JPS60224538A - Beam-accumulating enamel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a luminescent enamel used as a display enamel, a decorative enamel, or the like.

[Background technology]

Luminescent phosphors are widely known substances that have a so-called phosphorescent effect, and when stimulated by light such as electric lamps, they emit light due to the stored energy after the stimulation stops.

Currently, this substance is well-known as zinc sulfide with copper added, and it is dispersed in plastics and other materials to produce safety signs such as fire alarms, emergency exits, switches, lighters, ornaments in cosmetic boxes, toys, and other materials. etc., are widely used.

However, using plastic materials for some safety signs, decorations, etc. has poor durability, and the plastic itself may deteriorate or become scratched and dirty, making it impossible to function as signs or decorations. There are things that cannot be achieved.

Therefore, research has been carried out on using highly durable enamel and ceramics as signs, decorations, etc., and inserting luminescent phosphors into the transparent glass layer on their surfaces. the result,
It was proposed to make a phosphorescent enamel body using a special frit. In addition, as the Shiga Prefectural Zokuraku Ceramics Experiment Station announced in a newspaper in August 1981, a special glaze was used to envelop the phosphorescent material so that the phosphorescent material would not decompose even at high temperatures when the glaze was fired. Ceramics that glow (phosphorescent phosphorescent ceramics) have also been proposed. When making signs, decorations, etc. that are highly durable with enamel or pottery and also have phosphorescent properties, it is common to use glazes that contain phosphorescent phosphors. Since pressure is applied to bake onto the substrate, it is first necessary to prevent the phosphorescent material from being decomposed at high temperatures during baking, and secondly, it is necessary to prevent the glaze and the phosphorescent W from reacting. Therefore, as mentioned above, phosphorescent products are made using special frits or glazes. However, because special frits or glazes are used, the durability of enamel has deteriorated, even though enamel is inherently durable.

[Purpose of the invention]

This invention was made in view of these circumstances,
The aim is to provide durable phosphorescent enamel.

[Disclosure of the invention]

In order to achieve the above-mentioned objects, the gist of the present invention is a luminescent enamel in which a luminescent phosphor layer is provided between a base and a transparent glass layer. The present invention will be explained in detail below.

Figure @1 and Figure 2 show the luminescent enamel according to this invention. The phosphorescent enamel shown in FIG. A phosphorescent phosphor layer 3 and a transparent glass layer (transparent glaze layer) 4 are formed in this order, and the phosphorescent enamel shown in FIG. 2 has a lower glaze layer 2. Intermediate glaze layer 5. The luminescent phosphor layer 3 and the transparent glass bottle 4 are formed in this order. The transparent glass layer 4 may be colorless or colored, and the intermediate glaze layer 5 is white or a color close to white.

The phosphorescent enamel shown in Fig. @1 and Foil Fig. 2 are made as follows. First, a top glaze is applied onto the base 1 and then fired to form the citron layer 2. When making the one shown in FIG. 2, next, an intermediate glaze is applied onto the F glaze layer 2 and then fired to form an intermediate glaze layer 5 of white or a light color close to white. In the case shown in Fig. 1, a paste containing a luminescent phosphor is applied onto the lower glaze layer 2, and in the case shown in Fig. 2, a paste containing a luminous phosphor is applied onto the intermediate glaze layer 5, so that the phosphorescent material does not decompose. A luminescent phosphor layer 3 is formed by firing. If necessary, a pattern may be created using paste or the like.

As a paste containing a phosphorescent phosphor, a phosphorescent phosphor such as one whose composition is ZnS and Cu is dispersed in a vehicle whose main component is nitrocell (a-nolose), etc. is used.Nitrocellulose is the main component. A product in which luminous phosphor is dispersed in a vehicle is suitable for coating by screen printing, but if this product is mixed with a binder other than nitrocellulose, water or alcohol,
It may also be sprayed, brushed, etc. after this,
A top glaze is applied and fired to form a transparent glass layer 4 to obtain luminous enamel.

Note that the intermediate glaze layer of white or a bright color close to white is not necessarily required. However, since the lower glaze layer is usually black, dark blue, or dark brown in color, when pressure is applied to provide a luminous phosphor layer on top of the lower glaze layer, the light from the luminous phosphor is transferred to the lower glaze. There is a high possibility that the light will be absorbed by the layer, making it difficult to see the light clearly from the outside. On the other hand, if a phosphorescent layer is provided on the intermediate glaze layer that is white or a light color close to white, the light from the phosphorescent material will not be absorbed much by the intermediate glaze layer, so the light from the outside will be clearly visible. I can see it (4) I can see it. Therefore, it is preferable to provide an intermediate glaze layer.

When applying a phosphorescent material using a binder, if the top glaze is directly applied and fired, inorganic binders are good, but organic binders tend to burn insufficiently and may remain black. Therefore, when using an organic binder, it is preferable to blow off the binder before applying the top glaze. Furthermore, when blowing off the organic binder, there is a high risk that the luminescent phosphor will decompose if heated to 700° C. or higher, so it is advisable to choose a binder that decomposes or vaporizes even at low temperatures.

Next, examples will be described.

(Example 1) Nippon Ferro Co., Ltd. lower glaze fritz) #2232° #2
236 and 2240K" were used in the same amount, and the usual lower glaze mill mixing was carried out. The obtained upper glaze was sprayed onto the ultra-low carbon steel for enameling (S
PP) plate was coated and fired at 850°C to create an enameled plate.

Next, a phosphorescent phosphor manufactured by Hinami Denshi (NP-3201, composition ZnS;
A paste was prepared by dispersing Cu)k.

After applying the previously prepared enamel plate K and the luminescent phosphor paste by Nuclean printing, it was fired at 550° C. to remove the binder. Then 5iOz60mol'A + 820
37.5 moles4. Ti025 mol'6 + Zr022
-5 mol%, NazO12,5 mol%, Liz
Using a transparent glass frit containing 2.5 moles of F2 as a flux and 5 moles of F2 as a flux, a top glaze made by normal top-shaft mill compounding was sprayed onto the print.
By firing at .degree. C., a luminescent enamel as shown in FIG. 1 was obtained. When the resulting phosphorescent enamel was exposed to electric light and left in the dark, it emitted a beautiful green glow. In addition, in terms of durability, an acid resistance test according to JISR-4301 was conducted, and the result was AA grade, which was extremely excellent.

(Example 2) In the same manner as in Example 1, a steel plate was coated with top glaze and fired to obtain an enameled plate. Next, an intermediate glaze obtained by mill-blending titanium milky white frit #1573B manufactured by Nippon Ferro Co., Ltd. was spray-painted on the enamel plate, and 820
℃ to form an intermediate glaze layer. On top of that, the same label pattern as in Example 1 was screen printed. After firing at 550°C to remove the binder, a top glaze made using transparent glaze XF-44 manufactured by Nippon Ferro Co., Ltd. was fired at 800°C using spray L to obtain luminous enamel. Like the one in Example 1, this phosphorescent enamel also emits beautiful light in the dark and has a durability that meets JISR-4.
As a result of carrying out the acid resistance test of No. 01, it was found to be extremely excellent at grade AA.

〔Effect of the invention〕

The phosphorescent enamel according to the present invention has a phosphorescent phosphor layer between the base and the transparent glass layer, so compared to the case where the phosphorescent phosphor is included in the transparent glass layer. i
! During manufacturing, there is less contact between the luminescent phosphor and the top glaze. Moreover, when the top glaze is fired, the glass component in the top glaze softens and covers the phosphorescent layer, so the temperature of the phosphorescent material does not rise much and decomposition is prevented. Normally, the luminescent phosphor is 7
It decomposes when heated above 20℃, but at the firing temperature of a normal top glaze, the temperature of the luminescent phosphor is estimated to be 300 to 600℃.
It only rises to about ℃. Therefore, there is no need to use special frits or glazes as in the past, and it is possible to select a frit or glaze that can provide a transparent glass layer with excellent durability. can.

[Reference]

Next, a phosphorescent enamel having an excellent ability to phosphorescently emit light will be explained.

When the phosphorescent material is heated to high temperatures, it decomposes and stores light.

The ability to emit light is lost. For example, a luminescent phosphor made by adding copper to zinc sulfide decomposes when heated above 720°C. When a glaze containing a phosphorescent phosphor is baked onto a substrate to create phosphorescent enamel, the phosphorescent phosphor is heated to high temperatures and decomposes, and the resulting phosphorescent enamel is
The ability to phosphorescent and emit light becomes inferior.

Therefore, the inventors conducted repeated research in an attempt to obtain a phosphorescent enamel with excellent phosphorescent and light-emitting ability. As a result, it has been found that the structure of the luminescent enamel can be such that a transparent low-melting glass layer containing a luminescent phosphor is provided on the base. This is because low melting point glass can be fired at a low temperature, and baking at a low temperature will prevent the luminescent phosphor from decomposing.

It is necessary to select a type of low melting point glass that can be fired at a temperature lower than the decomposition temperature of the phosphorescent material.

In the case of a luminescent phosphor made of zinc sulfide and steel, it is necessary to use a low melting point glass that can be fired at 720° C. or lower. Examples of such low-melting glasses include compositions in which the proportions of active ingredients are varied.

5iOz: 56-63 mol B2O3: 3-1O mol Ti0z + Zr0z: 5-10 mol (However, both Ti0z and Zr0z are not O) 20 to Na2O+LizO+: 23-26 mok
% (However, NazO and LizO are not 0. F20 may be 0.) Fluoride 3 to 7 mol as diF2 Next, the raw materials of this low melting point glass composition will be explained.

The raw materials for the components constituting this low melting point glass composition include raw materials that produce oxides of the aforementioned components or mixtures of these oxides upon firing, or materials that produce fluorides of some of the oxides of the aforementioned components upon firing, and F2 components. Any raw material may be used as long as it produces fluorine. For example, silicic anhydride, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride,
Sodium silicate, potassium silicate, boric acid, sodium borate, lithium carbonate, zirconium oxide.

Titanium oxide, zirconium silicate, sodium fluoride,
Potassium fluoride, lithium fluoride, sodium nitrate, potassium nitrate, sodium silicofluoride.

Examples include potassium silicofluoride.

Next, a method for producing this low melting point glass composition will be explained. That is, the low melting point glass composition of the present invention is produced as follows.

(b) Select appropriate raw materials from the aforementioned raw materials and thoroughly grind and mix them at room temperature, heating if necessary. Of course, the glass may be melted without pulverization and mixing.

(Forward) The above mixture is heated and fired in a furnace to melt and vitrify it.

(c) 800 to 1300°C in the final stage of glass melting
Melt for 1 to 4 hours. Stir in between if necessary.

Note that pongee firing may be performed when melting the glass, if necessary. For example, when sodium carbonate and boric acid are used, the raw materials are first thoroughly mixed and reacted at room temperature. At this time, heat if necessary. Next, 1-3 at 150-500℃
Dehydrate while reacting for a while. In this way, solids 4r
obtain. Next, crush it. Next, (c) glass melting is performed. If this method (11) is used, dehydration and decarbonation hardly occur during glass melting, so the melt will not boil over from the inside, making it safe and convenient.

(e) In addition to the above, materials containing water as raw materials, carbonates,
If using ammonium salts, do the above before melting)
It is preferable to carry out a pre-calcination.

(f) Molten glass is either thrown into water to cool it quickly, or poured onto a thick iron plate to cool it.

()) The obtained glass is processed in a bot mill, vibratory mill.

Finely grind it using a grinder. In this way, the desired low melting point glass composition is obtained.

When making a phosphorescent enamel using a phosphor made of zinc sulfate and copper and a low melting point glass composition as described above, it is preferable to make it as follows.

First, 100 parts by weight of a low melting point glass composition (glass frit) is made into a slip by conventional mill blending, and then 5 to 50 parts by weight of a luminescent phosphor is added and mixed for a short time to form a slip for enamel. Create. Next, a slip is applied to the substrate by a conventional method such as spraying or dipping, and baked at 720°C (12) or lower to obtain luminous enamel (IL). It is clean and has excellent durability.

Next, reference examples and reference comparative examples will be explained. (Reference Example 1) Si0258.12 moles + 82037.5 moles +
T i O24,69mo” 4 + Zr0z 4.
69 mo”% + 12.5 moles of Na2O, LhO
A glass composition containing 12.5 mol of fluoride and 5 mol of fluoride in F2 equivalent amount (as 02 replacement amount) was made into a slip by the following mill formulation.

Glass frit 100 parts by weight Bentonite 0.41 Fine particle silicic acid 1.0' Sodium silicofluoride 0.1' Potassium chloride 0.41 Water 48 〃 The particle size of the slip is 2.7 g/200 mesh 0n15
It was a 0cc slip. The measurement method is described below. After accurately weighing 50 cc of slip and transferring it to a 200-mesh sieve, wash it with a gently flowing stream of water, being careful not to let it splatter.

After drying the residue on the sieve together with the sieve, accurately weigh the residue.

Next, add a luminescent phosphor (NP-3 manufactured by Hinami Electronics Co., Ltd.) to this slip.
201, composition ZnS: Cu) 20 parts by weight added.

A slip was obtained by mixing in a bot mill.

A white enamel plate prepared in advance by a conventional method was coated with this slip with Nubray and fired at 720°C to obtain luminous enamel.

This phosphorescent enamel had excellent phosphorescence and luminescence abilities, emitting a beautiful green glow when left in the dark after being exposed to the light of an electric lamp.

(Reference Example 2) Luminescent enamel was obtained in the same manner as in Reference Example 1, except that 10 parts by weight of the luminescent phosphor was added to the slip made in the same manner as in Reference Example 1. Although the amount of light emitted from this book was slightly lower than that of Reference Example 1, it still glowed brightly enough to be used for standard mh4, and had excellent phosphorescence and light emission abilities.

(Reference Example 3) Si0250 mol'1, B2O37.5 mol%,
Ti0z 4 mol%, Zr0z 3.5 mol%
, Nazo 9.5 mol%.

Using a glass composition with 12 mol% of Li2O, 5 mol% of K2O3, and 5.0 mol% of F2 substitution amount of fluoride,
Slip was made using the following mill formulation: Glass frit 100% No. 9 clay 51 Potassium chloride 0.51 Water 45 I Slip particle size was 1.8g/200mesh on 150c
It was a c-slip.

Next, 15 parts by weight of a phosphorescent phosphor was added to this slip to obtain a phosphorescent enamel in the same manner as in Reference Example 1. This phosphorescent enamel emitted beautiful light and had excellent phosphorescence and luminescence abilities.

(Reference Comparative Example 1) Luminescent enamel #1 was obtained in the same manner as Reference Example 3 using transparent frit hXF-44 manufactured by Nippon Ferro Co., Ltd. as the glass frit.

However, when fired at 720°C, a beautiful glossy enamel surface could not be obtained. Therefore, pressure was applied to perform firing at 820°C, but the resulting phosphorescent enamel had a slightly grayish color, the glass layer was devitrified, and the phosphorescent and light emitting effects were lost.

[Brief explanation of the drawing]

FIGS. 1 and 2 are longitudinal cross-sectional views of the luminescent enamel according to the present invention. 1... Substrate 3... Luminescent phosphor layer 4... Transparent glass layer Agent Patent attorney Takehiko Matsumoto Figure 1 IM Dear June 25, 159 Mr. Commissioner of the Patent Office! , Indication of the case 1980 Patent Application No. 080392 2 Name of the invention Luminescent Enamel 3 Relationship with the person making the amendment Patent applicant Address 1048 Kadoma, Kadoma City, Osaka Prefecture Name (5)
83) Matsushita Electric Works Co., Ltd. Representative Iku Kobayashi 4, Agent 5, Specification to be amended 6, Contents of the amendment ill In the 7th line of page 4 of the specification, the word ``is'' is replaced with ``is''.
is preferable,” he corrected. (2)

Claims (1)

[Claims] (1) A phosphorescent enamel in which a phosphorescent layer is provided between a base and a transparent glass layer.