有機銀化合物の添加による効果がみられる。しかし、金微粒子、有機銀化合物を同量配合した実施例１と比較すると、吸収ピークの極大値が低く、その効果が充分に発揮されていないことがわかる。また、比較例２で用いた着色剤処理液には有機銀化合物の沈殿が確認され、得られた着色膜付きガラス板は外観不良や耐久性の低下が見られた。一方、実施例１〜４においては、有機銀化合物の配合量が多くなっても沈殿物の発生は見られず、吸収ピークの極大値は大きく、形状もシャープであり、より鮮やかでより濃い色を呈することが確認できた。また有機珪素化合物の配合量を増量した実施例４では吸収ピークが短波長にシフトしており、膜形成化合物の配合量によって透過色調を変化させることが可能なことが判明した。
【００４０】
【発明の効果】
以上のように本願の請求項記載の発明では、（Ａ）金微粒子、（Ｂ）有機銀化合物、（Ｃ）アミノ基を有する有機化合物、（Ｄ）膜形成用化合物、（Ｅ）バインダー樹脂、（Ｆ）有機溶剤が配合されてなるガラス用着色剤、並びにこれを用いた着色ガラスの製造方法にあって、外観不良がなく、鮮やかでより濃い着色が可能なガラス用着色剤、並びに前記着色剤を用いて形成された着色被膜を有する着色ガラスの製造方法を提供することができた。
【図面の簡単な説明】
【図１】実施例で作製した着色ガラス基板の透過スペクトルを示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a colorant for glass and a method for producing a colored glass, and more particularly, to a colorant for glass using gold and silver as a coloring source, and a method for producing a colored glass having a colored film formed using the colorant. About.
[0002]
[Prior art]
For example, glass base materials such as glass cups, glass bottles, indoor interiors, window glasses, and windshields for automobiles are colored with a coloring agent to impart a design change by giving a color change. I have. As a coloring method, there is a method in which a colorant composed of a pigment, a binder, and a solvent is applied to the surface of a glass plate by a method such as screen printing, spraying, or brushing, and then baked to form a colored film on the glass substrate.
[0003]
Noble metal fine particles, organometallic compounds, or the like are used alone or in combination as a coloring source in this coloring method. Specifically, there has been proposed a coloring method in which a vivid and deep coloring effect is obtained by coexisting gold fine particles and organic silver compounds, gold fine particles and silver fine particles, or these and other organic metal compounds. (For example, see Patent Document 1)
[0004]
[Patent Document 1]
JP-A-11-228175
[Problems to be solved by the invention]
However, when gold fine particles and an organic silver compound are used in combination, there is a problem that the amount of the organic silver compound is limited because the organic silver compound is hardly soluble in an organic solvent. Specifically, the compounding amount of the organic silver compound with respect to the fine gold particles could be added only up to about silver / gold = 1.5 in terms of the atomic ratio of the metal, and as a result, the effect was low. The organic silver compound becomes a precipitate when blended in an amount not less than the above-mentioned addition amount, and when colored using a coloring agent in which the precipitate is formed, poor appearance, adhesion of a coating film, and a decrease in durability may be caused. is there.
[0006]
In addition, when the gold fine particles and the silver fine particles coexist, the above-mentioned problem is solved. However, since the silver fine particles are expensive, there is a cost problem. In addition, since the gold fine particles and the silver fine particles are independently present in the colorant, silver can exert an effect on the gold fine particles only during firing, and as a result, an effect corresponding to the blending amount of the silver fine particles is obtained. Hateful.
[0007]
The present invention is intended to solve such a problem, and a paint composition having excellent storage stability without causing deterioration of quality due to sedimentation over time, and various durability and adhesive properties. An object of the present invention is to provide an excellent method for producing a coating film.
[0008]
[Means for Solving the Problems]
That is, the invention according to claim 1 of the present application is a colorant for glass, which comprises (A) gold fine particles, (B) an organic silver compound, (C) an organic compound having an amino group, (D) a film-forming compound, (E) a binder resin, and (F) an organic solvent.
[0009]
The invention according to claim 2 of the present application is the colorant for glass according to claim 1, wherein (D) the film-forming compound is at least one metal selected from titanium, zirconia, tin, iron, and nickel. It is characterized in that it is selected from at least one selected from the group consisting of organometallic compounds and organosilicon compounds.
[0010]
The invention according to claim 3 of the present application is the glass colorant according to claim 1 or 2, wherein the atomic ratio of the metal content of (A) the fine gold particles and (B) the organic silver compound contained in the colorant is: , Silver / gold = 0.1 to 20.
[0011]
The invention according to claim 4 of the present application is the colorant for glass according to any one of claims 1 to 3, wherein the molar ratio of the organic silver compound (B) to the organic compound having an amino group (C) is an amino group. Organic compound / organic silver compound = 2 to 15,000.
[0012]
The invention according to claim 5 of the present application is characterized in that the colorant for glass (E) binder resin according to any one of claims 1 to 4 is a cellulose resin.
[0013]
The invention according to claim 6 of the present application resides in a method for producing a colored glass, wherein (A) gold fine particles, (B) an organic silver compound, (C) an organic compound having an amino group, and (D) film formation on the surface of a glass substrate. A coloring agent comprising a compound for use, (E) a binder resin, and (F) an organic solvent is applied and fired at 400 to 800 ° C.
[0014]
The invention according to claim 7 of the present application is the method for producing a colored glass according to claim 6, wherein (D) the film-forming compound is at least one metal selected from titanium, zirconia, tin, iron, and nickel. And at least one selected from organometallic compounds and organosilicon compounds.
[0015]
The invention according to claim 8 of the present application is the method for producing colored glass according to claim 6 or 7, wherein the atomic ratio of the metal content of (A) the fine gold particles and (B) the organic silver compound contained in the colorant. Is characterized in that silver / gold = 0.1 to 20.
[0016]
The invention according to claim 9 of the present application is the method for producing colored glass according to any one of claims 6 to 6, wherein the molar ratio of (B) the organic silver compound to (C) the organic compound having an amino group is amino. Organic compound / organic silver compound having a group = 2 to 15,000.
[0017]
The invention according to claim 10 of the present application is the method for producing colored glass according to any one of claims 6 to 9, wherein (E) the binder resin is a cellulose resin.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
The (A) gold fine particles used in the present invention can be produced, for example, by the method described in JP-A-11-76800. That is, when a gold compound is dissolved in a solvent and gold ions in the solvent are reduced in the presence of a polymer pigment dispersant, gold fine particles having a particle size of 1 to 100 nm, preferably 1 to 50 nm are obtained. The fine particles are protected by a polymer pigment dispersant, and can be dispersed in a solvent such as alcohol, ketone, ether, and toluene.
[0019]
The polymer pigment dispersant used here is not particularly limited, but (1) has a pigment affinity group in a main chain and / or a plurality of side chains, and has a plurality of side chains constituting a solvent affinity portion. A polymer having a comb structure, (2) a polymer having a plurality of pigment-affinity portions having a pigment-affinity group in the main chain, and (3) a polymer having a pigment-affinity portion having a pigment-affinity group at one end of the main chain. Specific examples of commercially available products include Solsperse series (manufactured by Zeneca), Dispervic series (manufactured by Big Chemie), EFKA series (manufactured by EFKA Chemical), Ajispar-PB711, and Ajispar. PA111 (manufactured by Ajinomoto Co.).
[0020]
Further, for example, a solution in which gold fine particles are independently dispersed in an organic solvent is prepared by a method called an in-gas evaporation method as disclosed in JP-A-3-34211. That is, the above metal is evaporated by introducing a helium inert gas into the chamber, and cooled and condensed by collision with the inert gas. In this case, the organic solvent is obtained at a stage where the particles immediately after generation are in an isolated state. Is introduced to coat the particle surface. As the organic solvent, a solvent such as p-xylene, toluene, α-terpineol is used, and the particle diameter is 1 to 100 nm, more preferably 1 to 50 nm, and gold fine particles independently dispersed in the organic solvent are obtained. .
[0021]
Further, gold fine particles having a particle size of 1 to 100 nm, more preferably 1 to 50 nm are dispersed in a polymer soluble in alcohol, ketone, ether, toluene and the like. Specifically, a polymer or oligomer having at least one functional group selected from a cyano group (—CN), an amino group (—NH ₂ ), and a thiol group (—SH) at the terminal or side chain of the polymer molecule Is used. Specifically, the cyano group (-CN) at the terminal or side chain of the molecule, amino (-NH _2), and has at least one functional group selected from a thiol group (-SH), Its skeleton is made of polyethylene oxide, polyethylene glycol, polyvinyl alcohol, nylon 11, nylon 6, nylon 66, nylon 6.10, polyethylene terephthalate, polystyrene and the like, and its melting point or softening point is 40 to 100 ° C. The number average molecular weight of the oligomer is not particularly limited, but is about 500 to 6,000. The functional group particularly easily forms a covalent bond or a coordination bond with gold atoms on the surface of the fine gold particles, suppresses grain growth, and enhances the dispersibility of the fine gold particles.
[0022]
The (B) organic silver compound used in the present invention affects (A) the fine gold particles, and enables more vivid and deeper coloring. Specifically, organic acid salts such as silver acetate, silver propionate, silver benzoate and silver lactate are preferably used.
[0023]
In the present invention, the compounding ratio of (A) the fine gold particles and (B) the organic silver compound can be adjusted so that the atomic ratio of each metal contained in the colorant is 0.1 to 20. preferable. (A) If the mixing ratio of the fine gold particles is more than the above ratio, the effect of the fine silver particles is weak, so that the saturation is poor and a vivid coloring cannot be obtained. On the other hand, when the blending ratio of the organic silver compound (B) is higher than the above ratio, the coloring property is the same as that of the case where silver fine particles are used alone as a color forming source, and the effect of adding gold fine particles is extremely small.
[0024]
The compound (C) having an amino group reacts with the organic silver compound (B) to form a complex, thereby making the organic silver compound soluble in a colorant solvent. When a compound soluble in cellulose is used, an action as an organic solvent can be expected. For example, primary amines such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine and dodecylamine, and quaternary amines such as tetrahexylamine, tetraheptylamine and tetraoctylamine are preferred. The amount of silver is preferably two or more moles with respect to the organic silver compound (B) because silver has two coordinates. Specifically, the molar ratio of the organic compound having an amino group / organic silver compound is preferably adjusted to be 2 to 15,000. When the molar ratio is less than 2, a part of the organic silver compound cannot be dissolved and is present as a precipitate, so that the adhesion and durability of the coating film may be reduced and the appearance may be adversely affected. . On the other hand, if it exceeds 15,000, practical use is difficult.
[0025]
The (D) film-forming compound used in the present invention serves as a matrix of a colored film, and includes at least one kind of organometallic compound having a metal selected from titanium, zirconia, tin, iron, and nickel; and At least one selected from organic silicon compounds. The type of the film-forming compound to be used varies depending on the purpose of use. For example, when the durability of the colored film, particularly chemical resistance, water resistance, and moisture resistance are required, such as an automobile windshield, an organosilicon compound may be used. And a titanium compound are preferably used in combination. In order to change the color tone, it is preferable to mix an organic titanium compound or an organic iron compound when absorbing light with a longer wavelength, and to mix an organic silicon compound when absorbing light with a shorter wavelength.
[0026]
Examples of the organic silicon compound include alkoxides such as ethoxide, propoxide and butoxide, silicon oils and silicon varnishes having a polysiloxane skeleton, and silica sol in which silicon oxide ultrafine particles are dispersed in water, an organic solvent, and the like. .
[0027]
As the organic titanium compound, titanium ethoxide, propoxide, butoxides such as alkoxides, acetylacetonate, chelates such as aminates, organic acid esters such as stearate, and other oligomers obtained by polycondensation of glycolates and alkoxides. No.
[0028]
Examples of the organic zirconium compound include alkoxides such as ethoxide, propoxide and butoxide of zirconia; chelates such as acetylacetonate; organic acid esters; glycolates; and oligomers obtained by polycondensation of alkoxides.
[0029]
Examples of the organic tin compound include alkoxides such as ethoxide, propoxide and butoxide of tin, chelates such as acetylacetonate, and organic acid esters such as stearate, octylate and naphthenate.
[0030]
Examples of the organic iron compound include alkoxides such as ethoxide, propoxide and butoxide of iron, chelates such as acetylacetonate, and organic acid esters such as stearate, octylate and naphthenate.
[0031]
Examples of the organic nickel compound include alkoxides such as ethoxide, propoxide and butoxide of nickel; chelates such as acetylacetonate; and organic acid esters such as stearate, octylate and naphthenate.
[0032]
The binder resin (E) used in the present invention functions to (A) suppress the grain growth of the fine gold particles, maintain the colorant at an appropriate viscosity, and improve the application to the glass surface and the handling after drying. Having. Cellulose resin is preferably used as the binder resin, and needs to be soluble in an organic solvent. Specifically, for example, nitrocellulose, ethyl cellulose, cellulose acetate, butyl cellulose and the like can be mentioned. This amount is determined by the viscosity of the colorant and the desired color strength.
[0033]
The (F) organic solvent used in the present invention can stably disperse gold fine particles without agglomeration, and can dissolve (C) a compound having an amino group, (D) a compound for forming a film, and (E) a binder resin. There is no particular limitation so long as it is appropriately selected depending on the method of applying the coloring agent. For example, when applying by a dipping method, a relatively volatile organic solvent such as toluene, propanol, methyl ethyl ketone, and octene is preferable.
[0034]
The prepared coloring agent is applied on a transparent glass substrate by a method such as spraying, dipping, roll coating, spin coating, flexographic printing, screen printing and the like. The coating amount of the treatment liquid varies depending on the viscosity of the treatment liquid, but is adjusted to a wet film thickness of 0.2 to 40 μm, dried, baked in a furnace at 400 to 800 ° C. in an air atmosphere, and cooled. Through the above, a glass covered with a colored film can be obtained. The firing time is preferably 1 to 10 minutes.
[0035]
The glass substrate treated with the coloring agent is not limited to colorless and transparent, and may be colored as long as the transmittance does not impair the object of the present invention. For example, as the glass used as the glass substrate, in addition to colorless and transparent float glass (glass manufactured by a float method), colored float glass, colored heat ray absorbing glass, and the like can be given. In particular, when the colored glass formed according to the present invention is used as an automotive glass, it is preferable to use a heat ray absorbing glass as the glass substrate from the viewpoint of reducing solar energy incident on the interior of the vehicle. Further, tempered glass can be used as the glass substrate.
[0036]
【Example】
Next, the present invention will be described in detail with reference to specific examples.
[0037]
Examples 1 to 4, Comparative Examples 1 and 2
The treatment liquid shown in Table 1 was applied on a transparent glass substrate having a thickness of 3 mm by a screen printing method, dried in a hot air circulation oven at 100 ° C. for 5 minutes, and then in a belt furnace at 600 ° C. in an air atmosphere for 10 minutes. Baking was performed to obtain each colored glass plate.
[0038]
[Table 1]

[0039]
FIG. 1 shows a transmission spectrum of the obtained colored glass plate. As a result, in Comparative Example 1 in which the organic silver compound was not blended, the maximum value of the absorption peak was very small, and the shape of the absorption peak was wide. This indicates that the color of the colored glass is light and has a dull color tone. In Comparative Example 2 in which the compound having an amino group was not blended, the maximum value of the absorption peak was larger and the shape of the absorption peak was sharper than that in Comparative Example 1, and the effect of the addition of the organic silver compound was less. Be looked at. However, as compared with Example 1 in which the same amount of the fine gold particles and the organic silver compound was blended, the maximum value of the absorption peak was low, and it was found that the effect was not sufficiently exhibited. Further, precipitation of the organic silver compound was confirmed in the colorant treatment liquid used in Comparative Example 2, and the obtained glass plate with a colored film showed poor appearance and reduced durability. On the other hand, in Examples 1 to 4, no precipitation was observed even when the amount of the organic silver compound was increased, the maximum value of the absorption peak was large, the shape was sharp, and the color was brighter and darker. Was confirmed. In Example 4 in which the blending amount of the organosilicon compound was increased, the absorption peak was shifted to a shorter wavelength, and it was found that the transmission color tone could be changed by the blending amount of the film-forming compound.
[0040]
【The invention's effect】
As described above, in the invention described in the claims of the present application, (A) gold fine particles, (B) an organic silver compound, (C) an organic compound having an amino group, (D) a film-forming compound, (E) a binder resin, (F) A colorant for glass comprising an organic solvent, and a method for producing a colored glass using the same, wherein the colorant for glass is free from defective appearance and can be colored more vividly and deeply, and the coloring It was possible to provide a method for producing a colored glass having a colored film formed using the agent.
[Brief description of the drawings]
FIG. 1 is a diagram showing a transmission spectrum of a colored glass substrate manufactured in an example.

Claims (10)

(A) gold fine particles, (B) an organic silver compound, (C) an organic compound having an amino group, (D) a film-forming compound, (E) a binder resin, and (F) an organic solvent. Colorant for glass. The (D) film-forming compound is an organic metal compound containing at least one metal selected from titanium, zirconia, tin, iron and nickel, and at least one selected from organic silicon compounds. Colorant for glass. The colorant for glass according to claim 1 or 2, wherein the atomic ratio of the metal component of the (A) gold fine particles to the (B) organic silver compound contained in the colorant is silver / gold = 0.1 to 20. The glass according to any one of claims 1 to 3, wherein the molar ratio of (B) the organic silver compound and (C) the organic compound having an amino group is such that the organic compound having an amino group / the organic silver compound is 2 to 15,000. Colorant. The colorant for glass according to any one of claims 1 to 4, wherein (E) the binder resin is a cellulosic resin. (A) gold fine particles, (B) an organic silver compound, (C) an organic compound having an amino group, (D) a film forming compound, (E) a binder resin, and (F) an organic solvent are compounded on the surface of the glass substrate. A method for producing a colored glass, comprising applying a coloring agent and firing at 400 to 800 ° C. 7. The method according to claim 6, wherein (D) the film-forming compound is at least one selected from an organometallic compound containing at least one metal selected from titanium, zirconia, tin, iron and nickel, and an organosilicon compound. Method for producing colored glass. The method for producing a colored glass according to claim 6 or 7, wherein the atomic ratio of the metal component of (A) the fine gold particles to the (B) organic silver compound contained in the coloring agent is silver / gold = 0.1 to 20. . The coloring according to any one of claims 6 to 6, wherein the molar ratio of (B) the organic silver compound and (C) the organic compound having an amino group is such that the organic compound having an amino group / the organic silver compound = 2 to 15,000. Glass manufacturing method. The method for producing a colored glass according to any one of claims 6 to 9, wherein (E) the binder resin is a cellulosic resin.

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