JP2657748B2 - Production method of colored glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colored glass, and more particularly to a method for producing colored glass in which the surface of a base glass is transparently colored.

[0002]

2. Description of the Related Art Colored glass has greatly expanded its applications due to the tremendously developed optical application technology. Examples of applications include a color display, an optical filter, and the like, and a high-speed response element utilizing an optical nonlinear effect is expected in the future. For the characteristics required here, transparency is important in addition to color. Now, such a method for producing colored glass generally involves mixing a colorant with a low softening point glass (frit) powder, attaching the colorant to a glass substrate, and then baking. Such a method is disclosed in JP-A-61-6150. Further, the colorant colloidal coloring of Ag ₂ S-CuS system attached to the glass substrate, a method of coloring has been proposed by ion exchange.

[0003]

However, according to the conventional method,
First, dissolve the colorant in the frit when performing transparent coloring.
Powdered after melting at high temperature
That the glass substrate
Impairing mechanical properties, impure impurities for firing powder
Opaque colored glass
Problem. The present invention addresses such problems.
To improve the mechanical properties of the glass substrate.
Transparent glass with simple process
It is intended to provide a method for obtaining such information.

[0004]

That is, the present invention is characterized in that a thermodynamically unstable polymer layer is prepared, and a metal layer is adhered to the surface of the polymer layer. By heating the molecular layer below the melting temperature of the polymer and stabilizing the polymer layer, the ultrafine particles of metal or metal oxide that have been micronized from the metal layer can be dispersed in the polymer without agglomeration. The obtained polymer composite is dissolved in an organic solvent, and then the resulting solution is applied to a glass substrate, dried to remove the organic solvent, and then baked to diffuse and infiltrate ultrafine metal particles into the glass substrate. In a method for producing colored glass.

[0005] In addition, the polymer composite is obtained by evaporating and solidifying the polymer, or rapidly quenching the polymer, or applying a polymer dissolved in a solvent onto a substrate and then degassing at a high speed to remove the solvent. After preparing a thermodynamically unstable polymer layer obtained by the above, a metal layer is adhered to the surface of the polymer layer, and the polymer layer is heated below the melting temperature of the polymer to form a polymer layer. Is obtained by dispersing ultrafine particles of metal or metal oxide from the metal layer without coagulation in the polymer layer.

The polymer composite is prepared by dispersing the ultrafine particles of the metal or metal oxide obtained by the above-mentioned method without aggregating in the polymer layer, and then dispersing the polymer layer in sulfur vapor or H _The ultrafine particles are sulfurized by heat treatment in a 2S atmosphere.

In the method for producing a glassy material with ultrafine particles dispersed therein according to the present invention, a step of obtaining a polymer composite in which ultrafine particles of a metal or metal oxide are uniformly dispersed in a polymer, and dissolving this in an organic solvent. The method comprises a step of applying the melted substance on a substrate to form a dried film, followed by baking. First, in obtaining a polymer composite, first, the polymer layer is formed into a thermodynamically unstable state. Specifically, this is a vacuum deposition method in which a polymer is heated in a vacuum and evaporated to solidify a polymer layer on a substrate, and the polymer is melted at or above the melting temperature of the polymer. In this state, it is immediately poured into liquid nitrogen or the like, rapidly cooled, and rapidly cooled to adhere a polymer layer on the substrate. Alternatively, the polymer is dissolved in a solvent (concentration of 60% or less, preferably 20% or less).
There is a high-speed desolvation method in which a solvent is removed by degassing at a high speed (at least 240 l / min) while maintaining a constant temperature in a closed container after coating on a substrate. In this high-speed desolvation method, the polymer tends to return to a stable structure as the solvent decreases, but if the desolvation rate is high, it is not possible to return to a stable structure, and molding into a thermodynamically unstable state Can be.

In the case of the vacuum deposition method, the degree of vacuum of 10 ^-4 to 10 ^-6 Torr and the deposition rate of 0.1 to 100 μm / min, preferably 0.5 to 5 μm, using an ordinary vacuum deposition apparatus.
At m / min, a polymer layer can be obtained on a substrate such as glass. In the quenching and solidification method, a polymer is melted or melted, and cooled at a rate higher than the critical cooling rate inherent to the polymer to obtain a polymer layer. The resulting polymer layer is placed in a thermodynamically unstable state and shifts to an equilibrium state with the passage of time.

The polymer used in the present invention includes, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET),
Polyvinyl alcohol, polyphenylene sulfide (P
PS), polystyrene (PS), polycarbonate and the like.

Subsequently, the thermodynamically unstable polymer layer is transferred to a step of adhering a metal layer to its surface. In this step, the metal layer is laminated on the polymer layer by a method such as vapor deposition of a metal on the polymer layer by a vacuum vapor deposition device, or by directly adhering a metal plate to the polymer layer.

The metals used here are gold, silver, copper, iron,
Nickel, cobalt, tin, zinc, yttrium, indium, cadmium, chromium, titanium, palladium, manganese and the like.

The composite in which the metal layer and the polymer layer are in intimate contact with each other is heated at a temperature not lower than the glass transition point of the polymer and not higher than the melting temperature to shift the polymer layer to a stable state. as a result,
The metal becomes ultrafine particles of metal and metal oxide (Cu ₂ O) having a maximum particle size distribution in the range of 1 to 10 nm at 100 nm or less, and diffuses and penetrates into the polymer layer. The process continues until the layer is completely relaxed, and the metal layer adhering to the polymer layer also decreases in thickness and eventually disappears. The ultrafine particles are distributed in the polymer layer without aggregation.

Needless to say, in the present invention, the above-mentioned polymer composite may be subjected to a heat treatment in a sulfur vapor or an H ₂ S atmosphere to sulfide the ultrafine particles.

The obtained polymer composite is mixed and dissolved in a solvent comprising an organic solvent such as meta-cresol, dimethylformamide, dichloromethane, formic acid and the like, and the metal, metal oxide or ultrafine particles of the metal oxide are uniformly dispersed. The resulting ultrafine particle dispersion paste is used. Since the ultrafine particles have a small particle size and interact with the polymer, separation and precipitation from the polymer and aggregation of the ultrafine particles do not occur in the paste. In this case, the content of the ultrafine particles of metal or metal oxide is 0.01 to 80% by weight.

[0015] In some cases, the polymer composite is dissolved in an organic solvent such as meta-cresol, dimethylformamide, dichloromethane, and formic acid, and the dissolved product is placed in a container and centrifuged. As a result, the melt is separated into two layers, a concentrated layer containing a large amount of ultrafine particles and a polymer layer containing almost no ultrafine particles, and only the concentrated layer is recovered. The content of ultrafine particles in this concentrated layer is as high as 90% by weight or more.

The concentrated layer of the polymer composite thus prepared is applied to a glass substrate and dried at 60 to 120 ° C. in the atmosphere for 10 minutes to remove the organic solvent, or deaerated in a closed container. While drying to obtain a sample. Subsequently, the sample thus obtained is fired in air, in a vacuum, or in an inert gas. Specifically, it is a method of baking at a temperature of 300 to 800 ° C., which is higher than the decomposition temperature of the polymer in the polymer composite. The ultrafine metal particles that have been diffused and permeated are ionized.

[0017]

Next, the present invention will be described in more detail with reference to specific examples. Example 1 Using a vacuum evaporation apparatus, 5 g of nylon 11 polymer pellets were put into a tungsten board, and 10 ^-6 Torr
Reduce the pressure. Next, a voltage is applied to heat the tungsten board in a vacuum to melt the polymer, and the substrate is placed on a substrate (glass plate) placed on the tungsten board.
A polymer layer of a vapor deposited film having a thickness of about 5 μm was obtained at a rate of about 1 μm / min at a degree of vacuum of ⁻⁴ to 10 ⁻⁶ Torr. The molecular weight of the polymer layer is about 1/2 to 1/10 of the polymer pellet.

Further, the gold chip was placed in a tungsten board, heated and melted, and vapor-deposited at a degree of vacuum of ^{10.sup.- 4} to ^10.sup.-6 Torr to deposit a gold vapor-deposited film on the polymer layer. This was taken out of the vacuum evaporation apparatus and left in a thermostat kept at 120 ° C. for 10 minutes to obtain a composite. as a result,
This polymer composite contained about 40% by weight of ultrafine gold particles and had a size of 4 to 8 nm.

[0019] The polymer mixture composite into m- cresol in a weight ratio proportion of polymer composite / m- cresol = 1/1, dissolved, which was coated on a soda-lime glass substrate, 10 ^-3 It was dried at 100 ° C. for 10 minutes under a reduced pressure of Torr to remove m-cresol. The obtained sample was
When baked in air at 00 ° C. and 700 ° C. for 20 minutes, the glass surface was colored red in each case. Also,
Even if this colored surface was polished with a stainless steel nonwoven fabric, the color was not erased and the colored layer did not fall off.

Example 2 In the same manner as in Example 1, copper was used instead of gold, and Cu ₂
A polymer composite containing ultrafine particles of O was obtained. This polymer composite contained about 80% by weight of ultra-fine particles of Cu ₂ O, and its size was 1 to 5 nm. The polymer composite is m
-Polymer complex with cresol / m-cresol = 1/1
Were mixed and dissolved at a weight ratio of 10%, and this was applied onto a soda-lime glass substrate, and then dried under reduced pressure of 10 ⁻³ Torr.
After drying at 0 ° C. for 10 minutes, m-cresol was removed.
When the obtained sample was baked at 700 ° C. for 20 minutes in air, the glass surface was colored blue. Even when the colored surface was polished with a stainless steel nonwoven fabric, the color did not disappear, and the colored layer did not fall off.

COMPARATIVE EXAMPLE 1 Gold powder (particle size: 1 μm) corresponding to a gold content of 40% by weight and nylon 11 were added to m-cresol (gold powder and nylon 1).
1 / m-cresol) = 1/1 at a weight ratio.
This is soda. Apply on lime glass substrate, 10 ^-3 T
It was dried at 100 ° C. for 10 minutes under reduced pressure of orr to remove m-cresol. When the obtained sample was baked at 700 ° C. for 20 minutes in air, the glass surface was not colored.

[0022] Comparative Example 2 Cu ₂ Cu ₂ O powder corresponding to the O content 80% by weight (particle size 0.5 [mu] m) and nylon 11, and m- cresol (Cu ₂ O powder nylon 11 / m- cresol ) = 1 /
The mixture was applied on a soda-lime glass substrate at a weight ratio of 1 and was heated to 100 ° C. under a reduced pressure of 10 ⁻³ Torr.
For 10 minutes to remove m-cresol. When the obtained sample was baked at 700 ° C. for 20 minutes in air, the glass surface was not colored. As a result, in this example, since the particle diameter of the metal or metal oxide in the polymer composite was extremely small as compared with that of the comparative example, the ultrafine particles of the metal or metal oxide diffused and penetrated into the glass substrate. You can see that

[0023]

As described above, according to the present invention, a polymer layer which is unstable thermodynamically is prepared, and a metal layer is adhered to the surface of the polymer layer. To stabilize the polymer layer by heating below the melting temperature, to use the polymer composite obtained by dispersing ultrafine particles from the metal layer without agglomeration in the polymer Since it can be fired at a relatively low temperature and does not use a glass frit, there is an effect that a transparent colored glass can be obtained by a simple process without impairing the mechanical properties of the glass substrate.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yoshio Yamaguchi 4-1-1-21 Hamazoedori, Nagata-ku, Kobe Examiner of Mitsuboshi Belting Co., Ltd. Hitoshi Misaki

Claims (2)

(57) [Claims] 1. A method for producing a thermodynamically unstable polymer layer,
After the metal layer is brought into close contact with the surface of the polymer layer, the polymer layer is heated below the melting temperature of the polymer to stabilize the polymer layer, thereby making the metal or metal oxide ultra-fine particles from the metal layer. The polymer composite obtained by dispersing the ultrafine particles of the product without aggregating in the polymer was dissolved in an organic solvent, and then the dissolved product was applied on a glass substrate and dried to remove the organic solvent. Thereafter, the method is fired to diffuse and infiltrate ultrafine metal particles into a glass substrate. 2. A polymer composite forms a thermodynamically unstable polymer layer, a metal layer is adhered to the surface of the polymer layer, and the polymer layer is heated to a melting temperature of the polymer. By heating below to stabilize the polymer layer, the ultrafine particles of the metal or metal oxide converted into ultrafine particles from the metal layer are dispersed without agglomeration in the polymer, and the polymer layer is further dispersed in sulfur vapor. or method for producing a colored glass according to claim 1, wherein by heat treatment in a H ₂ S atmosphere is obtained by sulfurization of the ultrafine particles.