JPH03193384A - Noble-metal decorative glass product and manufacture thereof - Google Patents

Abstract

PURPOSE:To inhibit the generation of nondefectives extremely low, and to form a brilliant decorative bump of a noble metal on the surface of a glass product, etc. by making adhesive affinity to the surface of a body to be printed of a finishing layer smaller than that to the surface of a foundation layer and removing the section of the finishing layer extruded from the foundation layer. CONSTITUTION:Foundation flux, which has quite the same geometry as decorating to be worked by enamelled flux and adhesion of which is reinforced, is printed onto the surface of the base body of a glass product, etc. to be decorated and baked. The layer of an organic compound mainly comprising a noble metal such as pure gold, palladium, platinum, etc. having thickness to the base body remarkably lower than that to a foundation is printed so as to completely cover the surface of at least the foundation section or a front is printed within a range largely exceeding the tolerance of positional displacement or extremely in size larger than the foundation and baked, the glass product, etc. are applied to the process of pickling, and the extruded section of a finishing layer using the noble metal extruded from the foundation as a main component is removed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a precious metal decorative glass product and a method for manufacturing the same. More specifically, the present invention relates to a decorative glass product whose surface is decorated with 5% precious metal, and a method for manufacturing the same.

(Prior art and problems to be solved) Conventionally, in the case of a printing material with a smooth surface such as glossy enamel or glass that has not been matte processed, after firing, resin acid firmly adheres to the material. Printing is done with different brilliance depending on the proportion of precious metals contained in the salt, but there is no or little bulge, so the print on the text is not legible due to lack of beauty. There were also quite a few. When processing the same decoration on the surface of matte glass, matte enamel, or matte enamel substrate, the precious metal does not have any bulges, and the brightness of the upper layer deteriorates, resulting in In some cases, the lack of brightness may improve the readability of letters compared to decorations made from glass products with smooth surfaces, but this always causes the print to lack beauty. .

In addition, when processed on the surface of glass, the fastness of precious metals deteriorates over time due to the movement of soda that occurs near the surface of the glass. further deteriorates. For this reason, the method proposed for producing decorative decorations with good glitter and raised textures is to first bake the surface of the printing material and then finish it with a raised appearance, ensuring that the surface is completely smooth. A base printing of enamel flux is performed to make it taut and taut, and then a layer containing precious metal resinate as a main component is applied to the base, adjusting the layer of resin acid solution so that it overlaps exactly with the base. A method is used to completely cover the area. After the second firing at approximately 500°C, the desired effect of bulge and glitter can be obtained, but this effect cannot be obtained unless the two layers are perfectly superimposed. . For industrial decorative processing of bottles and glass, continuous printing of flux and precious metals in two speeds is generally carried out by silk screen printing, which allows printing in two speeds to be accurately overlapped. For alignment, in the case of cylindrical small bottles, cosmetics, alcoholic beverages, medicine bottles, etc.) For flat bottles with no thickness, attach a very precise jig to the bottom of the 1g bottle. This is even more difficult when the bottle has a complicated shape.

In any case, it is difficult to avoid misalignment of these two layers, resulting in an unacceptable decorative finish and a fairly high rate of defective products. The degree of the measured positional deviation is 10
Since the thickness of characters does not exceed two-tenths of a millimeter in most cases, this value can be used as a clue to predict the average rate of defects when printing fine characters. Become.

(Means for Solving the Problems) The present invention makes it possible to obtain high-grade precious metal decorative glass products, that is, decorations with excellent brightness and ridges and high fastness, under highly precise conditions and with industrial advantage. This article relates to precious metal decorative glass products and their manufacturing method. The present invention includes glass,
A base printing layer is printed and formed on the surface of a printing material such as enamel or ceramics using an enamel flask, and then an organic compound containing a noble metal such as pure gold, palladium, or platinum is coated so as to completely cover the base printing layer. The printed finishing layer is fired, and at least the adhesive affinity of the finishing layer to the surface of the printing object is inferior to the adhesive affinity to the surface of the base layer, and the part of the finishing layer protrudes from the base layer. The present invention relates to a noble metal decorative glass product characterized by having a structure in which the glass is removed, and a method for manufacturing the same.

(Function) As a first step, the present invention involves screen printing, etc., on the surface of a substrate, such as a glass product, to which decoration is to be applied, with a base FlexFix having the exact same shape and size as the decoration to be processed, and which has enhanced adhesion to the substrate. After printing and firing, the second
In this step, a layer of an organic compound mainly composed of precious metals, whose adhesive strength to the substrate is much inferior to that to the base, is printed by screen printing or the like so as to completely cover at least the surface of the base, or to prevent misalignment. After printing the front side to a size that greatly exceeds the allowable range, or in extreme cases thicker than the base, it is fired, and then in the third step, the product whose surface is covered with two-speed pudding 1 to processing is pickled. This product relates to high-quality, raised precious metal decorative glass products obtained by removing the protruding parts of the finishing layer mainly composed of precious metals that protrude from the base, and the manufacturing method for the same. It makes it possible to display various designs, characters, and fine lines that are not possible with printing.

In the present invention, the base is an enamel with a high content of lead oxide, and this content is preferably at least 60% by weight, 70% by weight, or more. can also be set to 60% or less. This lead oxide allows the base to have adhesive strength to the product base, but the reason why the organic compound layer has inferior adhesive strength to the product base compared to the base is the adhesive strength of the organic compound layer. That is, it is obtained by not containing bismuth (blue lead), boron oxide, and chromium.

(Example) An example of the present invention will be described based on the drawings below. 1 and 2 are cross-sectional explanatory views of the conventional method, and FIGS. 3 to 5 are cross-sectional explanatory views of noble metal decorative glass products according to the method of the present invention.

Figures 1 and 2 show the manufacturing process in which the surface portion of a glass product substrate is decorated using metal, particularly noble metal.

For example, by the first printing performed by silk screen printing, the enamel base 2 containing lead, which has exactly the same shape and dimensions as the decoration to be processed, is printed on the surface of the glass product base material ■, covering the surface. The heated substrate is placed in a high temperature of 540°C to 590°C or about 600°C depending on the glass material or the lead content in Furanox, and this high temperature causes the firing of the base 2. At this time, the base As shown in Figure 1, the surface is raised and has a taut appearance.

In a second working step, a second printing is carried out with a finishing layer having exactly the same shape and dimensions as the decoration to be processed, as well as the base, for example by silk screen printing in the same way. To fix the substrate very precisely in the same position so that the two speed prints carried out successively at this time match as perfectly as possible, and to fix the substrate in the same position very precisely and as a mark for alignment of the substrate. In this process, marks for positioning the glass product substrate and extremely precise jigs are used.

However, it often happens that the alignment is not perfect, and as shown in Figure 2, there is a misalignment between the first print 2 and the second print 3 after firing, and sometimes the precious metal is directly attached to the glass substrate. The parts that are in contact with each other and have poor shine compared to other parts may appear protruding like a border, or
In some cases, the underlying enamel layer appears as a band as shown in 5. In all of these cases, the finished product of the decoration is poor, and products decorated in such a state end up being defective.

3 to 5 are cross-sectional explanatory views showing noble metal decorative glass products according to the present invention, and the techniques illustrated by these diagrams improve the drawbacks of existing manufacturing methods. As in the case described above, first, a base 6 having exactly the same shape and size as the decoration to be processed is printed on the surface of the glass product base 1 by silk screen printing, for example. In this case as well, it is enamel flex as in the previous case, but the enamel used here has a property that the lead oxide content strengthens its adhesion to the printing material; is generally higher than that of enamel, which is commonly used for glass, ceramics, and enamel. This content is at least 60~
It is preferably 62% or more, or 70% or more.

However, as mentioned above, depending on the use of tableware, etc., it can be reduced to 60% or less if necessary.

The product whose surface is covered with the base 6 in this way makes it possible to fire enamel with a very high lead content, so for example, if the lead oxide content is at least 60%, the
00℃, and 460-65 if below 60-62%
It can be processed at temperatures as high as 0°C. At this time, as shown in FIG. 3, the surface of the base 6 is raised and taut, just like the state obtained by the conventional manufacturing method shown in FIG.

In the second step, for example, in this case as well, silk screen printing is used to coat the resinate layer 7 of a metal, particularly a noble metal such as pure gold, palladium, or platinum, on top of the base 6 so that it at least completely covers the base 6, or rather completely. In order to ensure coverage, the resinate layer 7 is printed so that it does not protrude slightly from the base. Of course, the second print 7 should be exactly overlaid on the first print 6, and the allowed overhang is generally a few tenths of a millimeter, but can be a little more if necessary.
This allows the receiver to accommodate small deviations. As is clear from FIG. 4, the portions 8 where the metal resinate scales 7 protrude on both sides of the base 6 in some cases.
and 9 do not necessarily have to be symmetrical, and the only requirement is that the base 6 be completely covered.

The component of the noble metal resinate is such that the adhesion force to the unprocessed surface of the glass product substrate 1 due to the above-mentioned resinate is
It is selected so that its adhesion to the base 2 is significantly inferior. For this reason, these resinates usually contain glass, ceramic, pure silver, and compounds containing pure silver, such as bismuth, boron oxide, and chromium, which are commonly used as adhesives in the preparation process for silk-screen printing of precious metals. Contains no adhesive for glass type glass product substrates.

Moreover, the percentage of pure silver contained in pure gold resinates is lower than that used in traditional preparation stages because pure silver and compounds containing pure silver have adhesion to the glass-type substrate of the product. is kept at a lower rate. After this second printing, the product substrate is once again exposed to a high temperature 20-50° C. lower than the first firing, so that the organic matter of the precious metal resin acid solution is removed, so that only the precious metal remains.

In a third step, the decorated product is pickled, and in this pickling process, any protruding portions 8, 9 of the precious metal that may protrude outside the base 6 are washed away and removed. This pickling combines chemical action and ultrasonic action, and has the effect of promoting layer etching and removal of protruding portions. The pickling time varies depending on various conditions such as the output of the ultrasonic transmitter used, the position of the transmitter, the nature of the pickling removal solution, and the temperature of the solution.

These removal liquids may be either acidic or basic depending on the nature of the decorated printing substrate and the decoration itself.

There are differences depending on the product and glass material, but for soda glass bottles, pickling liquid, such as sulfuric acid, 0.3 to 5% of the above acid solution that does not cause clouding on the glass, or 0.1 to 1% hydrofluoric acid. submerged in a tank containing an acidic aqueous solution containing

In this same tank, an ultrasonic transmitter is submerged and its position and output relative to the product to be pickled can be adjusted.

The temperature of the pickling solution was about 30 to 40° C., and the time for processing the product in the solution was from 30 seconds to several minutes, with test results showing that 2 minutes, for example, was good. The ultrasound can be applied throughout the entire time the product is submerged in the liquid, or the ultrasound operation can be applied only partially while the product is submerged in the liquid. The product itself can be fixed, but if necessary, some movement, such as parallel movement or vibration of the product, or stirring or changing the flow of the solution, may be used to stimulate the pickling process so that it is evenly distributed throughout the pickling process. is desirable.

After immersion in this first liquid, e.g. an acidic liquid, the product is removed from the liquid and washed with water. Neutralized with liquid. Afterwards, to increase the effect, perform Susugi once or several times under running water, for example. Depending on the case, it is also possible to use light brushing or strong showering. The brushes are then placed in a liquid, for example in a tank adjacent to the ultrasound tank. After neutralization, it is preferable to remove water droplets with hot water or hot air and dry.

Although the present invention uses an organic compound of a noble metal, it can be similarly applied to other metals.

(Effects of the Invention) According to the present invention, it is possible to apply a highly glittering and raised decorative finish using a precious metal to the surface of a glass product, etc., while suppressing the occurrence of defective products to a non-electronically low level. Since positioning is easier than conventional overprinting, processing with high productivity can be performed, and precious metal decoration processing can be carried out with industrial advantages.

Furthermore, in the present invention, bismuth (blue lead) is not included in the organic compound mainly composed of precious metals in the finishing layer, or is contained in a small amount, and the content of lead oxide in the enamel flex of the base printing is 60% or less. Firing temperature range 460-650
Even under conditions in the temperature range of 'C, it is possible to obtain the same brightness and raised properties as conventional methods, reducing production costs.
Furthermore, it can be used in the field of tableware, etc.

[Brief explanation of drawings]

1-2 are i-plane explanatory views showing the conventional method, and FIGS. 3-5 are cross-sectional explanatory views showing the method of the present invention. ■...Glass product base, 2, 6... Base, 5... Enamel layer, 7... Metal resinate layer 8.9... Protruding portion Figure 1 Figure 2 Figure 3 Figure 4 Figure 5

Claims (1)

[Scope of Claims] 1) A base printing layer printed with enamel flux is fired on the substrate surface of a printing material such as glass, enamel, ceramics, etc., and then pure gold or palladium is added so as to completely cover the base printing layer. , a finishing layer printed and formed using an organic compound containing a noble metal such as platinum is fired, and at least the adhesion affinity of the finishing layer to the surface of the printed material is inferior to the adhesion affinity to the surface of the base layer, and the finishing layer is A noble metal decorative glass product characterized by having a structure in which the portion protruding from the base layer of the layer is removed. 2) The noble metal decorative glass product according to claim 1, wherein the enamel flux of the base printing layer has a lead oxide content of 60% or less. 3) The noble metal decorative glass product according to claim 1 or 2, wherein the metal organic compound of the finishing layer does not contain bismuth, boron oxide, or chromium. 4) After forming a base printing layer by screen printing desired characters and designs using enamel flux on the substrate surface of the substrate to be printed such as glass, enamel, ceramics, etc., it is fired, and then pure gold is added so as to completely cover the base printing layer. , palladium, platinum, etc., after forming and firing a finishing layer of a precious metal-containing organic compound, the portion of the finishing layer made of the metal-containing organic compound layer protruding from the base layer is removed by pickling. A method of manufacturing decorative glass products. 5) The manufacturing method according to claim 4, wherein the firing temperature range is 450 to 600°C.