WO1994020974A1

WO1994020974A1 - Method for forming fluorescent film, and transfer material for formation of the fluorescent film

Info

Publication number: WO1994020974A1
Application number: PCT/JP1994/000359
Authority: WO
Inventors: Katsutoshi Ohno; Masaru Ihara; Hideo Shinohara; Katsuhiko Kuroda; Yasuo Oguri; Hiroshi Uchida
Original assignee: Sony Corporation; Kasei Optonix, Ltd.; Mitsubishi Chemical Corporation
Priority date: 1993-03-11
Filing date: 1994-03-07
Publication date: 1994-09-15
Also published as: EP0641008A1; EP0641008A4; KR950701764A

Abstract

This method makes it possible to form a fluorescent film (10) easily and efficiently on a glass plate (18), particularly on the face plate (8) of a cathode ray tube. A transfer material for its use is also provided. The method comprises the steps of, by use of the transfer material (7) in which at least thermally transferable phospher layers (11, 12 and 13) containing phosphers and thermally fusible binder are formed on a base film (3), transferring the patterns of the thermally transferrable phospher layers (11, 12 and 13) to the glass plate (8) one after another; and baking the glass plate (8) to remove the binder from the fluorescent film (10) and to form the fluorescence film on the glass plate. The transfer material has a thermally transferable phosphor layer (4) containing at least phosphs (1) and thermally fusible binder (2) on the base film (3).

Description

Description Phosphor film formation method and transfer material for phosphor film formation

The present invention relates to a method for easily and efficiently forming a fluorescent film on a glass substrate, particularly on a fuse plate of a cathode ray tube, and a transfer material used for the method. Background art

Conventionally, a slurry coating exposure method or a sedimentation method has been used as a method for forming a fluorescent film on a cathode ray tube flute.

By the way, the above-mentioned slurry coating exposure method for forming a fluorescent film involves spin-coating a slurry in which a phosphor, for example, a photosensitive resin composed of polyvinyl alcohol and ammonium bichromate, is dispersed on a fuse plate. Dry and expose the desired pattern with UV light. After that, it is developed with water to remove the unexposed portions to form a fluorescent film.

Therefore, forming a fluorescent film by the slurry coating exposure method has the disadvantage that the number of steps is large, the equipment is complicated, and productivity is lacking.

In addition, a method for forming a fluorescent film by a sedimentation method is as follows. A phosphor is settled on a fusing plate in a suspension containing a phosphor and a binder (water glass or the like), and then the supernatant is gently removed. It is a method of pouring out and forming a fluorescent film.

Therefore, it takes time to settle the phosphor, and it is difficult to form a predetermined pattern.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a fluorescent film forming method capable of easily and efficiently forming a fluorescent film on a glass substrate, particularly on a fuse plate of an anode tube, and a method of forming the same. An object of the present invention is to provide a transfer material used in the method. Disclosure of the invention

The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, if a thermal transfer method often used in printers and the like is used in recent years, the fuse plate of a cathode ray tube can be very simply and efficiently used. A fluorescent film can be formed on Was found. The thermal transfer method, which is currently widely used in personal word processors and color printers, for example, is to transfer an ink ribbon with a heat-meltable ink on a substrate to the thermal layer from the back side of the ink layer. This is a method in which the ink is melt-transferred onto the recording paper in a predetermined pattern by heating and pressing with a heating element such as a pad.

That is, the gist of the present invention is to use at least a transfer material in which a heat transferable phosphor layer including a phosphor and a heat-fusible binder is formed on a base film, and the heat transferable phosphor layer is The present invention is a method for forming a fluorescent film, wherein a predetermined pattern is sequentially transferred onto a glass substrate by a thermal transfer method, and the resultant is baked to remove a binder of the phosphor layer, thereby forming a fluorescent film on the glass substrate. As a heating source, there is a laser thermal head or the like.

Another aspect of the present invention resides in a transfer material for forming a fluorescent film, in which at least a heat transferable phosphor layer including a phosphor and a heat-fusible binder is formed on a base film.

Hereinafter, the present invention will be described in detail with reference to an example in which a fluorescent film is formed on a fuse plate of a cathode ray tube.

As the base film, a film suitable for a base film such as a conventionally known film or paper can be used. For example, a resin film having relatively high heat resistance such as polyester, polypropylene, boriamid, polycarbonate, polyimid, cellophane and the like, and paper such as glassine paper and condenser paper are exemplified. The thickness is desirably 1 to 200 μm. This base film may be provided with a heat-resistant lubricating layer such as a silicone resin on the side that comes into contact with the thermal head in order to increase the running resistance of the heat-resistant thermal head. Examples of the phosphor used in the present invention include a silver-activated zinc sulfide-based phosphor as a blue light-emitting component phosphor, for example, at least one of ZnS: Ag, ZnS: Ag, and A1. As the green light emitting component phosphor, a copper-activated zinc sulfide-based phosphor, for example, ZnS: Cu, a mixed phosphor of A1 phosphor and ZnS: Au, A1 phosphor, ZnS: CuA1 phosphor, gold, copper, and aluminum activated zinc sulfide phosphor (ZnS: Au, Cu, Al), copper and aluminum activated zinc sulfide phosphor , Cd) S: Cu, Al], at least one europium-activated rare earth oxide-based phosphor as a red light-emitting component phosphor, such as Eu Katsusan sulfide I Tsu Toriumu phosphor with mouth Piumu _{_{(Y 2 0 2 S: E}} u), europium-activated oxide I Tsu Toriumu phosphor _{_{(Y 2 0 3: E u}} ) cathode lines conventionally, such as at least one The phosphor used in the tube can be used. In addition, those phosphors to which pigments having a filter effect are attached are also used. As this kind of pigment, for example, blue light emission in the phosphor a blue pigment such as cobalt aluminate or ultramarine green emission phosphor _{T i 0 2 - Z n O} - C o O - N i 0 based green such as Pigments and red light-emitting phosphors include red pigments such as slag selenide power domes. The size of the phosphor is preferably in the range of 1 to 20 m, and more preferably in the range of 2 to 8.

Examples of heat-fusible binders include resins such as Nora's raffin wax, microcrystalline and carnaubax, various synthetic resins, ethylene-butyl acetate copolymer, ethylene-ethyl acrylate copolymer, and polyester resin. Thermoplastic resins such as polyamide resins and the like can be used. In addition, if necessary, petroleum resins, rosin derivatives, various plasticizers, flexible materials such as liquid paraffin, and various dispersants for dispersing the phosphor can be used.

The ratio of the phosphor to the heat-fusible binder is preferably from 80 to 90% by weight to the phosphor of 20 to 90% by weight. Further, in the present invention, if a transfer material having phosphor layers corresponding to red, green, and blue adjacent to each other in a pattern on the same ^^ '-film is used, the transfer material and the head can be used. This is preferable because the red, green and blue phosphor layers can be transferred very efficiently without the need for replacement.

Furthermore, in addition to the heat transferable phosphor layer, the heat transferable phosphor layer and the heat transferable pigment layer may be laminated such that the heat transferable pigment layer is on top or may be the same in a parallel form. By using the transfer material above, compared to the method of attaching the pigment to the phosphor, the pigment does not peel off, and the pigment does not adhere to the phosphor of another color to cause color mixing. It is preferable because a more excellent fluorescent color can be obtained. The transfer material used at this time includes a heat transfer phosphor layer containing at least a phosphor and a heat-fusible binder on a base film, and at least a pigment and a heat-fusible binder. The heat transfer pigment layer is provided on the base film in a form of being laminated for each color or in a form in which the heat transfer phosphor layer of each color and the heat transfer pigment layer of each color are all arranged in parallel. And the phosphor layers corresponding to these red, green and blue Each area of the pigment layer has almost the same area and is adjacent to the same film, and if the area of each area is necessary and sufficient for the amount of transfer to one glass substrate, Since the component transfer to one glass substrate can be performed in one area without excess or deficiency, it is possible to reduce the transfer operation and waste of material, which is preferable. As the pigment, the pigments exemplified above are suitably used. The size of the pigment is preferably in the range of 0.01 to 0.5 m.

The ratio of the pigment to the hot-melt binder is preferably 20 to 90% by weight and 80 to 10% by weight of the hot-melt binder.

As a method of providing the heat transferable phosphor layer or the heat transferable pigment layer on the base film, a hot melt coating with a phosphor or a pigment dispersed therein may be used as a hot melt coating, a solvent coating, or an emulsion coating. It can be provided by coating with a method such as coating. In addition, the phosphor layer and the pigment layer corresponding to red, green, and blue can be easily applied and laminated on the same base film in order by using a printing machine. . The thickness of the heat transferable phosphor layer is preferably in the range of 3 to 60 / m, and more preferably 5 to 30 / m. If the thickness is too thin, the amount of phosphor in the phosphor film formed on the glass substrate tends to be insufficient.If the thickness is too thick, heat conduction to the heat transferable phosphor layer becomes insufficient, and a predetermined pattern is formed. This tends to be difficult. The thickness of the heat transferable pigment layer is preferably in the range of 1 to 10 m.

The transfer material described above may be used, if necessary, to improve the adhesiveness of the heat transferable phosphor layer and the heat transferable pigment layer to the base film and, conversely, the release property from the base film. An adhesive layer and a release layer can be provided between the conductive phosphor layers and between the base film and the heat transferable pigment layer, respectively. The thickness of the adhesive layer and the release layer is preferably in the range of 0.1 to 2 / m. In addition, in order to increase the adhesiveness to the faceplate surface, a force for providing an additional adhesive layer on the opposite side of the heat transferable phosphor layer and the heat transferable pigment layer from the base film, or the faceplate surface It is also possible to provide an adhesive layer on top. The thickness of the adhesive layer is preferably in the range of 0.1 to 2.

1 to 3 show examples of the transfer material of the present invention. In each figure, 1 represents a phosphor and 2 represents a heat-fusible binder. Fig. 1 shows an example in which a heat transferable phosphor layer 4 is provided on a base film 3. Fig. 2 shows the base film 3 and a heat transferable phosphor layer. An example in which an adhesive layer or a separation layer is provided between 4 and 5 is shown in FIG. 3, and FIG. 3 is an example in which an adhesive layer 6 is further provided in the configuration example of FIG.

Using the heat transferable transfer material described above, a fluorescent film is formed on the fuse plate of the cathode ray tube. First, a detection device such as an optical sensor is driven on the face plate in the direction of driving the thermal head to detect the position and interval of the black matrix.

As shown in FIG. 4, the transfer material 7 is superimposed on the face plate 8 and applied and run while being pressed by the thermal head 9, and when the transfer material is peeled off, the thermal transfer phosphor layer 10 having a predetermined pattern is formed. Is transferred. The surface of the phosphor layer has excellent smoothness. In order to obtain a color cathode ray tube having the blue, green, and red stripes or dots, the transfer material 7 containing each phosphor is transferred once or more than once to each color. Good.

Next, the base plate is fired together with the transferred phosphor layer. This firing is mainly intended to remove organic components other than the phosphor and the pigment, and therefore, unless the phosphor and the pigment are adversely affected. Although a suitable temperature according to the above purpose may be arbitrarily adopted, it is usually desirable to select from a range of 400 to 50 CTC. Thus, a fluorescent film is formed.

FIG. 5 shows an embodiment of the transfer material of the present invention. The red, green, and blue heat transferable phosphor layers 11, 12, and 13 are provided adjacent to each other on the base film 3, and a detection pattern 23 for detecting each color is usually provided between the coating portions. Is provided.

Using the heat transferable transfer material described above, a fluorescent film is formed on the fuse plate of the cathode ray tube. First, a detecting means such as an optical sensor is driven on the face plate in the driving direction of the thermal head to detect the position and interval of the black matrix and to form a film corresponding to red, green and blue regularly. Identify the location. Next, for example, as shown in FIG. 6, the red-coated portion 11 of the transfer material 7 is overlaid on the fuse plate 8 and is applied and run while being pressed by the line thermal head 9 to peel off the transfer material. And the transfer layer of the red phosphor layer is transferred. Next, the green coating section 12 is again placed on the face plate, and the printing is performed while pressing the line thermal head in the same manner as before, and the transfer material is peeled off. Is transferred. At that time, the timing is applied at a different timing from the timing applied at the first red part. Next, if the same is repeated for the blue coating section 13, the red, green, and blue fireflies The optical body layers 10 are sequentially formed in a strip shape on the fuse plate. The surface of the phosphor layer has excellent smoothness.

Then, when the fuse plate is fired to remove organic components other than the phosphor, phosphor films of three colors, red, green, and blue, are sequentially formed in a stripe shape.

7 and 8 show examples of the transfer material of the present invention. Fig. 7 shows an example in which a laminate consisting of a red, green, and blue heat transferable phosphor layer and a heat transferable pigment layer is coated adjacently on base film 3, and Fig. 8 shows the heat transfer properties of red, green, and blue. This is an example in which a pigment layer and red, blue, and blue heat transferable phosphor layers are applied in parallel. FIG. 9 is a diagram showing a cross section of the laminated body portion of the heat transferable phosphor layer and the heat transferable pigment layer of FIG. 7, and FIGS. 10 and 11 are respectively the heat transferable pigment layer portion of FIG. 1 shows a cross-sectional view of a heat transferable phosphor layer portion. In FIG. 9 to FIG. 11, 1 indicates a phosphor, 17 indicates a pigment, and 2 indicates a heat-fusible binder. Also, 11, 12, and 13 represent a heat transferable phosphor layer, and 14, 15, 15 and 16 represent a heat transferable pigment layer.

Using the heat transferable transfer material described above, a fluorescent film is formed on the fuse plate of the cathode ray tube.

For example, the red coating part of the transfer material, on which the phosphor layer and the pigment layer are laminated, is superimposed on the fuse plate, and is applied and run while pressing with the line thermal head. When the transfer material is peeled off, the red pigment layer The transfer layer on which the phosphor layers are laminated is transferred. Next, the green coating part is again placed on the face plate, the line thermal head is returned to the original position, and the line thermal head is pressed and run as before, and the transfer material is peeled off. The transfer layer on which the pigment layer and the phosphor layer are laminated is transferred. At that time, apply a timing different from the timing applied in the first red part. Next, if the same procedure is repeated for the blue coating part, the laminated body of the red, green, and blue pigment layers 18 and the phosphor layer 10 is striped on the plate in this order as shown in Fig. 12. It is formed in a shape. When using a transfer material in which the phosphor layer and the pigment layer are arranged in parallel as shown in Fig. 8, first transfer the red, green, and blue pigment layers, and then transfer the red, green, and blue phosphor layers. May be transferred so as to overlap the pigment layers of the same color.

Note that the transfer order of the three colors of red, green, and blue is not limited to the order of red, green, and blue, and may be another order. Also, when using a transfer material in which the phosphor layer and the pigment layer are arranged in parallel, the pigment layer is transferred to the same cylinder location before the phosphor layer. For this reason, the phosphor layer and the pigment layer of the same color may be arranged adjacent to each other. The surface of the obtained phosphor layer has excellent smoothness.

'Then, when the fuse plate is baked together with the transferred phosphor layer to remove organic components other than the phosphor and pigment, phosphor films of three colors, red, green, and blue, are sequentially formed in a stripe shape.

In particular, when a laser is used as a heating source, the following advantages are generated as compared with the case where a thermal head is used.

(1) Scanning can not be performed very fast in the thermal head because thermal head stores heat in the thermal head, but scanning can be performed very quickly because there is no such thing in the laser, and the thermal head is used. Transfer can be performed in a shorter time than in the case _c

(2) With a thermal head method, a heating laser with a heating dot size of about 50 to 200 // m can produce a heating dot of about 10 / m, which is formed. Bataan's ability to follow is very good.

The transfer material for forming a fluorescent film used together with the laser has a heat transferable phosphor layer containing at least a phosphor and a heat-fusible binder formed on a base film. It is preferable that the transfer material has an infrared absorber in at least one of the thermal transfer phosphor layer, the base film, and the intermediate layer between the thermal transfer phosphor layer and the base film. The reason for this is that the use of an infrared absorber increases the light-to-heat conversion efficiency of the laser, making it possible to use a semiconductor laser that has relatively low output but is easy to handle. Examples of the infrared absorbing agent include carbon black, cyanine dyes, squarium dyes, naphthoquinone dyes, and anthraquino dyes described in JP-A-63-199191. Known infrared absorbers, such as a cyanine dye, an azulhenium dye, and a phthalocyanine dye, can be used. In order to include the infrared absorbing agent in the heat transferable phosphor layer, it may be dispersed together with the phosphor in a heat-fusible binder and coated. In addition, in order to disperse the film in the base film, it can be easily manufactured by kneading the film in advance with the resin when extruding the film. When it is provided as an intermediate layer, it can be formed by preparing a solution with an appropriate resin binder and applying the same before coating the thermal transfer phosphor layer. When the heat transferable phosphor layer and the intermediate layer generate heat, it is preferable that the base film is transparent to a laser. FIGS. 13 to 15 show examples of the transfer material of the present invention.

In each figure, 1 represents a phosphor, 2 represents a heat-fusible binder, and 19 represents an infrared absorber. FIG. 13 shows an example in which a heat transferable phosphor layer 4 containing an infrared absorber 19 is provided on a base film 3, and FIG. 14 shows an example in which a heat transfer phosphor layer 4 is provided between the base film 3 and the heat transfer phosphor layer 4. FIG. 15 shows an example in which an adhesive layer or a release layer 5 having an infrared absorbent 19 is provided. FIG. 15 shows an example in which an adhesive layer 6 is further provided in the configuration example of FIG.

This is an example in which an infrared absorber 19 is owned in 3.

Various lasers can be used to transfer the heat transferable phosphor layer from the heat transfer material. For example, ion gas lasers such as argon and krypton; metal vapor lasers such as copper, gold, and cadmium; solid state lasers such as ruby and YAG; gallimum in the infrared region of 750 to 870 nm. Diode lasers such as arsenic radiation; In practice, it is desirable to use a YAG laser or diode laser because of its small size, low cost, stability, reliability, and ease of adjustment.

The transfer material is overlaid on the plate and brought into contact, and then pressed with a transparent glass plate 20, or the space between the transfer material and the plate is evacuated to vacuum. Adhere. For example, after running with a laser using an apparatus as shown in FIG. 16, the thermal transfer phosphor layer is transferred when the transfer material is pulled off. The surface of the phosphor layer has excellent smoothness. Next, the fuse plate is fired together with the transferred phosphor layer.

Furthermore, the present inventors use a thermal transfer method, and preheat the paste before heating the thermal transferable phosphor layer or the thermal transferable pigment layer with a thermal head laser. The heat from the thermal head and the laser did not escape to the ferrite plate, and it was found that the phosphor layer or the pigment layer could be successfully transferred onto the face plate without applying excessive pressure. The preheating temperature is equal to or lower than the blocking temperature of the heat transferable phosphor layer or the heat transferable pigment layer, and the room temperature or higher is used. Particularly, when a phosphor film having a plurality of emission colors is formed on the same glass substrate, the preheating temperature is lower than the blocking temperature. It is recommended that the value be lowered by at least 10 more preferably. In general, the preheating temperature of the present invention is 4 A range of 0 to 100 is desirable. In the thermal transfer method using a thermal head laser, if a thermal transfer phosphor layer or a thermal transfer pigment layer is transferred onto the face plate without preheating the face plate, the face plate becomes thick and has a very large heat capacity. Due to the large size, heat from the thermal head laser escapes to the first plate, and an excessive amount of heat must be applied to transfer the heat transferable phosphor layer. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross-sectional view illustrating an embodiment of the transfer material for forming a fluorescent film of the present invention, FIG. 2 is a cross-sectional view illustrating an embodiment of the transfer material for forming a fluorescent film of the present invention, and FIG. FIG. 4 is a cross-sectional view illustrating an example of a transfer material for forming a fluorescent film according to an embodiment of the present invention. FIG. 4 is an explanatory diagram of an example of a thermal transfer system according to the present invention. FIG. FIG. 6 is an explanatory view of one embodiment of the thermal transfer system of the present invention, FIG. 7 is a view showing an embodiment of the transfer material for forming a fluorescent film of the present invention, and FIG. FIG. 9 is a cross-sectional view of a transfer material for forming a fluorescent film in FIG. 8, and FIG. 10 is a cross-sectional view of a pigment layer coated portion of the transfer material for forming a fluorescent film in FIG. FIG. 11, I 11 is a cross-sectional view of the phosphor layer coating portion of the transfer material for forming a fluorescent film in FIG. 8, FIG. 12 is an explanatory view of one embodiment of the thermal transfer method of the present invention, and FIG. The transfer material for forming a fluorescent film of the present invention FIG. 14 is a cross-sectional view illustrating an example of the transfer material for forming a fluorescent film of the present invention. FIG. 15 is a cross-sectional view illustrating an example of the transfer material for forming a fluorescent film of the present invention. FIG. 16 is an explanatory diagram of one embodiment of the transfer system of the present invention.

In the figure, 1 is a phosphor, 2 is a heat-fusible binder, 3 is a base film, 4 is a heat transferable phosphor layer, 5 is an adhesive or release layer, 6 is an adhesive layer, 7 is a transfer material, and 8 is a face plate. , 9 is a thermal head, 10 is a transferred phosphor layer, 11 is a red heat transfer phosphor layer, 12 is a green heat transfer phosphor layer, 13 is a blue heat transfer phosphor layer, 1 4 is a red heat transfer pigment layer, 15 is a green heat transfer pigment layer, 16 is a blue heat transfer pigment layer, 17 is a pigment, 18 is a transferred pigment layer, and 19 is infrared absorption. 20 is a glass plate, 21 is a lens, 22 is a laser light source, and 23 is a detection pattern. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited to the following Examples without departing from the gist thereof. In the examples, “parts” indicates “parts by weight”. Example 1

On a polyethylene terephthalate film (6 um layer thickness) with a heat-resistant lubricated back surface, apply a phosphor ink of the following composition to a dry coating thickness of 15 μm. Coating was performed by a gravure method to obtain a transfer material. Composition

Ethylene vinyl acetate resin emulsion 10 parts

(Solid content 40%)

No, 'Raffin Wax Emarjion 20

(Solid content 40%)

Phosphor powder (ZnS: Cu, Al) 24 parts

30 parts of water

This transfer material is placed on a face plate and applied and run under the following conditions while pressing with a prototype line thermal head having a heating element of 6 dot mm, and the transfer material is peeled off. A striped phosphor layer was obtained on the faceplate. Condition

Recording line density 6 dots / mm

Thermal head applied power 0.2 W node

Thermal head applied pulse width 1 2 ms

Application pattern 1 Line applied 2 lines Not applied repeatedly The above-mentioned fuse plate was baked at 450'C for 30 minutes to remove organic components and form a fluorescent film. , Example 2 On a polyethylene terephthalate film (6111 thickness) with a heat-resistant lubricated back surface, apply a phosphor ink of the following composition so that the dry coating thickness is 15 m. Coating was performed by the melt microgravure method to obtain a transfer material.

Composition

1 part of ethylene vinyl acetate resin

No ,. Raffin Wax 8 parts

1 part synthetic wax

Phosphor powder (ZnS: Cu, Al) 40 parts

When this transfer material was overlaid on the plate and treated in the same manner as in Example 1, a clean striped phosphor layer was obtained on the plate.

The above-mentioned fuse plate was baked at 45 ° C. for 30 minutes to remove organic components, thereby forming a fluorescent film. Example 3

On the polyethylene terephthalate film (thickness: 6 m), the back of which is coated with heat-resistant lubrication, a phosphor ink of the following composition is printed to a dry coating thickness of 15 / m. Coating was performed by a press to obtain a transfer material in which red, green, and blue phosphor layers were adjacent in this order. Composition (red phosphor ink)

Emulsion of ethylene monoacetate resin 10 parts

(Solid content 40%)

No 'Raffinwaxe Marjon 20

(Solid content 40%)

Phosphor powder _{_{(Y 2 0 2 S: E}} u) ( particle size 4.5 m) 2 4 parts

Composition of water 30 parts (green phosphor ink)

Ethylene-butyl acetate resin emulsion 10 parts

(Solid content 40%) No 'Raffinwaxe Marjon 20

(Solid content 40%)

Phosphor powder (ZnS: Cu, A1) (particle size 4.5 μm) 24 parts

Composition of water 30 parts (blue phosphor ink)

Ethylene-butyl acetate resin emulsion 10 parts

(Solid content 40%)

No, 'Raffin Wax Emarjion 20

(Solid content 40%)

Phosphor powder (ZnS: Ag) (particle size 4.5 m) 24 parts

30 parts of water

When the red-coated portion of the transfer material was placed on a fuse plate and the same transfer material as in Example 1 was peeled off, the transfer layer of the red phosphor layer was transferred.

Next, the green coating part is again put on the face plate, the liner head is returned to the original position, and the printing material is moved while pressing with the line thermal head in the same manner as above. Then, the transfer layer of the green phosphor layer was transferred. At that time, the timing was applied at a different timing from the timing applied at the first red part. When the same procedure was repeated for the blue coating, red, green, and blue phosphor layers were sequentially formed in stripes on the fuse plate. The surface of the phosphor layer has excellent smoothness.

The base plate was baked at 450 ° for 30 minutes to remove organic components, thereby forming red, green, and blue phosphor films in a stripe shape. Example 4

On a polyethylene terephthalate film (6 μm thick), the back surface of which is coated with a heat-resistant lubricator, apply the following composition phosphor ink so that the dry coating thickness is 15 m. Coating was performed by a printing machine using the melt method to obtain a transfer material in which red, green, and blue phosphor layers were sequentially adjacent. , Composition (red phosphor ink) 1 part ethylene-butyl acetate resin

No, * Raffin Wax 8 parts

1 synthetic wax

Phosphor powder _{_{(Y z 0 2 S: E}} u) ( particle diameter 4. 5 m) 4 0 parts set adult (phosphor I link in the Color G)

1 part ethylene-butyl acetate resin

No, 'Raffin Wax 8

1 part of synthetic box

Phosphor powder (ZnS: Cu, A1) (particle size: 4.5 m) 40 parts composition (blue phosphor ink)

1 part of ethylene vinyl acetate resin

Norafin Wax 8 parts

1 part of synthetic box

Phosphor powder (ZnS: Ag) (particle size: 4.5 urn) 40 parts

The transfer material was applied and swept in the order of red, green, and blue in the same manner as in Example 3. When the transfer material was peeled off, a clean three-color striped phosphor layer was obtained on the fuse plate.

Use the above-mentioned metal plate, 450. By baking for 30 minutes at C, the organic components were removed, and the red, green, and blue fluorescent films could be formed in a stripe shape. Example 5

On a polyethylene terephthalate film (6 m thick), the back side of which is coated with heat-resistant lube, a pigment ink of the following composition is applied to a dry coating thickness of 3 m. Further, a phosphor ink having the same composition as in Example 3 was applied thereon by a printing machine so as to have a dry thickness of 15 m, and a laminate comprising a red, green, and blue pigment layer and a phosphor layer was formed. Were obtained in order. Composition (red pigment ink)

Ethylene-butyl acetate resin emulsion 10 parts (Solid content 40%)

NO 'Raffin Wax Emano Region 20

(Solid content 40%)

Bengal red pigment 2 4 parts

Water 30 parts composition (green pigment ink)

Ethylene monoacetate butyl ester 10 parts

(Solid content 40%)

No, 'Raffin wax emulsion' 20 parts

(Solid content 40%)

Composite oxide green pigment 24 parts

Water 30 parts composition (blue pigment ink)

Ethylene-butyl acetate resin emulsion 10 parts

(Solid content 40%)

No ,. Raffinwax Xmalmarion 20 parts

(Solid content 40%)

Cobalt aluminate blue pigment 24 parts

30 parts of water

The transfer material was applied and swept in the order of red, green, and blue in the same manner as in Example 3. When the transfer material was peeled off, a laminate composed of the red, green, and blue pigment layers and the phosphor layer was sequentially formed on the fuse plate. A strip was formed. The surface of the phosphor layer was excellent in smoothness.

The face plate was baked at 45 ° C. for 30 minutes to remove organic components, thereby forming red, green, and blue phosphor films in a stripe shape. Example 6,

On a 6 m thick polyethylene terephthalate film, the back side of which is coated with a heat-resistant ink, a pigment ink of the following composition is applied with a dry coating thickness of 3 μπι , A phosphor ink having the same composition as in Example 4 was applied with a printing machine by a hot melt method so as to have a dry coating thickness of 15 μm. A transfer material was obtained in which the pigment layer and the phosphor layer were sequentially adjacent to each other in a pattern. Composition (red pigment ink)

1 part of ethylene vinyl acetate resin

No, 'Raffin Wax 8

1 part synthetic wax

Behe / S υ 7, Puri-, -fe

Composition (green pigment ink)

1 part ethylene-butyl acetate resin

No ,. Raffin Wax 8 parts

1 synthetic wax

Composite oxide green pigment 40 parts Composition (blue pigment ink)

1 part of ethylene vinyl acetate resin

No ,. Raffin Wax 8 parts

1 part of synthetic box

Cobalt aluminate blue pigment 40 parts

In the same manner as in Example 3, the above-mentioned transfer material is first applied and drawn in the order of red, green, and blue of the pigment layer, and when the transfer material is peeled off, a clean three-color striped pigment layer is used. Obtained on the plate. Next, the phosphor layer is applied in the order of red, green, and blue so that the same color is applied on the pigment layer, and the transfer material is peeled off. As a result, the laminate of the pigment layer and the phosphor layer is formed. Obtained on fusing plates.

The base plate was baked at 450 ° C. for 30 minutes to remove organic components, thereby forming three red, green and blue fluorescent films in a stripe shape. Example Ί

Transparent instead of heat-resistant lubricated polyethylene terephthalate film A transfer material similar to that in Example 1 was used, except that a transparent polyethylene terephthalate film was used. The transfer material was placed on a face plate and pressed with a transparent glass plate. Then, a laser beam (YAG laser output 0.5 W Scanning exposure was performed in a stripe shape with a beam diameter of 20 m). When the transfer material was peeled off, a clean, phosphor-like phosphor layer was obtained on the face plate. 450 for the above paste. The organic component was removed by baking for 30 minutes at C to form a fluorescent film. Example 8

Ink of the following composition is coated on a transparent polyethylene terephthalate film (6! M thick) by hot gravure gravure method to a dry coating thickness of 15 μm to obtain a transfer material. Was.

Composition

1 part ethylene monoacetate bur resin

Noraffin wax 8 parts

1 part synthetic wax

Phosphor powder (ZnS: Cu, A1: particle size 4. b μm) 40 parts

Infrared absorbing dye 2 parts

Scanning exposure was performed in the same manner as in Example 7, except that the above-described transfer material and laser light (diode laser: 830 nm; output: 0.1 W, beam diameter: 15 m) were used. When the transfer material was peeled off, a clean striped phosphor layer was obtained on the plate.

The above-mentioned fuse plate was baked at 450 ° C. for 30 minutes to remove organic components, thereby forming a fluorescent film. Example 9

When a phosphor film was formed in the same manner as in Example 1 except that the preheated fuse plate was used at 50, a very clean phosphor film was formed on the face plate. , Example 10 When a fluorescent film was formed in the same manner as in Example 2 except that the heat plate preheated at 40 was used, a very clean fluorescent film was formed on the surface plate. Industrial applicability

According to the present invention, since the fluorescent film can be easily formed on the glass substrate by using the heat transferable phosphor layer, the productivity of forming the fluorescent film is greatly improved. Further, since the phosphor layer can be transferred to an arbitrary pattern by a thermal head or a laser, a phosphor film can be produced very efficiently by using a transfer material having a heat transferable phosphor layer.

7

Claims

Scope of claim

1. At least, using a transfer material in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder is formed on a base film, the heat transferable phosphor layer is formed on a glass substrate by a heat transfer method. A method of forming a fluorescent film, comprising sequentially transferring a predetermined pattern, firing and removing a binder of the fluorescent layer to form a fluorescent film on the glass substrate.

2. The method for forming a phosphor film according to claim 1, wherein a transfer material is used in which phosphor layers corresponding to red, green, and blue are formed on the same film.

3. The method according to claim 1, wherein the glass substrate is preheated before transferring the phosphor layer onto the glass substrate.

4. At least a transfer material in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder and a heat transferable pigment layer containing a pigment and a heat-fusible binder are laminated on a base film in this order. The laminate of the heat transferable phosphor layer and the heat transferable pigment layer is transferred onto a glass substrate by a heat transfer method, and baked to remove the binder of the phosphor layer, the pigment layer, and the pigment film layer. The phosphor film forming method according to claim 1, wherein a laminate comprising a phosphor film layer is formed on the glass substrate.

5. At least a transfer material in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder and a heat transferable pigment layer containing a pigment and a heat-fusible binder are formed in parallel on a base film. The heat transferable phosphor layer and the heat transferable pigment layer are transferred onto a glass substrate in the order of a pigment layer and a phosphor layer by a heat transfer method, and then baked to remove the binder between the pigment layer and the phosphor layer. 2. The phosphor film forming method according to claim 1, wherein a laminate comprising a pigment film layer and a phosphor film layer is formed on the glass substrate.

2. The method for forming a fluorescent film according to claim 1, wherein the thermal transfer method is a method using a thermal head as a heating source.

The phosphor film according to claim 1, wherein at least one of the heat transfer phosphor layer, the base film, and the intermediate layer between the heat transfer phosphor layer and the base film uses a transfer material having an infrared absorbent. Forming method.

Claim 1. The thermal transfer method is a method using a laser as a heating source. The forming method as described above.

9. At least a transfer material for forming a fluorescent film in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder is formed on a base film.

10. The transfer material for forming a fluorescent film according to claim 9, wherein the phosphor layers corresponding to red, green, and blue are formed on the same ^^-film.

11. At least, a transfer material in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder and a heat transferable pigment layer containing a pigment and a heat-fusible binder are laminated on a base film in this order. Wherein red, green, and blue regions are provided on the same ^^ '-film, and a phosphor layer and a pigment layer of the same color are laminated in the same region. Item 10. The transfer material for forming a fluorescent film according to Item 9.

12. At least a transfer material in which a heat transferable phosphor layer containing a phosphor and a heat-fusible binder, and a heat transferable pigment layer containing a pigment and a heat-fusible binder are formed in parallel on a base film. 10. The method according to claim 9, wherein a heat transferable phosphor layer and a heat transferable pigment layer corresponding to red, green, and blue are provided in parallel on the same film. The transfer material for forming a fluorescent film according to the above.

13. The transfer for forming a fluorescent film according to claim 9, wherein at least one of the thermal transfer phosphor layer, the base film, and the intermediate layer between the thermal transfer phosphor layer and the base film has an infrared absorber. Wood.