JP2003201149A - Method of coloring glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of coloring glass by coloring the glass with a laser beam, thereby enabling fine writing and providing the easily decolorable and recyclable glass in spite of coloring the glass. <P>SOLUTION: The method of coloring the glass by irradiating the glass into which silver ions are incorporated with a laser beam from a laser irradiator consisting of a laser oscillator, optical modulator, galvanometer, and a condenser lens and objective lens or fθ lens mounted on a linear translator, thereby coloring the glass with the silver ions flocculated as silver particulates. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for coloring glass by irradiating it with high energy light.

[0002]

2. Description of the Related Art A method of irradiating a transparent material with a laser beam to perform laser marking is disclosed in JP-A-2-242220, JP-A-3-124486, and JP-A-4-71.
It is disclosed in Japanese Patent Laid-Open No. 792 and Japanese Patent Laid-Open No. 11-156568.

For example, in Japanese Unexamined Patent Publication No. 2-242220, in a spectacle frame provided with a transparent plastic that absorbs laser light, the plastic is irradiated with laser light to cause a burnt pattern to appear inside. And a framed spectacle frame component having a pattern is disclosed. However, the method described in this publication has a problem that the object is limited to a material such as plastic that causes a charring by irradiation with laser light.

Further, Japanese Patent Laid-Open No. 3-124486 discloses a laser marking method in which a laser beam is focused on the inside of an object to mark the inside without damaging the surface. However, in the laser marking method described in the publication, when the object is glass, there is a problem that when the laser light is focused inside, a crack may occur and reach the surface, which makes the object fragile. It was

Further, in Japanese Patent Laid-Open No. 4-71792,
There is disclosed a method of marking by selectively opaqueizing the inside of the transparent substrate by irradiating the inside of the transparent substrate with a laser beam so as to focus. However, in the marking method described in this publication, it is possible to mark the inside of the glass by laser irradiation,
Since the focus position of the laser beam cannot be strictly controlled in the depth direction of the material, there is a problem that it is not suitable for marking a thin transparent material.

Further, in Japanese Patent Application Laid-Open No. 11-156568, laser light in a wavelength range which transmits a marking object is
A method of marking by focusing on the inside of an object using an fθ lens is disclosed. However, in the marking method described in the publication, since the marking is due to internal cracks caused by irradiation with laser light,
There is a problem that marking objects are limited to transparent materials.

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
No. 0, JP-A-3-124486, JP-A-4-124
The method described in Japanese Patent No. 71792 or Japanese Patent Application Laid-Open No. 11-156568 is a method of laser-marking characters, patterns, etc. on a transparent material such as plastic or glass, but the laser light is condensed inside the transparent material. As a result, since marking is performed by using a scorching pattern inside the plastic or making the glass opaque due to the occurrence of cracks, there is a problem that it is difficult to make extremely fine marking in the unit of micron (μm).

Further, the colored glass is usually colored with a transition metal ion by adding a transition metal to the glass raw material as a coloring source, and the colored film-coated glass is
It is manufactured by coating a colored film in which an inorganic pigment or a metal oxide is dispersed in a transparent matrix such as silica or titania. Thus, the colored glass and the glass with the colored film are
Since it is colored with a metal such as a transition metal ion or a metal oxide, it is difficult to recycle. That is, there is a problem that the color remains even after melting, and glasses of different colors cannot be melted in the same melting furnace and cannot be recycled.

It is an object of the present invention to provide a method for coloring recyclable glass, in which not only fine writing can be performed by coloring the glass with laser light, but also the glass can be easily erased even if it is colored. To do.

[0010]

Means for Solving the Problems The present invention irradiates a glass containing silver ions with a laser beam to agglomerate silver ions to deposit silver fine particles, and by colloid resonance absorption of the deposited silver fine particles, In this method, the transmitted color is yellow and the reflected color is silver.

When the glass colored according to the present invention is heated to the softening point or higher, silver fine particles as a coloring source diffuse into the inside of the glass to erase the color, so that the glass can be colored and erased.

The present invention can also be applied to recycling colored glass.

As a result of earnest studies, the present inventors have found that a glass obtained by immersing a molten salt containing heated silver in the glass and ion-exchanging sodium ions inside the glass with silver ions in the molten salt is transparent. If silver particles are aggregated on the surface by focusing and irradiating high-energy light, for example, high-intensity laser light, the transmission color is colored yellow and the reflection color is silver due to colloid resonance absorption of the silver particles. I found that.

Although it is possible to color the entire silver ion-containing glass by radiant heating to a temperature below the softening point in a heating furnace or the like, if radiant heating is used, fine writing due to coloring cannot be performed. . By irradiating a laser beam without radiative heating in a heating furnace or the like, silver ions in the above-mentioned glass containing silver ions are aggregated to precipitate fine silver particles, and coloring can be performed to enable fine drawing. .

Furthermore, the inventors of the present invention heat the above-mentioned colored glass colored in a transmitted color of yellow and a reflected color of silver by irradiation of a laser beam to a temperature equal to or higher than the softening point, thereby agglomerating the silver fine particles on the surface. It was found that the pigment diffused inside the glass and disappeared.

The present invention is a method for coloring glass, characterized in that the glass containing silver ions is irradiated with high energy light to aggregate the silver ions to form fine silver particles for coloring.

Furthermore, the present invention is a method of coloring a glass as described above, wherein a silver irradiation is performed by a laser irradiation device including a laser oscillator, an optical modulator, a condenser lens mounted on a linear translator, an objective lens and a galvanometer mirror. The glass coloring method is characterized by irradiating a glass containing the above with a laser beam to agglomerate silver ions to form silver fine particles and coloring.

Furthermore, the present invention relates to the above glass coloring method, wherein the glass containing silver ions is irradiated with laser light from a laser irradiation device comprising a laser oscillator, an optical modulator, a galvanometer mirror and an fθ lens. By so doing, silver ions are aggregated to form fine silver particles, which are colored.

Further, in the present invention, the laser oscillator is a carbon dioxide laser oscillator, a UV pulse laser oscillator or an argon ion laser oscillator, and the type of laser light used is infrared light, near infrared light, visible light or ultraviolet light. The above method for coloring glass is characterized by the above.

Furthermore, the present invention is the above glass coloring method, wherein the light modulator is an acousto-optic modulator or an electro-optic modulator.

Furthermore, the present invention is the above glass coloring method characterized in that the irradiation position of the laser light on the glass is moved by a plurality of galvanometer mirrors.

Further, the present invention is the glass coloring method as described in any one of the above, characterized in that the glass is moved by a stage movable in the horizontal direction and / or the vertical direction.

Further, the present invention is a glass which is colored by the above glass coloring method.

Further, the present invention is a glass characterized in that a character, a pattern, or a bar code is drawn by the above glass coloring method.

Further, the present invention is a method for erasing the colored portion by heating the above glass to a temperature above its softening point.

The laser oscillator, which is a component of the laser irradiation apparatus used in the method for coloring glass of the present invention, includes a continuous laser oscillator that continuously emits laser light and a pulse laser oscillator that emits laser light in a pulsed manner. Either one may be used. For example, a carbon dioxide laser oscillator, a YAG laser oscillator, a UV pulse laser oscillator, an argon ion laser oscillator, or the like, which is a high-power laser oscillator, can be used.

The type of laser light used is infrared light,
Near-infrared light, visible light or ultraviolet light can be mentioned, and a wavelength of 100
Light having a wavelength of not less than 1 nm and not more than 1 mm (10 ⁶ nm) can be used, and for example, a carbon dioxide gas laser oscillator, a UV pulse laser oscillator or an argon ion laser oscillator can be used.

The optical modulator, which is a constituent of the laser irradiation apparatus used in the glass coloring method of the present invention, functions as a switching element. That is, by changing the traveling direction of the laser light or switching between shielding and transmitting, the ON / OFF of the irradiation of the laser light on the workpiece is accurately controlled. By turning on / off, characters and drawings become discontinuous, and various drawing can be supported. As the optical modulator, either an acousto-optic modulator (hereinafter abbreviated as AOM) or an electro-optic modulator (hereinafter abbreviated as EOM) may be used.

In the ON state, the AOM propagates ultrasonic waves to quartz glass by a piezoelectric element, that is, a transducer that converts RF waves in the radio frequency range into ultrasonic waves, and forms a diffraction grating by the density fluctuations of the quartz glass. It is a switching element that diffracts the laser light and changes its optical path. When the laser light is OFF, the laser light goes straight into the quartz glass.

The EOM is a switching element for passing or blocking the laser light by a polarizing plate by applying a voltage to the laser light to change the polarization direction.

The galvanometer mirror, which is a component of the laser irradiation device used in the glass coloring method of the present invention, is composed of a plurality of movable mirrors, usually an X mirror and a Y mirror. It is possible to shake the optical axis of. It is possible to color the glass with high precision by adjusting the angle of the X mirror and the Y mirror while operating and adjusting the optical axis to move the irradiation position of the laser light onto the glass as the object. Characters, patterns or barcodes can be drawn on. For example, not only can character information such as manufacturing number, manufacturing date, and manufacturer name, or one-dimensional and two-dimensional bar codes be easily written on glass, but laser light can be narrowed down to 1 mm.
It is necessary to have a resolution capable of writing several tens of lines or more within the interval, and precise drawing can be performed.

Further, the method of the present invention using laser light irradiation has a small energy loss, a short tact time in actual production, and is excellent in economical production.

As a component of the laser irradiation device used in the glass coloring method of the present invention, a condenser lens and an objective lens mounted on a linear translator, or an fθ lens is a laser beam scanned in an arc shape by a galvanometer mirror. It corrects the focal point position of and collects it on a plane to play a role of improving the drawing resolution.

A stage which is a constituent of a laser irradiation apparatus used in the method for coloring glass of the present invention and which is movable in the horizontal direction and / or the vertical direction, for example, an X-Y axis which is movable in the horizontal direction with respect to the irradiation surface. The glass can be colored efficiently by moving the glass when the laser beam is scanned at a high speed by the Z-axis stage movable in the direction perpendicular to the stage. Further, by moving the glass attached to the movable stage at a constant interval and then making the glass stand still, the laser beam is scanned by the above-mentioned galvanometer mirror to perform drawing, thereby making it possible to draw a plurality of pieces at equal intervals. .

Further, since the silver ions of the glass containing the silver ions used in the present invention are present in a very small amount on the glass surface, the colored glass portion is heated to a temperature above its softening point and melted by heating. Since it returns to colorless and transparent, it is easy to recycle the removable colors.

The glass containing silver ions used in the present invention is not limited to plate glass and may be bottle glass, and its shape is not limited.

[0037]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is an explanatory view of an example of a laser drawing apparatus used in the present invention which uses a condenser lens and an objective lens for controlling the focal position of laser light.

The laser oscillator 1 shown in FIG. 1 is a carbon dioxide laser oscillator or an ultraviolet, that is, a UV pulse laser oscillator. A UV pulse laser oscillator is usually AO
An optical modulator consisting of M or EOM has already been incorporated, commonly known as a Q-switch. Of the condenser lens 2 and the objective lens 3, by moving the condenser lens 2 mounted on a linear translator (not shown) on the optical axis by the linear translator, a laser beam on the irradiation surface of the silver ion-containing glass as the target 6 is obtained. Control the diameter.

The laser beam emitted from the carbon dioxide gas laser oscillator or the UV pulse laser oscillator passes through the condenser lens 2 and then the objective lens 3, is reflected by the X mirror 4 and the Y mirror 5 which are galvanometer mirrors, and thereafter. The silver ion-containing glass, which is the target 6, is irradiated with the laser light to irradiate the silver ion-containing glass with a laser beam. The coloring of the silver ion-containing glass is carried on the XYZ-stage 7 composed of an XY axis stage movable horizontally with respect to the irradiation surface and a Z axis stage movable vertically, while moving the stage 7. It is also possible to scan the glass containing silver ions with laser light.

The control signal input to the computer 8 as digital command data and converted into an analog signal by the digital-analog converter 9 is
Received by the servo driver 10, the servo driver 10
However, the condensing lens 2 and the X mirror 4 and the Y mirror 5 which are galvanometer mirrors are driven while being controlled, and the irradiation position of the laser beam on the silver ion-containing glass is moved. Fine writing can be performed by the colored portion formed by irradiating the silver ion-containing glass with laser, and the written content can be easily changed by changing the digital command data.

FIG. 2 shows fθ for controlling the focus position of laser light.
It is explanatory drawing of an example of the laser drawing apparatus used for this invention using a lens.

The laser light emitted from the argon ion laser oscillator, which is the laser oscillator 1, passes through the AOM 12, which is a switching element, and then is reflected by the X mirror 4 and the Y mirror 5, which are galvanometer mirrors.
After passing through the θ lens 13, the silver ion-containing glass that is the target 6 is irradiated with the laser light, and the laser light irradiation portion on the silver ion-containing glass is colored. The fθ lens 13 focuses the laser beam scanned by the galvanometer mirror on the silver ion-containing glass that is the target 6.

The silver ion-containing glass is colored by an XYZ-stage 7 consisting of an X-Y axis stage movable in the horizontal direction and a Z axis stage movable in the vertical direction with respect to the irradiation surface.
It is also possible to scan the silver ion-containing glass with laser light while moving the stage 7.

The digital command data input to the computer 8 is converted into an analog signal by the digital-analog converter 9. AOM driver 11
Is transmitted from the computer 8 and is digital / analog /
The laser modulation signal converted into an analog signal by the converter 9 is converted into a radio frequency signal, that is, an RF signal, and ultrasonic waves are generated in the AOM 12 via a piezoelectric element (not shown), that is, a transducer. A
The laser light incident on the OM 12 is diffracted by the diffraction grating formed by the ultrasonic waves, and its optical path changes. As a result, the laser light is turned on / off. On the other hand, the control signal input to the computer 8 as digital command data and converted into an analog signal by the digital-analog converter 9 is received by the servo driver 10, and the servo driver 10 causes the X mirror 4 which is a galvanometer mirror. The Y mirror 5 is driven while being controlled, and the irradiation position of the laser light on the silver ion-containing glass that is the target 6 is moved. In addition, target 6
The content of writing to the silver ion-containing glass by laser light can be easily changed by changing the digital command data.

The stage 7, which is a component of the laser drawing apparatus used in the glass drawing method of the present invention, is, for example, an X-Y axis stage movable in the horizontal direction and a Z movable in the vertical direction with respect to the irradiation surface. It is composed of an axial stage, and when the laser beam is scanned at high speed, the glass containing silver ions can be moved to efficiently color the glass. In addition, the silver ion-containing glass attached to the movable stage 7 is moved at a constant interval, then is made to stand still, and the laser beam is scanned by the galvanometer mirror to perform coloring, so that the character is printed by the coloring portion. It is possible to draw a plurality of figures, patterns, barcodes, etc. at regular or irregular intervals.

The glass 6 colored by the coloring method of the present invention is the glass 6 containing silver ions. The glass 6 is obtained by immersing it in a molten salt of silver nitrate or the like to cause sodium ions inside the glass 6 and silver ions to be ion-exchanged to contain silver ions in the glass 6, and thus is transparent. By irradiating the glass 6 with laser light, for example, the transmission color of the irradiation portion can be colored yellow and the reflection color can be colored silver.

The glass coloring method of the present invention is superior in durability without damaging the glass and irradiating the glass with light, as compared with the conventional method of marking the glass which causes a crack in the condensing portion of the laser light. It has excellent contrast with the non-exposed portion, and may be applicable to a recording medium by the precise drawing of the laser irradiation apparatus used in the present invention.

A carbon dioxide gas laser oscillator or a UV pulse laser oscillator is used as the laser oscillator 1 shown in FIG.
A laser irradiation device using a condenser lens 2 and an objective lens 3 for controlling the focus position of laser light, and an argon ion laser oscillator as the laser oscillator 1 shown in FIG.
Differences when the laser irradiation device using the fθ lens 13 for controlling the focus position of the laser light is used in the method for coloring silver ion-containing glass of the present invention will be described.

The irradiation apparatus of FIG. 1 uses a carbon dioxide gas laser oscillator or a UV pulse laser oscillator. Compared with the argon ion laser oscillator used in the irradiation apparatus of FIG. A dark color density is obtained at the output.

In particular, when a carbon dioxide gas laser oscillator is used, the output of laser light is increased to scan the silver ion-containing glass at a high speed for coloring, and coloring of a large area of glass is possible.

The irradiation device of FIG. 1 can change the working distance, and the irradiation diameter of the laser light can be changed by moving the condenser lens 2 mounted on the linear translator on the optical axis of the laser light. It can be changed freely. The irradiation device shown in FIG. 2 uses an argon ion laser which is visible light as a light source, while the irradiation device shown in FIG.
The irradiation device uses a UV pulse laser which is ultraviolet light as a light source. Since the wavelength of ultraviolet light is shorter than that of visible light, the ultraviolet laser has a smaller irradiation diameter than the visible light laser, and the line width of the trace line when scanning the laser light is made thinner,
More precise drawing is possible. Since visible light generally passes through glass, the inside of the glass containing the photosensitive material can be colored by a visible light laser. Since infrared light is absorbed by the glass, the surface of the glass containing the photosensitizer can be colored by an infrared light laser. An infrared laser generally has a high output and a large spot diameter, so that a large area of glass can be colored at high speed.
It is preferable that the type of laser is appropriately selected in consideration of the light transmittance of glass and the absorptivity.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.

[0053]

EXAMPLE 1 A carbon dioxide laser oscillator was used as a laser oscillator 1, and as shown in FIG. 1, a condenser lens 2, an objective lens 3, an X mirror 4 in a galvanometer, and a Y mirror mounted on a linear translator. 5. Horizontally movable XY
It is composed of a holder attached to an XYZ-stage 7 composed of an axial stage and a Z-axis stage movable in the vertical direction, and a silver ion-containing glass as a target 6 is attached to the holder.

The glass containing silver ions was composed of a plate having a thickness of 5 mm, a size of 100 mm square, a composition of SiO ₂ , 72 wt% and Na.
₂ O, 16 wt%, CaO, 10 wt%, Al ₂ O ₃ , 2
a soda lime glass substrate by the wt% float method,
AgNO ₃ and NaN at a temperature of 590K (317 ° C)
5 minutes or 15 minutes in molten salt prepared by mixing O ₃ in a molar ratio of 1: 4
It was prepared by immersing for minutes and exchanging Na ions on the glass surface with silver ions.

From the carbon dioxide laser oscillator, the wavelength 1060
0 nm, repetition frequency 10 kHz or 20 kHz,
The laser beam oscillated with an average output of 1W, 2W, 5W, 10W, or 20W was focused by the condenser lens 2 into a laser beam, reflected by the X mirror 4 and the Y mirror 5, and attached to the holder. Board thickness 5 mm, size 100
A line interval of 25 μm, 100 μm or 250 μm on the surface of the silver ion-containing glass that is the mm-square target 6.
Scanning speed 240 mm / s, 1200 mm / s or 50
Scanned at 00 mm / s and colored yellow or brown with a size of 10 mm x 10 mm square or 10 mm x 90
A rectangle of mm was drawn.

The silver ion-containing glass is colored yellow or brown by irradiating a carbon dioxide laser on both the top surface and the bottom surface of the glass obtained by the float method, and outputs when the scanning speed is 240 mm / s. , The silver ion-containing glass was colored yellow in the range of 1 to 20 W. Output when the scanning speed is 1200 mm / s, 2
Not colored with W, but brown with 10W
In W, it was colored yellow. When the scanning speed was 5000 mm / s, coloring did not occur at the output of 2 W, but it was colored brown at the output of 20 W and yellow at 50 W.

Further, the color tone of the laser light irradiation portion is float.
Ion-exchange the plate glass by the method of
Ag at a temperature of 590K (317 ° C) at the time of manufacturing
NO ₃And NaNO₃Dip in molten salt mixed at a molar ratio of 1: 4
It did not change depending on the length of the pickling time.

The color density of the laser light irradiation portion was set to a temperature of 590 K (317 ° C.) when the plate glass by the float method was ion-exchanged to prepare a glass containing silver ions.
It was darker when the time of immersion in the molten salt in which gNO ₃ and NaNO ₃ were mixed at a molar ratio of 1: 4 was longer, the bottom surface was slightly darker than the top surface, and the narrower the line spacing, the darker.

Size 9 when the scanning speed is 5000 m / s
The coloring time for 0 mm × 10 mm (grating having a line interval of 10 lines / mm) was 2 seconds, and the silver ion-containing glass could be colored in a short time.

When the thus colored glass 6 was heated to a temperature above the softening point of the soda lime silver ion-containing glass and melted, the entire surface was decolored.

The stage 7 and the holder were devised so that not only plate glass but also colored bottles could be attached. Example 2 As a laser oscillator 1, a UV pulse laser oscillator is used, and as shown in FIG. 1, a condenser lens 2 mounted on a linear translator, an objective lens 3, an X mirror 4 in a galvanometer 4, a Y mirror 5, a horizontal mirror. XY that can move in any direction
It is composed of a holder attached to an XYZ-stage 7 composed of an axial stage and a Z-axis stage movable in the vertical direction, and a silver ion-containing glass as a target 6 is attached to the holder.

The silver ion-containing glass is composed of a plate having a thickness of 5 mm, a size of 100 mm square, a composition of SiO ₂ , 72 wt% and Na.
₂ O, 16 wt%, CaO, 10 wt%, Al ₂ O ₃ , 2
wt% soda lime glass substrate at a temperature of 590K (3
(17 ° C.) AgNO ₃ and NaNO ₃ molar ratio 1: 4
It was prepared by immersing in the molten salt mixed in 1. for 1 hour and exchanging Na ions on the glass surface with silver ions. The silver ion-containing glass had the same size as that used in Example 1,
A silicate glass having the same composition was ion-exchanged under the same conditions and was the same as that used in Example 1.

From the UV pulse laser oscillator, wavelength 355
nm, pulse width 20 ns, pulse energy 80 μJ,
A laser beam oscillated at an average output of 2 W and a repetition frequency of 25 kHz is focused by a condenser lens 2 into a laser beam, reflected by an X mirror 4 and a Y mirror 5, and attached to a holder. The surface of the silver ion-containing glass, which is a 100 mm square target 6, was scanned at a line width of 10 μm and a scanning speed of 250 mm / sec to draw a rectangle colored in yellow and having a size of 9 mm × 15 mm.

Next, by operating the XYZ-stage 7 to move it horizontally, a plurality of rectangles could be drawn at equal intervals.

Further, the line spacing of the trace lines of the laser beam is, for example, 2.5 μm, 5 μm, 10 μm, 15
It is possible to adjust to μm, 25 μm, 50 μm, 100 μm, 200 μm and the like.

Table 1 shows pulse energies of 80 μJ, shot intervals of 10 μm, and laser beam trace line intervals of 2.5 μm and 5 μm using the apparatus shown in FIG.
m, 10 μm, 15 μm, 25 μm, 50 μm, 100
9 mm x 15 at a scanning speed of 250 mm / sec on the surface of the glass containing silver ions in place of 100 μm and 200 μm.
It is a diagram in which a visible light transmittance is measured when a rectangle of mm is drawn and colored from pale yellow to brown.

[0067]

[Table 1]

The visible light transmittance was measured according to JIS Z 8722 and JIS by measuring the transmittance between wavelengths 340 and 1800 nm with a spectrophotometer (manufactured by Hitachi Ltd., model 340).
It was determined according to R3106 or JIS Z 8701.

As shown in Table 2, the line width of the trace line of the laser beam is 46% when the line width is 2.5 μm and 46% when the line width is 5 μm.
%, 10% at 55 μm, 59% at 15 μm, 64% at 25 μm, 72% at 50 μm, 79% at 100 μm, and 82% at 200 μm. If laser output is the same, the narrower the trace line spacing, the more visible The light transmittance becomes low, and it is possible to change the visible light transmittance by changing the line spacing.

On the other hand, the laser output is increased and the irradiation diameter of the UV laser is not narrowed down by the condenser lens 2 mounted on the linear translator.
When the stage 7 was moved horizontally at a speed of 100 mm / sec and the UV laser light was scanned on the silver ion-containing glass as the target 6, the entire surface of the silver ion-containing glass could be colored.

When the glass 6 was heated to a temperature above the softening point of the soda lime silver ion-containing glass and melted, the entire surface was decolored. Example 3 As shown in FIG. 2, the laser irradiation apparatus includes a laser oscillator 1
Argon ion laser oscillator, AOM 12, X mirror 4, Y mirror 5, fθ lens 1 in galvanometer
3 and a holder attached to an XYZ-stage 7 composed of an XY-axis stage movable horizontally with respect to the irradiation surface and a Z-axis stage movable vertically, and a silver ion as a target 6 in the holder. A containing glass is attached.

The silver ion-containing glass is a silicate glass of the same size and composition as used in Example 1, which is ion-exchanged under the same conditions, and is the same as that used in Example 1. .

The output of the laser beam oscillated from the argon ion laser oscillator is set to 2.2 W, the irradiation diameter of the laser beam is reduced to 50 μm by the fθ lens 13, the ON / OFF of the laser beam by the AOM 12 and the X mirror 4 and By manipulating the angle of the Y mirror 5, the optical axis of the laser light is shaken,
The pattern could be freely drawn by the trace line colored in yellow with a width of 50 μm.

Further, the irradiation diameter of the laser beam was adjusted to 50 μm, and the laser beam was scanned at a scanning speed of 10 mm / sec to draw the letter G in the range of 7 mm in length and 6 mm in width. Next, by operating the XYZ-stage 7 to move it horizontally at equal intervals, and then stationary, a plurality of G symbols could be drawn at equal intervals. The part irradiated with laser light,
That is, the trace line was colored with yellow as the transmission color and silver as the reflection color due to the deposition of silver fine particles.

Further, the laser output is increased and the irradiation diameter is not narrowed, irradiation is performed with an irradiation diameter of 2 mm, and the XYZ-stage 7 is horizontally moved at a speed of 100 mm / sec to scan the silver ion-containing glass with laser light. As a result, the entire surface of the glass containing silver ions could be colored in a short time.

When the silver ion-containing glass was heated to a temperature above the softening point of soda lime silicate glass and melted, the entire surface was decolored.

The stage 7 and the holder were devised so that not only plate glass but also colored bottles could be attached.

[0078]

Industrial Applicability The glass coloring method of the present invention is a method of accurately irradiating a laser beam on the surface of a glass containing silver ions which can be colored by laser light irradiation to color the glass, and partially coloring the glass. By coloring, letters, patterns, barcodes, etc. can be delicately drawn on the glass. Further, by moving the movable stage at regular intervals, it is possible to draw a plurality of characters, patterns, barcodes, etc. at regular intervals.

The laser device used in the present invention can color the entire surface of the glass by irradiating the entire surface of the glass with a laser beam while performing high-speed scanning. In particular, when a carbon dioxide laser oscillator is used as the laser oscillator, the transparent glass can be colored brown or yellow by laser irradiation in a short time, and a large-area plate glass can be colored at an extremely high speed.

When the glass colored by this method is heated to a temperature above its softening point and melted, the colored portion returns to colorless and transparent, which facilitates recycling.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of an example of a laser irradiation apparatus used in the present invention, which uses a condenser lens and an objective lens for controlling a focal position of laser light.

FIG. 2 is an explanatory diagram of an example of a laser irradiation apparatus used in the present invention, which uses an fθ lens for controlling the focus position of laser light.

[Explanation of symbols]

1 Laser oscillator 2 condenser lens 3 Objective lens 4 X mirror 5 Y mirror 6 target (silver ion containing glass) 7 XYZ-stage

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Takashi Yamate, the inventor             Central, 1510 Oguchi-cho, Matsusaka City, Mie Prefecture             Glass Co., Ltd. Glass Research Center (72) Inventor Shinji Nishikawa             Central, 1510 Oguchi-cho, Matsusaka City, Mie Prefecture             Glass Co., Ltd. Glass Research Center (72) Inventor Hiroyuki Tamon             Central, 1510 Oguchi-cho, Matsusaka City, Mie Prefecture             Glass Co., Ltd. Glass Research Center (72) Inventor Hiroshi Uemura             Central, 1510 Oguchi-cho, Matsusaka City, Mie Prefecture             Glass Co., Ltd. Glass Research Center (72) Inventor Shigeru Mori             Central, 1510 Oguchi-cho, Matsusaka City, Mie Prefecture             Glass Technology Co., Ltd. (72) Inventor Koji Utagawa             1-225 Nagara Nishi, Kita-ku, Osaka City, Osaka Prefecture             Within Osaka Seiko Glass Co., Ltd. (72) Inventor Yoshihide Mori             1-225 Nagara Nishi, Kita-ku, Osaka City, Osaka Prefecture             Within Osaka Seiko Glass Co., Ltd. (72) Inventor Kohei Kakuno             1-83-1 Midorigaoka, Ikeda, Osaka Prefecture             AIST Kansai Center             Within (72) Inventor Tomoko Akai             1-83-1 Midorigaoka, Ikeda, Osaka Prefecture             AIST Kansai Center             Within (72) Inventor Masaru Yamashita             1-83-1 Midorigaoka, Ikeda, Osaka Prefecture             AIST Kansai Center             Within (72) Inventor Tetsuo Yazawa             1-83-1 Midorigaoka, Ikeda, Osaka Prefecture             AIST Kansai Center             Within F-term (reference) 2C362 AA02 BA17 BA86 CB67                 4E068 AB00 CE03 CF03 DB13                 4G015 EA02 EA03                 4G059 AA01 AA11 AA13 AA14 AA18                       AB09 AB11 AC08                 4G062 AA01 AA04 AA11 BB03 DA07                       DB03 DC01 DD01 DE01 DF01                       EA01 EB04 EC01 ED01 EE03                       EE04 EF01 EG01 FA01 FB01                       FC01 FD01 FE01 FF01 FG01                       FH01 FJ01 FK01 FL01 GA01                       GB01 GC01 GD01 GE01 HH01                       HH03 HH05 HH07 HH09 HH11                       HH13 HH15 HH17 HH20 JJ01                       JJ03 JJ05 JJ07 JJ10 KK01                       KK03 KK05 KK07 KK10 MM01                       MM02 MM27 NN05 NN09 NN32                       PP12

Claims (10)

[Claims] 1. A method of coloring glass, which comprises irradiating glass containing silver ions with high-energy light to agglomerate silver ions to form fine silver particles. 2. The method for coloring glass according to claim 1, wherein the laser irradiation device comprises a laser oscillator, an optical modulator, a condenser lens mounted on a linear translator, an objective lens, and a galvanometer mirror. A method for coloring glass, which comprises irradiating a glass containing ions with laser light to agglomerate silver ions to form fine silver particles. 3. The glass coloring method according to claim 1, wherein the glass containing silver ions is irradiated with laser light from a laser irradiation device including a laser oscillator, an optical modulator, a galvanometer mirror and an fθ lens. By so doing, silver ions are aggregated to form fine silver particles and colored, whereby a method for coloring glass is provided. 4. The carbon dioxide gas laser oscillator is a U laser oscillator.
A V pulse laser oscillator or an argon ion laser oscillator, the types of laser light used are infrared light, near infrared light,
Visible light or ultraviolet light.
Alternatively, the glass coloring method according to claim 3. 5. The method for coloring glass according to claim 2, wherein the light modulator is an acousto-optic modulator or an electro-optic modulator. 6. The method for coloring glass according to claim 1, wherein the irradiation position of the laser light on the glass is moved by a plurality of galvanometer mirrors. 7. The method of coloring glass according to claim 1, wherein the glass is moved by a stage movable in the horizontal direction and / or the vertical direction. 8. A glass which is colored by the glass coloring method according to any one of claims 1 to 7. 9. A glass characterized in that a character, a pattern, or a bar code is drawn by the glass coloring method according to any one of claims 1 to 7. 10. A method for decoloring a colored portion by heating the glass according to claim 8 or 9 to a temperature above its softening point.