TW423023B - A water-soluble fluorescent material for color picture tubes and a process for manufacturing the same - Google Patents

Abstract

The present invention provides a water-soluble gallate fluorescent material with excellent luminous characteristics and a process for manufacturing of color CRT using the same material as above. The process improves luminous efficiency and color reproduction region and increases resolution due to decrease in electron spot from the current reduction by electron beams in luminance on the same fluorescent screen, by introduction of the electrophotographic dry screening process without using water.

Description

^ 423023 A7 B7_ V. Description of the Invention (1) The present invention relates to a fluorescent substance for a color cathode ray tube, and more specifically, it relates to a fluorescent substance for a color cathode ray tube. The luminous efficiency of the fluorescent layer of the color cathode ray tube, and according to the reduction of the current value of the electron beam in the same fluorescent layer, the resolution of the electron beam spot is reduced. This is by introducing a dry type The method is completed. This method does not use water, but uses a water-soluble fluorescent substance with excellent luminous efficiency in the method of Bra υη tube screen. The fluorescent layer of the cathode ray tube is the energy of the electron beam. Where it is converted into light energy, as shown in Figure 1, the electrons emit light by hitting the fluorescent substance of the fluorescent film. This film is formed on the side of the panel opposite to the observer, and the fluorescent layer The nature depends heavily on the nature of this fluorescent substance. Generally speaking, the fluorescent substance used in the fluorescent layer of a color picture tube (CPT) is a small amount of impurities such as zinc sulfide or yttrium vaporized (ie, the activator) is added to the substrate at 700 Manufactured by sintering at a temperature of ~ 130 ° C for 30 minutes to 1 hour. The aforementioned activators are copper, gold, olefinic elements, etc. The method for manufacturing a fluorescent layer for a color image tube consists of the following steps: Applying a photoresist to the inside of the panel, illuminating, developing, coating graphite, etching, and forming graphite chopsticks by photolithography to form a black matrix. The steps for forming a fluorescent film are as follows: Fluorescent paste-like composition is prepared by the following method : The fluorescent substance is suspended in a solution of polyvinyl alcohol (PVA) and saddle dichromate (ADC) by a slurrying method. This fluorescent slurry-like composition (22) is coated by a nozzle (21) The size of the rotating paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -------- „---- • Loading ------ Order ------ I (Please read the precautions on the back before filling out this page) The Central Government Standards Bureau, Ministry of Economic Affairs, Industrial Workers' Cooperative Cooperatives.) 7. Attack 3 〇2 3 A7 B7 Printed by the Ministry of Economic Affairs Central Standards Bureau Bureau Consumer Cooperative, i. Description of the invention (2) The panel (11) is made in-house, and the panel is dried with an infrared heater. • Place a shield and irradiate UV light to The photosensitive layer formed on the inside of the panel is cured, and this layer is developed with water to form a fluorescent substance pattern. Subsequently, a fluorescent layer is coated between the black substrates in the panel, and an organic film is deposited and aluminum is formed. Aluminum film. Organic matter remaining on the fluorescent layer is removed by heat treatment. As noted above | Fluorescent screens are formed by irradiating ultraviolet light onto a photosensitive coating layer, which is made of fluorescent material, polyethylene Alcohol, ammonium dichromate, water and surfactant, etc. However, the photosensitizing mechanism is essentially carried out by polyvinyl alcohol, ammonium dichromate and water. The mechanism m used to form the fluorescent layer is divided into one Dark reaction and a light reaction 3 The dark reaction indicates a redox reaction between polyvinyl alcohol and ammonium dichromate in a fluorescent substance slurry. The light reaction indicates that after the polyvinyl alcohol chain is broken, the ion Polyethylene produced by reduction to ions Enol cross-linking reaction. As a result, in this reaction, the solubility of polyvinyl alcohol in water is reduced. Because water is used in the photoreaction, if the water on the coating layer is insufficient, the reaction will be inhibited, relatively * Excess water will inhibit cross-linking in the third space.

Cr3 * ions, which are produced in the photoreaction and are needed again in this reaction, will react to react with water to form a stable compound. However, this compound does not contribute to the crosslinking reaction. This product can be obtained in a state where appropriate moisture is retained on the fluorescent layer during photoreaction. The image can be understood by illuminating the fluorescent material coated on the inner foot surface of the panel Π 1), and the energy is provided by the electron beam emitted by the electrons in the figure. In this paper standard, the Chinese National Standard (CNS) A4 (210 X 297 mm) is used. I m I----In-I i-HI-I n-: n — 11 I n.-* (Please first Read the notes on the back and fill in this page) 霱 4 of 3023 A7 __B7_ V. Description of the invention (3) In the method described here, the coating step is to pour the aqueous solution of fluorescent substance to apply S * and wait for fluorescence After precipitation, the material is illuminated, hardened and cleaned. If the fluorescent substance is soluble in water, it has the disadvantage that it does not precipitate and is easily removed during washing. This fluorescent substance must not react with water to retain its persistence. Therefore, the water-soluble fluorescent substance is not considered, even if it has outstanding fluorescent efficiency, color reconciliation, regeneration time, etc. = The purpose of the present invention is to improve the luminousness and visibility of the color image tube by means of a dry film This method allows the use of water-soluble fluorescent substances that have been excluded by conventional color image tubes. According to the present invention, a pseudo-continuation 1 margin 1 for a color image tube and expressed by the formula (I) * is provided, and the water-soluble fluorescent substance is blended with one to oi to 5 to reset seven percent. To control the touch! Positive charge _ Huang hides I:

MxGarOz · ΑI), where M is 鹾 x = l ~ 5, y = l ~ 5 and Z = 2 ~ 8: A is a kind of shake to explain the positive electric MU quality.

The coating substance used to control the positive charge is preferably selected from the group consisting of vitamin B and Jia Jia Yi T. Bright face brewing ...

In.--= 1 ^ 1 ^ 11----i ^^ 1 in —s ~-(Please read the notes on the back before filling this page)

Produced by the consumer cooperation agreement of the Central Bureau of Standards of the Ministry of Economic Affairs, the alkali metal is preferably selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium. The water-soluble fluorescent substance has a spinel-type groove. The present invention provides a prayer of a water-soluble fluorescent substance in a color image tube. The method includes the step of heating _Jinshu sulfur spicy (MGa (SO *) nhO) in the atmosphere: it may further include The following steps: Berry ^ ^; MG ^ n, M) i This paper size is applicable to China National Standard (CNS) A4 (210 X 2 ~ 7 mm) 423023 A7 B7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4. Description of the invention (4) Disperse with gallium, evaporate the mixed solution of gallium and gallium dispersion and co-precipitate this evaporated mixed solution > The present invention also provides a method comprising the following steps: Colloidal gallium hydroxide (Ga (0H) 3) is mixed with an alkali metal M gaseous compound, and at a temperature of 300 ~ 500 t ;, a mixture of gallium hydroxide and thallium metal hydroxide is suddenly mixed. The solution was dehydrated. The present invention provides a water-soluble fluorescent flow cross-cutting powder for a color image tube, which includes a fluorescent substance and a flow ». The water-soluble fluorescent substance is pseudo-represented by formula (I) | and the water-soluble fluorescent substance is incorporated with a coating substance for controlling positive charge of 0.1 to 5 weight percent:

MxGa> Oz: A (I) where M is an alkali metal; < = 1 to 5, y = 1 to 5 and Z = 2 to 3. —A coating material used to control positively charged mint. The coating substance for controlling the positive charge is preferably selected from the group consisting of ethyl cellulose, polymethyl methacrylate, nigrosine, and a quaternary ammonium salt. The alkali metal is preferably selected from the M group consisting of lithium, sodium, potassium, cargo 11, and absolute, and the water-soluble fluorescent substance preferably includes a lotus JgJi or an activator in one step. This fluid is not air or atmosphere. The present invention provides a method for preparing a fluorescent layer for a color image tube. The method includes the steps of: charging the color image tube with a black matrix established • shining light through a shield to remove a charge on a selected area of a glass panel * And disperse the positively-charged water-soluble fluorescent fluidized powder to the size of the exposed glass paper. Applicable to China National Standard (CNS) M (210 × 297 mm) --------------- -, ΤΓ ------ ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 2302 3, A7 ______B7_ V. Description of the invention (5) Glass panel. The charging method is an electric charging method, and the fluidized powder is composed of a water-soluble fluorescent substance and a flowing cross. The present invention provides a method for preparing a fluorescent film for a color image tube, in which a water-soluble fluorescent substance A coating substance that is represented by formula (I) and is used to control the positive electrode is 0.1 to 5 weight percent: MxGaH (I) where M is a metal test and χ = 1 to 5, y = l ~ 5 and Z = 2 ~ 8. A is a coating for controlling positive electricity The coating material used to control positive electricity is preferably selected from the group consisting of ethylcellulose, polymethylmethacrylate, nig “〇sine” and a quaternary ammonium salt. Medium: The alkali metal is preferably selected from the group consisting of lithium, sodium, potassium, thallium, and absolute, and the water-soluble fluorescent substance further includes a dye family and an activator and has a spinel type. The method includes the steps of heating rhenium gold gallium gallium sulfate (MGa (SO 4 :) ηΗζΰ) in the atmosphere, or dispersing an alkali metal gallium oxide (MGahii) with a gallium dispersion, evaporating and vaporizing gallium with a gallium dispersion. A step of mixing the solution and co-precipitating the evaporated mixed solution. In addition, the method includes the steps of mixing gallium hydrochloride (Ga (0H) 3) and an alkali metal hydroxide (M (0ΗΠ, and Suddenly dehydrate the mixed solution of gallium hydride and alkali metal hydride at a temperature of 300 ~ 5003C. This fluid is preferably air or atmosphere. (Please read the precautions on the back of Jing before filling this page), π This paper size applies to China National Standard (CNS) A4 specification (2 丨 0X 297 male 423023231 Μ Β7 Printed by the Central Laboratories and Consumer Cooperatives of the Ministry of Economic Affairs. 5. Description of the Invention (s) Figure 1 briefly illustrates a color image tube. Figure 2 shows a traditional water-soluble fluorescent tube used for color image tubes. One of the coating methods of the light composition is briefly sketched. FIG. 3 is a schematic sketch showing one of the coating methods of the water-soluble fluorescent composition for a color image tube according to the present invention. FIG. The internal state of a glass panel for a color image tube after being exposed to light is positively charged. Figure 5 is a sketch of a fluorescent layer for a color image tube prepared in accordance with the present invention. Fig. 6 is a flow chart of a method for splitting a fluorescent film for a color picture tube according to the practice of the present invention. The following is only an example and does not limit the scope of the invention: mm \ Yu Jiahua. Water soluble in the gluten vinegar. The material is prepared. 100 grams of LiGa (S〇4) 2 * ηΗϋΟ is heated in the atmosphere.俾 to make a water-soluble fluorescent substance Li GaO 2. 1% by weight of ethyl cellulose was incorporated into the water-soluble fluorescent substance L 丨 GaO 3 to control the positive charge. For the preparation of cyan-colored images, the light-emitting thin film is shown in Figure 6. Construct a layer of a conductive material (41) on a cleaned glass panel for a color image tube. A light-conducting material (42) is built on top of it, which is electrically charged with this layer | and illuminated by a photomask. At this time, it is necessary to remove the charge of the photoconductor area by three exposures from three different lamp positions. • Binding chanting (please read the precautions on the back before filling this page). (CNS) Α4 size U10X297 mm 2 3 0 2 A7 B7

£ Consumption Cooperatives of Employees' Cooperatives of the Central Bureau of the Ministry of Economic Affairs 5. Description of Invention (7) Required. The black matrix is subsequently shadowed by electrophotography using a liquid astringent for the black matrix. Subsequently • In the lithium gallium strip system, 50 g of powdery fluorescent substance LiGa〇2 _? (P is a living + chemical agent) (36) was sent to the feeder, and The syringe of the light substance powder tank (37), the powder is transferred to a fluorescent substance quantity control valve (35) through a screw propeller guided by a propelling motor. It is controlled by the number of fluorescent materials that are turned on and off. The density of the liquor and powdered fluorescent material supplied through the quantity control valve is adjusted to 5 g / m3. The water-soluble fluorescent substance in powder form dispersed in a fluid composed of air or nitrogen fluidized powder is supplied to a dispersion scavenger (33), and the fluorescent substance is charged with a positive charge. Fluorescent fluidization The powder material is built into a layered structure | and is fixed on the uncharged area inside the panel, where an electric latent image has been established. The above steps recognize that charging, illumination, development, and fixing in the battery are performed three times * in accordance with the order of the red, green, and blue fluorescent substances to obtain a water-soluble fluorescent tube for a color image tube. Enriched phosphonium 2 was carried out in substantially the same procedure as in Example 1, except that 5 g of Ga was added to 1 L of UGaO2 solution, and evaporated and co-precipitated. Base cellulose is blended with the water-soluble fluorescent substance to control positive electric anise. Example 3 was carried out in substantially the same procedure as in Example 1 except that colloidal Ga (OH) 3 was added to the LnOH solution, and it was suddenly removed at a temperature of 400 ° C. -10-^^ ^ 1 u ^^^ 1 —i--tin ϊ ^^^ 1-n (Please read the notes on the back before filling in this page) Order J · Paper Standards General National Standards (CNS) A4 Specifications (2t 〇X 297 mm) 4 2 3 0 2 3 A7 B7 Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yinhe V. Invention Description (δ) Water to generate water-soluble fluorescent substance LiGa〇2, and let 1 weight percent Ethyl cellulose is blended with the water-soluble fluorescent substance to control positive charge. Xuan. Example_4 The step which is substantially the same as that of Example 1 was performed except that the water-soluble fluorescent substance LiGaO2 was blended with a coating substance for controlling positive electroluminescence. Example 5. The procedure was substantially the same as that of Example 1, except that polymethyl methacrylate was added to the water-soluble fluorescent substance L 1 GaO 2 to control positive charge.窨 Example 6 The procedure was substantially the same as that of Example 1, except that ni-srosine was mixed with the water-soluble fluorescent substance LiGa〇2 to control the positive charge. Example 7 was performed substantially the same as the example. Step 1, except that the quaternary ammonium salt is mixed with the water-soluble fluorescent substance LiGaO2, to control the positive electrode. hh comparative example: A washed glass panel for a color image tube is dried, coated with a photoresist, dried, illuminated, and washed to remove unreacted photoresist. Graphite is then applied to the panel, dried, and washed with double air water to construct a black matrix. The fluorescent slurry of ZnS · CuAl is coated on a panel formed on the black substrate of FIG. 2 through a nozzle (21), and then dried, illuminated and dried to prepare a fluorescent layer as shown in FIG. 5 . Measure the relative luminosity to evaluate the properties of the fluorescent layers in real 1 to 7 and comparative ones. ·) -11-(Please read the precautions on the back before filling out this page) 丨 —bound paper Chinese National Standard (CNS) A4 specification (210X297 public director) 423023 A7 B7 V. Description of the invention (9) The relative luminescence of the fluorescent layers prepared in Examples 1 to 7 and Comparative Example is as follows: Relative luminescence chemical formula Relative luminescence LiGa〇2: Ethyl cellulose 131 Example 2 UGa02: Ethyl cellulose 125 Example 3 LiGa〇2: Ethyl cellulose 127 Example 4 L iGa〇2 (not used to control the Coating material. 85; Example 5 LiGaOz: PMHA 130 Example S LiGa〇2: aniline black 125 Example 7 UGa〇2: quaternary ammonium salt 100 Comparative example ZnS · CuA1 100 I ----------- Packing -------- Order ------ Silver < Please read the Note $ on the back before filling out this page) Printed on 14 ”color image tube The luminescence at Ικ = 500 ϋ A, 例 3 and Comparative Examples are 88Ft-L and 69Ft-L. This shows that the fluorescent substance according to the present invention has a higher Luminescence. Since the water-soluble fluorescent layer according to Yellow Example 4 does not blend with enough fluorescent light because it has too little electricity, it is true that the water-soluble fluorescent layer of 冽 4 is -12 paper Applicable to China National Standards (CNS) A4 gauge (210X297 mm) Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs M2302 3 A7 ----— _B7_ V. Description of the invention (i〇) Relative luminous comparison The example is low. The present invention provides a fluorescent layer with superior luminescence, which is derived from a water-soluble gallium fluorescent substance with significant luminous persistence obtained by the method in the s-th letter. In this method, The electrophotographic dry screening method for laser printers has been applied to the preparation of color cathode-ray tubes. The fluorescent substance according to the present invention is a gadolinium-gallium fluorescent substance, and its chemical formula is Mda, 〇z (M is lithium, sodium, potassium, ytterbium, absolute), and generally LiGafU, LiGa〇2, LiGaOtS: MGath (M: alkali metal). The developing method according to the present invention is performed as follows : Use crown charging on glass panel for color mapping The black matrix of the tube is positively charged and illuminated. A water-soluble fluorescent substance lumped powder is prepared as follows. First, a certain amount of fluorescent substance in powder form is placed in a storage tank for powder fluorescent substance. Inside the syringe • The powdery fluorescent material is sent to the fluorescent material control valve by a spiral propeller propelled by a horse. By opening or closing the quantity control valve of the fluorescent substance, the fluorescent light supplied by the quantity control valve suddenly dehydrates a mixture of gallium hydroxide and an alkali metal hydride at a temperature of 300 to 500'C. Tree quality and a fluid * such as air or gas are mixed to the proper ratio. After mixing, this fluorescent fluidized powder is supplied to a dispersion gun. A device for electromotive charging or crown charging is placed thereon to obtain a positive electroluminescent fluidized powder. As a result, the positively-charged fluorescent fluidized powder 刖 was dispersed in the inner panel via a syringe to form a latent image of electric mint. As shown in Figure 4, it was rejected by the electric 苘 and accumulated in the uncharged area. Paper size: China National Standard (CNS) A4 (210 X297 mm) ------------ installation ------ order ------ line ί (please first (Read the notes on the back and fill out this page)

Claims (1)

4 2 3 0 2 3-A8 Β8 C8 D8 k. The scope of application for patents No. 85 1 135 No. 18 Patent application for amendments to the scope of patent applications Amendment date: October 89 1_ A water-soluble fluorescent substance for color image tubes, which is represented by the general formula ⑴, and It is coated with a coating substance (A) of 0 to 5 weight percent (A): MxGayOz: A (I) where M is an alkali metal 'and x = 1-5' y = i_5 and p2_8, and a is A coating substance for controlling positive charge; and wherein the water-soluble fluorescent substance further comprises an activator (Mp 2. The water-soluble fluorescent substance according to item 1 of the patent application scope, wherein the coating substance is selected From the following groups: ethylcellulose, polymethylisobutyrate, nigrosine, and quaternary salt. 3. If the water-soluble fluorescent substance of the first scope of the patent application, the metal test It is selected from the following groups: Lithium, Sodium, Potassium, and Rare and Absolute. 4. For the water-soluble light-emitting substance in the scope of patent application, the MxGayOz has a spinel structure. (Please read the back Please fill in this page for the matters needing attention.) Xihui Shi, the Ministry of Economic Affairs, is a consumer cooperative of the Bureau. This paper has made of the applicable Chinese National Standard (CNS > A4 size (210X297 mm)