WO2007100016A1 - Envelope for display and method for sealing the same - Google Patents

Abstract

This invention provides an envelope for a display, which, even when used in an atmosphere which undergoes a temperature change, does not substantially cause any lowering in strength of a sealed part and has improved practical durability, and a method for sealing members constituting the envelope and a composition for sealing. The envelope for a display comprises two or more glass members constituting an envelope for a display which have been sealed through a sealing layer, and is characterized in that the sealing layer is formed of a sinter of a sealing material composed mainly of at least one compound selected from polyimide compounds and polyamic acid compounds and containing an inorganic oxide filler, the inorganic oxide filler is at least one filler selected from the group consisting of glass, silica, alumina and titania, and the alkali metal oxide is contained in an amount of not more than 1% by mass based on the inorganic oxide filler.

Description

 Specification

 Envelope for display and sealing method thereof

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a display envelope, a sealing method, and a sealing material composition used for a television broadcast receiver, a monitor device and the like in video equipment.

 Background art

 In general, a display (FED), a plasma display (PDP), a cathode ray tube (CRT), etc. (hereinafter collectively referred to as a display device) having a field emission type cold cathode include two or more. Components, specifically, in the case of CRT, a display panel (glass panel) on which an image is displayed, a glass funnel with an electron gun, and in the case of FED, typically the front panel (Display panel portion), a rear panel portion having a cold cathode disposed opposite to the front panel portion, and an outer frame that surrounds and surrounds the front panel portion and the rear panel portion. It is formed from an envelope obtained by wearing.

 [0003] Conventionally, as described in Patent Document 1, these sealing methods include frit glass made into a slurry, applied to an end face, dried at a relatively low temperature, and then fired at a higher temperature. It is carried out by attaching a sheet-like material to the end face and firing. As the above-mentioned flit glass, lead content is high, and PbO_BO—ZnO—SiO series crystalline low melting point solder glass is used.

[0004] The sealed envelope is evacuated at a high temperature of about 250 to 380 ° C in order to make the inside of the envelope a high vacuum. At this time, the sealing portion is loaded with tensile vacuum stress caused by the vacuum inside the envelope and tensile thermal stress caused by the temperature difference between the inside and outside. Strength that can be withstood is required. Moreover, in order to ensure the long-term reliability of the display device, the sealing part is required to have a pressure strength of 0.3 MPa or more, high airtightness, and insulation.

[0005] On the other hand, in the case of FED, the back substrate arranged in the vacuum envelope has a multilayer structure such as a force sword electrode, a resistance layer, an emitter, an insulating layer, etc. , It is desired that the heat treatment be performed at as low a temperature as possible. Also, depending on the type of emitter

At a sealing temperature of 400 ° C or higher, the emitter may be oxidized and the electron emission characteristics may be deteriorated. Therefore, a sealing material that can be sealed at less than 400 ° C. is desired.

 [0006] In addition, CRTs have become larger and flattened, and the undue force and deformation of metal members such as built-in shadow masks have caused the position of the electron beam to shift and have an adverse effect on images. Therefore, the thermal deformation of metals in the sealing process, which was not a problem before, has been brought up, and it is desired to lower the sealing temperature. It has become obvious that these thermal deformations are almost completely suppressed by making the sealing temperature below 400 ° C.

 [0007] However, in sealing using frit glass, a firing temperature of 400 ° C or higher is required, and when sealing is performed at a firing temperature of less than 400 ° C, the strength of the sealed portion is reduced. Insufficient, there was a problem that the sealing part could be broken in the subsequent high-temperature evacuation process, and there was a problem that the long-term reliability of the vacuum envelope could not be secured. In addition, frit glass contains 60% by mass or more of lead, and it is desired to make it lead-free in view of environmental impact.

 [0008] Patent document i and patent document 2 disclose sealing materials such as epoxy resins and silicone resins that can be sealed at a temperature of less than 400 ° C and do not contain lead. However, these conventional sealing materials have (1) insufficient adhesive strength with glass, (2) insufficient strength at high temperature, and (3) the sealing material itself decomposes during high-temperature vacuum evacuation, causing gas to escape. There are problems such as (4) high gas permeability and inability to maintain a high vacuum.

 As examples of other sealing materials, Patent Documents 3 to 6 describe adhesives containing polybenzimidazole rosin, polyimide resin, or a polyphenyl compound. However, these sealing materials do not sufficiently solve the problems (1) to (4).

[0009] Previously, the present applicant has proposed a sealing material mainly comprising a polyimide compound or a polyamic acid compound as Patent Document 7. A sealing material mainly composed of a strong polyimide compound or a polyamic acid compound can be sealed at a low temperature, and has excellent properties such as high bending strength, bending elastic modulus and electrical breakdown strength of the sealed portion. It aims to eliminate the conventional problems (1) to (4) above.

A sealing material mainly composed of a polyimide compound or a polyamic acid compound. It has been found that when the sealed display envelope is used in the atmosphere for a long time, the strength of the sealed portion of the display envelope is reduced and the degree of vacuum is reduced. did.

 This is particularly noticeable when the change in temperature is large even in the use atmosphere. In many cases, it is inevitable to use the display device in an atmosphere with a temperature change. Therefore, the sealing material mainly composed of a polyimide compound or a polyamic acid compound is required to be improved. .

 Patent Document 1: JP-A 52-124854

 Patent Document 2: Japanese Patent Laid-Open No. 245153

 Patent Document 3: Japanese Patent Laid-Open No. 2000-21298

 Patent Document 4: Japanese Patent Laid-Open No. 2000-251768

 Patent Document 5: Japanese Unexamined Patent Publication No. 2000-251769

 Patent Document 6: JP-A-10-275573

 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-319448

 Disclosure of the invention

 Problems to be solved by the invention

[0010] The present invention has been made in view of the above-described problems in the prior art, and is selected from a polyimide compound and a polyamic acid compound for sealing a constituent member of a display envelope made of glass. With respect to the sealing material containing at least one kind of compound, the above-mentioned problems (1) to (4) can be solved, without impairing the excellent sealing properties, and in an atmosphere with temperature changes. When used, an envelope for display that hardly causes a decrease in strength of the sealing portion or a decrease in vacuum, a sealing method for the constituent member of the envelope, and a sealing composition The purpose is to provide.

 Means for solving the problem

[0011] The present inventor has intensively studied to achieve the above-mentioned object. As a result, at least one member selected from a polyimide compound and a polyamide oxide compound is used as a constituent member of two or more display envelopes made of glass. When sealing using a sealing material containing more than one kind of compound, the decrease in the strength of the sealing part and the decrease in the degree of vacuum, etc., occur from the specific material in the sealing material. It was found that this was basically eliminated by adding the inorganic oxide filler. This is presumably because the thermal expansion coefficient of the sealing layer was lowered by the addition of the inorganic oxide filler, and approached the thermal expansion coefficient of the glass of the display envelope constituting member.

 However, when a strong inorganic oxide filler is added, the above-mentioned purpose is achieved, but bubbles are generated in the sealing layer made of the polyimide resin containing the inorganic oxide filler, and the sealing portion It has been found that this causes a decrease in the airtightness due to a decrease in strength and a lack of seal.

 As a result of research to eliminate such problems, it was found that the generation of bubbles in the sealed part of the force and the crack was based on the alkali metal component contained in the inorganic oxide filler to be added. It was found that the use of an inorganic oxide filler having a mass strength of S; L mass% or less can be eliminated. This is because when an alkali metal oxide is contained in the inorganic oxide filler, hydrolysis of the polyimide compound or polyamic acid compound in the sealing material is accelerated by the alkali metal, and bubbles are generated. This is because the hydrolysis is suppressed when the content of the alkali metal oxide is 1% by mass or less.

 This invention is based on said novel knowledge, and has the following summary.

 (1) Two or more display envelope components made of glass are display envelopes sealed via a sealing layer,

 The sealing layer is made of a fired body of a sealing material mainly containing at least one compound selected from a polyimide compound and a polyamide oxide compound containing an inorganic oxide filler, and the inorganic oxide filler is And at least one filler selected from the group consisting of glass, silica, alumina and titania, and an alkali metal oxide is contained in an amount of 1% by mass or less based on the inorganic oxide filler. Envelope.

(2) the sealing layer, 38 X 10- ⁶ / ° de Lee spray envelope according to the above (1) having a C or less coefficient of thermal expansion.

 (3) The envelope for a display according to the above (1) or (2), wherein the inorganic oxide filler is glass fiber.

(4) The envelope for display according to any one of the above (1) to (3), wherein the inorganic oxide filler has an aspect ratio of 2 to 100. (5) The envelope for display according to any one of (1) to (4), wherein the inorganic oxide filler is contained in the sealing layer in an amount of 10 to 60% by mass.

 (6) The envelope for display according to (1) to (5) above, wherein the inorganic oxide filler is treated with a silane coupling agent.

 (7) In the above (1) to (6), there is a primer layer containing a fired body of at least one compound selected from an organometallic compound and a hydrolyzate thereof on at least one side of the sealing layer. Envelope for display according to crab.

 (8) The envelope for display according to (7), wherein the organometallic compound is a compound represented by the following formula (A).

R ² MR ¹ ---(A)

 n (4— n)

(Wherein, M represents at least one element selected from the group consisting of Si, Ti and Zr, R ¹ represents a hydrolyzable group, R ² represents an alkyl group or a phenyl group having 1 to 4 carbon atoms. N represents an integer of 0 to 2.)

 (9) The image display envelope according to any one of (1) to (8), wherein the envelope is a vacuum envelope.

 (10) The sealing surface of two or more display envelope components made of glass contains at least one compound selected from a polyimide compound and a polyamic acid compound as a main component and contains an inorganic oxide filler. A step of forming a layer of a sealing material containing 1% by mass or less of an alkali metal oxide in the inorganic oxide filler, and the sealing surfaces of the two or more display envelope constituent members are: A step of bonding through the layer of the sealing material, and a step of solidifying the sealing material by heating to a temperature of 250 to 400 ° C. Sealing method.

(11) Before forming the sealing material layer, on the sealing surface of the envelope component member, at least one selected from the organometallic compound represented by the formula (A) and a hydrolyzate thereof. The method for sealing an envelope constituting member for display according to the above (10), comprising a step of applying a primer layer forming material containing a compound. (12) An inorganic oxide filler comprising at least one compound selected from a polyimide compound and a polyamic acid compound as a main component and an alkali metal oxide content of 1% by mass or less. A composition for sealing an envelope constituting member for display. The invention's effect

 [0013] According to the present invention, (1) the adhesive strength with the glass is sufficient, (2) the strength is insufficient at high temperature, (3) the sealing layer itself is decomposed during high-temperature evacuation. (4) The problem of conventional sealing materials, such as high gas permeability and inability to maintain a high vacuum, has been improved, and in an atmosphere with temperature changes. Even when used, there is almost no drop in the strength of the sealing part or a decrease in the degree of vacuum.In addition, the strength of the sealing part due to the generation of bubbles in the sealing layer or the airtightness due to insufficient sealing. A display envelope having sealing properties that do not cause degradation is provided.

[0014] According to the present invention, there are also provided a sealing method for efficiently producing a powerful display envelope, and a sealing material composition used therefor.

 Brief Description of Drawings

 FIG. 1 is a partially cutaway side view of an embodiment of a display device according to the present invention, in which the display device is configured as a CRT.

 FIG. 2 is a partially cutaway side view of another embodiment of a display device according to the present invention, wherein the display device is configured as a typical FED.

 Explanation of symbols

 [0016] 1: Display device 1: Display device

 11: Vacuum envelope 11 ': Vacuum envelope

 13: Phosphor 14: Aluminum film

 15: Shadow mask 16: Electron gun

 17: Explosion-proof reinforcement band 18: Stud pin

 2: Display panel

 2 ': Display panel (front panel)

21: Display area 22: Skirt part 3: Glass funnel part

 3: Rear panel 31: Neck 咅 B

 4: Outer frame: Sealing layer

 61: Cathode 62: Field emission cold cathode

 63: Gate electrode 64: Insulating layer

 65: Anode 66: Phosphor pixel

 BEST MODE FOR CARRYING OUT THE INVENTION

[0017] (I) Sealing layer

 The sealing layer in the present invention is characterized by comprising a fired body of a sealing material containing as a main component at least one compound selected from a polyimide compound and a polyamic acid compound. Here, “main component” means that one or more compounds selected from a polyimide compound and a polyamic acid compound are based on the total mass excluding the inorganic oxide filler in the solid content of the sealing material, It means preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.

 As the polyimide compound, those having a structure represented by the following formula 1 are preferable. In addition, since a polyamic acid compound is a precursor of a polyimide compound, even when a polyamic acid compound is used, it is preferable to use a polyamide oxide that forms a polyimide compound having a structure represented by the following formula 1.

[0018] [Chemical 1]

 In the above formula 1, X represents the main skeleton of the diamine compound, and Y represents the main skeleton of the tetracarboxylic dianhydride. Here, the main skeleton of the diamine compound means the main chain excluding the amino group of the diamine compound, and the main skeleton of the tetracarboxylic dianhydride means the main chain excluding the carboxylic dianhydride group. means.

 [0020] More specifically, X and Y mean the following.

(A) When X is any one of the following formulas 4 to 8, Y is the following formulas 9 to 14. Any one of them. In the following formulas 4 to 8, each R is independently O CO— —SO 2 S—, —CH— and one C (CH 2) — force group force is one selected, and n is each independently And Z is each independently CH or a phenyl group.

 (B) When X is Formula 15 below, Y is Formula 16 or Formula 17 below. In the following formula 15, R is one selected from the group consisting of one, one O—, one CO—, —SO—, one S—, —CH—, and one C (CH 2) —. is there.

 (C) When X is the following formula 18, Y is the following formula 19.

[0021] [Chemical 2]

[0022] [Chemical 3]

[0023] [Chemical 4]

[0024] [Chemical 5]

 [0025] [Chemical 6]

[0026] [Chemical 7] [0027] [Chemical 8]

[0028] [Chemical 9]

[0029] [Chemical 10]

[0030] [Chemical 11]

[0031] [Chemical 12]

 [0032] [Chemical 13]

[0033] [Chemical 14]

 [0037] The polyimide compound may be composed of only the structure represented by Formula 1, but it is preferable that the terminal portion is sealed with a monoamine or dicarboxylic anhydride. The polyimide compound whose end is sealed with monoamine or dicarboxylic anhydride preferably has a structure represented by the following formula 2 or formula 3. In the following formulas 2 and 3, X and Y are as defined in formula 1.

 [0038] [Chemical 18]

[0039] [Chemical 19]

 In the polyimide compound of the formula 2, X ′ in the formula 2 is preferably the following formula 20 or formula 21.

-Si- (OR ⁴ ) R ⁵ '''Formula 20

3-rr In formula 20, R 4 is an alkyl group having 1 to ⁴ carbon atoms, R ⁵ is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and r is an integer of 0 to 2, preferably 0 to 1. Is an integer.

[0041] [Chemical 20]

 [0042] When the sealing layer in the present invention uses at least one compound selected from the group consisting of a polyimide compound and a polyamic acid compound having a structure represented by the formula 20 and a hydrolyzate thereof. In particular, it is preferable because a sealing portion having particularly high strength and sealing physical properties can be obtained.

 On the other hand, when the polyimide compound of the formula 3 is used, Y ′ in the formula 3 represents the following formula 22 to formula 2

It is preferable to be 6 or a gap.

[0044] [Chemical 21]

 [0045] [Chemical 22]

\ = /… 3

[0046] [Chemical 23]

[0047] [Chemical 24]

[0048] [Chemical 25]

 [0049] The polyimide compound of Formula 3 in which Y 'is any one of Formulas 22 to 26 is excellent in adhesive strength in a high-temperature environment experienced during a high-temperature evacuation process because it is thermoset during firing.

 [0050] In the present invention, the polyimide compounds of the formulas 1 to 3 are vinylene group, ethynino group, vinylidene group, benzocyclobutene-4'-yl group, isocyanato group, aryl group, oxsilane group, oxetane group. It preferably has at least one bridging group selected from the group consisting of a cyano group and an isopropenyl group. The polyimide compounds of the formulas 1 to 3 are thermally cured at the time of firing due to the introduction of these crosslinking groups, and are excellent in the adhesive strength under the high temperature environment experienced during the high temperature evacuation process.

 [0051] For the sealing material of the present invention, a polyamic acid compound having a structure represented by the following formulas 27 to 29 can also be used.

[0052] [Chemical 26]

[0053] [Chemical 27]

[0054] [Chemical 28]

... Formula 29

 In Formulas 27 to 29, X is a main skeleton of a diamine compound, X ′ is a main skeleton of a monoamine compound, Y is a main skeleton of a tetracarboxylic dianhydride, and Y ′ is a dicarboxylic acid. It is the main skeleton of anhydride.

 [0056] More specifically, XY means the following.

 (A) When X is any one of the above formulas 4 to 8, Y is any one of the above formulas 9 to 14. In the above Equations 4 to 8, each R is independently selected from one of —, —O_, —CO_—SO— —S——CH—, and —C (CH) —force, group force, and so on. Each of n is independently 0 7 and each Z is independently CH or a phenyl group.

 (B) When X is Formula 15 above, Y is Formula 16 or Formula 17 above. In the above formula 15, R is at least one selected from the group consisting of O 2 CO 3 —SO 2 S——CH— and 1 C (CH 3) —.

 (C) When X is the above formula 18, Y is the above formula 19.

 [0057] When the polyamic acid compound of the formula 28 is used, X 'in the formula 28 is preferably the above formula 20 or the formula 21.

 [0058] By using the polyamic acid compound of the formula 28 in which X 'is the formula 20 or the formula 21 as the sealing material of the present invention, the adhesion to glass can be improved. In addition, the polyamic acid compound of the formula 28 in which X ′ is the formula 20 or the formula 21 is excellent in adhesive strength in a high-temperature environment experienced during a high-temperature vacuum exhaust process because it is thermoset during firing.

 [0059] When the polyamic acid compound of the formula 29 is used, Y 'in the formula 29 is preferably any one of the above formulas 22 to 26. Since the polyamic acid compound of Formula 29 in which Y ′ is any one of Formulas 22 to 26 is thermally cured during firing, it has excellent adhesive strength under a high temperature environment experienced during a high temperature vacuum exhaust process.

[0060] The polyamic acid compounds represented by the above formulas 27 to 29 are vinylene group, ethur group, vinylidene group. It preferably has at least one bridging group selected from the group consisting of a group, a benzocyclobutene 4′-yl group, an isocyanate group, an aryl group, an oxsilane group, an oxetane group, a cyano group, and an isopropenyl group. The polyamic acid compounds of the above formulas 27 to 29 become thermosetting upon firing due to the introduction of these crosslinking groups, and are excellent in adhesive strength under a high temperature environment experienced during a high temperature evacuation process.

 [0061] The polyimide compound having the structure of Formula 1 and the polyamic acid compound of Formula 27 are synthesized by condensation of a diamine compound and tetracarboxylic dianhydride. As in the case of ordinary polycondensation polymers, these can control the molecular weight by adjusting the molar ratio of the monomer components. That is, a high molecular weight product can be formed by using 0.8 to 1.2 mol of diamine compound for 1 mol of tetracarboxylic dianhydride. When at least one compound selected from a polyimide compound and a polyamic acid compound is a high molecular weight compound, the fired product is excellent in mechanical strength, electrical insulation and the like, and is outgassed in a high temperature environment. Therefore, it is preferable as a sealing material. The molar ratio is more preferably 0.9 to 1.1 mol of the diamine compound per 1 mol of acid dianhydride.

 [0062] Specific examples of diamines that can be used to synthesize the polyimide compound having the structure of formula 1 or the polyamic acid compound of formula 27 include the following (a) to (1) diamine compounds.

 (a) Diamine having one benzene ring; p-phenylenediamine, m-phenylenediamine

(b) Diamine having two benzene rings; 3, 3, -diaminodiphenylenoate, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfur Id, 3, 4, 1-Diaminodiphenylsulfide, 4, 4'-Diaminodiphenyl-2-sulfenolide, 3, 3'-Diaminodiphenylsulfone, 3, 4'-Diaminodiphenylsulfone

4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 2, 2-di (3aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2 _ (3-aminophenyl) _ 2 _ (4-Aminophenyl) propane, 2,2-di (3-aminophenyl) 1,1,1,1,3,3 , 3 Hepros 2, 2 Di (4-aminophenol) 1, 1, 1, 3, 3, 3— Hexafluoropropane, 2— (3-Aminophenyl) 2— (4-Aminophenyl) 1, 1, 1, 1, 3, 3, 3—Hempaphnole-born Loprono. N.

 (c) Diamine having three benzene rings; 1, 1-di (3_aminophenyl) _ 1_phenylethane, 1,1-di (4-aminophenyl) -1-1-phenylethane, 1- (3-aminophenol 1) 1- (4-aminophenol) 1 1-phenylethane, 1,3 bis (3 aminophenoxy) benzene, 1,3 bis (4 aminophenoxy) benzene, 1,4 bis (3 aminophenoxy) benzene, 1,4 bis (4 aminophenoxy) benzene, 1,3 bis (3 aminobenzoyl) benzene, 1,3 bis (4 aminobenzoyl) benzene, 1,4 bis (3 aminobenzoyl) benzene, 1,4 Bis (4-aminobenzoyl) benzene, 1,3 Bis (3-aminobenzene, dimethylbenzyl) benzene, 1,3_Bis (4-aminobenzene, a-dimethylbenzen) benzene, 1, 4_ Bis (3-amino), One dimethylbenzyl) benzene, 1, 4 - bis (4-amino-alpha, alpha-dimethylbenzyl) benzene, 1, 3- bis (3-amino-alpha

, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine.

(d) Diamine having four benzene rings; 4, 4, 1-bis (3-aminophenoxy) biphenyl, 4, 4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) ) Phenenole] snorephone, bis [4_ (4_aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2 , 2_bis [4— (3 aminophenoxy) phenyl] bread, 2, 2_bis [4— (4 aminophenoxy) phenyl] propane, 2, 2_bis [3_ (3_aminophenoxy) phenyl] — 1, 1, 1, 3, 3, 3 _Hexafluoropropane, 2, 2 —bis [4— (4 aminophenoxy) phenyl] — 1, 1, 1, 3, 3, 3_hexafluoropro Bread.

 (e) Diamine having five benzene rings; 1,3-bis [4 (3- (aminophenoxy) benzoinole] benzene, 1,3-bis [4- (4-aminophenoxy) benzoinole] benzene, 1,4— Bis [4— (3-Aminophenoxy) benzoyl] benzene, 1,4_bis [4 -— (4-Aminophenoxy) benzoyl] benzene, 1,3 bis [4— (3 aminophenoxy) one, dimethyl benzyl ] Benzene, 1,3_bis [4- (4-Aminophenoxy) 1, dimethyl benzyl] benzene, 1,4 bis [4- (3 Aminophenoxy), 1, dimethylbenzyl] benzene, 1 , 4_bis [4- (4 aminophenoxy) -1, dimethylbenzyl] benzene.

 (f) Diamine having 6 benzene rings; 4, 4, 1 bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4, 4'-bis [4- (4-amino), 1 Dimethylbenzyl) phenoxy] benzophenone, 4, 4'-bis [4- (4-amino), dimethylbenzyl) phenoxy] diphenylsulfone, 4, 4'-bis [4- (4-aminophenoxy) phenoxy] Gifu Nino Resnorehon.

 (g) Diamine having an aromatic substituent; 3, 3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3, 3'-diamino-4-phenoxybenzophenone, 3, 3'-diamino-4-biphenoxybenzophenone.

 (h) Diamine having a spirobiindane ring; 6, 6, monobis (3-aminophenoxy) 3, 3, 3, 3, 4, monotetramethyl 1, 1, monospirobiindane, 6, 6, monobis (4-aminophenoxy) ) 3, 3, 3, '3,, tetramethyl 1, 1, spirobiindane.

 (i) Diamine which is a siloxane diamine; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4aminobutyl) tetramethyldisiloxane, ω-bis (3— Aminopropyl) polydimethylsiloxane, ω-bis (3-aminobutyl) polydimethylsiloxane.

(j) Diamine which is an ethylene glycol diamine; bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2aminomethoxy) ethyl] ether, bis [2 _ (2_aminoethoxy) ethyl] ether, bis [2_ (3-aminopropoxy) ethyl] ether, 1,2_bis (aminomethoxy) ethane, 1,2_bis (2 Aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2 aminoethoxy) ethoxy] ethane, ethylene glycol bis (3 aminopropyl) ether, diethylene glycol bis ( 3-Aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether.

 (k) Diamine which is a methylenediamine; ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Talented Kutan, 1,9-Diaminononane, 1,10-Diaminodecane, 1,11-Diaminoundecane, 1,12-Diaminododecane.

 (1) Diamine, an alicyclic diamine; 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2 aminoethyl) cyclo Hexane, 1,3-di (2aminoethyl) cyclohexane, 1,4-di (2aminoethyl) cyclohexane, bis (4aminocyclohexyl) methane, 2, 6_bis (aminomethyl) ) Bicyclo [2 • 2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2 · 2.1] heptane.

[0063] The diamine compounds exemplified above can be used alone or in combination as appropriate. Further, the diamine compound has at least one selected from the group consisting of a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group, with some or all of the hydrogen atoms on the aromatic ring of the diamine compound. It can be diamine substituted with two substituents. For the purpose of introducing branching, a part of the diamine compound may be replaced with triamines or tetraamines. Specific examples of such triamines include, for example, pararozuaniline.

[0064] Specific examples of tetracarboxylic dianhydrides that can be used to synthesize the polyimide compound having the structure of Formula 1 and the polyamic acid compound of Formula 27 include the following. Pyromellitic dianhydride, 3, 3 ', 4, 4' _biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4' _benzophenone tetracarboxylic dianhydride, bis ( 3,4-dicanoloxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2_bis (3,4-dicarboxyphenyl) propane dianhydride, 2, 2_bis (3,4-dicarboxyphenyl 1,1,3,3,3_hexafluoropropane dianhydride, 1 , 3 _bis (3, 4—Zicanol Boxyphenoxy) benzene dianhydride, 1,4 bis (3,4-dicanolevoxyphenoxy) benzene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2bis [(3,4 dicarboxyphenoxy) phenyl] propane dianhydride, 2, 3, 6, 7_naphthalene tetracarboxylic dianhydride, 1, 4, 5, 8 _naphthalene tetracarboxylic acid Dianhydride, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 2, 2 ', 3, 3, _benzophenone tetracarboxylic dianhydride, 2, 2 ', 3, 3' _biphenyltetracarboxylic dianhydride, 2, 2_bis (2,3-dicarboxyphenyl) propane dianhydride, 2, 2_bis (2, 3— Dicarboxyphenyl) 1,1,1,1,3,3,3_hexafluoropropane dianhydride Bis (2,3-dicarboxyphenylphenol) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,3_bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4_bis (2,3-dicarboxyphenoxy) benzene dianhydride, and 1, 2, 5, 6 Naphthalene tetracarboxylic dianhydride. The tetracarboxylic dianhydrides exemplified above can be used alone or in combination as appropriate.

 [0065] In any of the above tetracarboxylic dianhydrides, some or all of the hydrogen atoms on the aromatic ring are derived from a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. It can be used by being substituted with at least one substituent selected from the group consisting of

 [0066] Further, the ethynyl group, benzocyclobutene 4'-yl group, vinyl group, aryl group, cyano group, isocyanate group, ditrimethyl group, or isopropenyl group serving as a crosslinking point may be converted to the above diacid group. It can be used even if it is introduced as a substituent on some or all of the hydrogen atoms on the aromatic ring of water. Furthermore, it can also be incorporated into the main chain skeleton in which the vinylene group, vinylidene group, or ethynylidene group serving as a crosslinking point is not a substituent, as long as it does not impair the moldability.

 [0067] Further, for the purpose of introducing a branch, a part of tetracarboxylic dianhydride may be replaced with hexacarboxylic dianhydride or otatacarboxylic dianhydride.

In order to give heat resistance to the sealing layer, a polyimide compound or a polyamic acid compound is added. At the time of synthesis, a dicarboxylic acid anhydride or a monoamine compound may be included as a terminal sealing material. By sealing the ends of the polyimide compound and the polyamic acid compound with a dicarboxylic acid anhydride or a monoamine compound, the polyimide compound of the above formulas 2 and 3 and the polyamic acid compound of the above formulas 28 and 29 can be obtained. .

[0068] Specific examples of the dicarboxylic acid anhydride that can be used as the end-capping agent include the following compounds.

 Phthalic anhydride, 2, 3_benzophenone dicarboxylic anhydride, 3, 4_benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3, 4—dicarboxyphenol Phenyl ether anhydride, 2,3-Biphenyldicarboxylic acid anhydrous, 3,4_biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylsulfone anhydride, 3,4-dicarboxylヱ Urphenylsulfone anhydride, 2,3-dicarboxylphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1, 2 naphthalenedicarboxylic anhydride, 2, 3 Naphthalene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3 anthracene dicarboxylic anhydride, 1,9 anthra Njikarubon acid anhydride.

 These may be used alone or in combination of two or more. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used.

[0069] Specific examples of the monoamine compound that can be used as the end-capping agent include the following. Aniline, o toluidine, m-toluidine, p-toluidine, 2,3-xylysine, 2,6 xylidine, 3,4 xylidine, 3,5 xylidine, o chloroaniline, m-chloroaniline, p-chloroaniline, o —Bromoaniline, m-Bromoaniline, p-Bromoaniline, o_Nitroanilin, p-Nitroaniline, _m —Nitroaniline, o_Aminophenol, ρaminophenol, _m -Aminophenol, o anisidine, m anisidine, p_anisidine, o-phenetidine, m_phenetidine, p_phenetidine, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminominobe Zononitrile, ρ-aminobenzonitrile, m-aminobenzonitrile, 2_aminobiphenyl, 3 aminobiphenyl, 4 aminobiphenyl , 2 Amino Feuyl Phenylate Nore, 3-aminophenyl phenyl ether, 4-aminophenol phenyl ether, 2-aminobenzofenone, 3-aminobenzofenone, 4-aminominobenzophenone, 2-aminominophenylsulfide, 3-aminophenol Phenylsulfide, 4-aminophenylphenylsulfide, 2-aminophenylsulfonesulfone, 3-aminophenylsulfonylsulfone, 4-aminophenylphenylsulfone, naphthylamine, β-naphthylamine, 1-aminomino 2_Naphthol, 5—Amino 1 _Naphthol, 2—Amino 1 1 _Naphthonore, 4—Amino 1 _Naflor, 5—Amino 1 2_Naphthol, 7—Amino 1 2 Naphthonore, 8 Amino 1—Naphthol , 8 amino 1-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-a Roh anthracene and the like. Usually, among these aromatic monoamines, derivatives of aniline are preferably used. These can be used alone or in admixture of two or more.

 [0070] These monoamine compounds and dicarboxylic acid anhydrides may be used alone or in admixture of two or more. The amount of these end-capping agents used is 1 to several times the difference in the number of moles used between the diamine compound and tetracarboxylic dianhydride (excess component is tetracarboxylic dianhydride), or dicarboxylic anhydride However, it is generally used in an amount of about 0.01 mol times at least one of the components.

 [0071] The synthesis reaction of the polyimide compound or polyamic acid compound is usually carried out in an organic solvent. As the organic solvent used in this reaction, any solvent can be used as long as it can dissolve the polyimide compound and the polyamide oxide compound, which have no problem in producing the polyimide compound and the polyamide oxide compound, and also generate a force. Specific examples include amide solvents, ether solvents, and phenol solvents, and more specifically, the following organic solvents are exemplified. These may be used alone or in combination of two or more.

Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν, Ν-jetylacetamide, Ν, Ν-dimethylmethoxyacetamide, メ チ ル methyl_2_pyrrolidone, 1,3-dimethyl-1-amide Lidinone, メ チ ル Methylcaprolatatam, 1,2-dimethoxyethane monobis (2-methoxyethyl) ether, 1,2_bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethynole] Ethereal, tetrahydrofuran, 1,3_dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl Urea, Hexamethylphosphoramide, Phenols, o-Cresol, m-Cresol, p-Crezo Monore, Crezo Monoreic Acid, o-Crocuo Fenenore, m-Crocuo Fenenore, p-Crocao Fou Nore, Anisole etc.

 In particular, amide solvents are preferred from the standpoints of solution stability and workability.

[0072] At least one compound selected from the synthesized polyimide compounds and polyamic acid compounds can be used as a sealing material to be described later while being dissolved in these organic solvents. When used in such an embodiment, the solvent for the polyimide compound is preferably cresol. N-methylpyrrolidone is preferred as the solvent for the polyamic acid compound. These organic solvents can also be used as a solvent when using at least one compound selected from a synthesized polyimide compound and polyamic acid compound as a solution.

 [0073] It is also possible to coexist a known organic base catalyst in the synthesis of the polyimide compound and the polyamic acid compound. Pyridine and γ-picoline are preferred. The amount of these catalysts to be used is 0.001 to 0.50 mol with respect to 1 mol of the total amount of tetracarboxylic dianhydride. Particularly preferably, it is 0 · 01 to 0.1 mol.

 [0074] The reaction temperature for synthesizing the polyamic acid compound is -20 to 60 ° C, preferably 0 to 40 ° C. The reaction time varies depending on the type of tetracarboxylic dianhydride used, the type of solvent and the reaction temperature.

 In the present invention, the obtained organic solvent solution containing a polyamic acid compound is referred to as a sealing material containing a polyamic acid compound. Since the polyamic acid compound is a precursor of the polyimide compound, it can be used as a sealing material by heating and dehydrating the obtained polyamic acid compound to 150 to 400 ° C. to imidize it.

 [0075] The reaction temperature when synthesizing the polyimide compound is 100 ° C or higher, preferably 150 to

The temperature is generally 300 ° C., and it is generally performed while extracting water generated by the reaction. Prior to imidization, the precursor polyamic acid compound is first synthesized at a low temperature of 100 ° C or lower, and then the temperature can be raised to 100 ° C or higher to be imidized. After mixing the product and the diamine compound, imidization can be performed by immediately raising the temperature to 100 ° C or higher in the presence of an organic base. The reaction time is the tetracarboxylic acid used. It depends on the type of acid dianhydride, the type of solvent, the type and amount of the organic base catalyst, and the reaction temperature. In this case, it is common and effective to remove water by azeotropic distillation by removing azeotropic agent such as toluene in the reaction system.

 It is also possible to first synthesize a polyamic acid compound as a precursor and then chemically imidize it using an imidizing agent such as acetic anhydride.

 [0076] In the present invention, an organic solvent solution containing the obtained polyimide compound dissolved or dispersed is referred to as a sealing material solution containing a polyimide compound. The sealing liquid containing the polyimide compound has good storage stability, and is coated on the sealing surface of the envelope component made of glass and then heat-dried or pre-fired, then compared by firing. Even when fired at a low temperature and low pressure, a sufficient 90 degree sealing peel strength can be obtained. Here, the temperature of drying or pre-baking varies depending on the boiling point of the solvent, and cannot be specified, but is usually 150 to 300 ° C. On the other hand, the main firing is performed at 250 to 400 ° C.

 The polyimide compound may be used after being formed into a film by a known method, not as a solution dissolved in an organic solvent.

 [0077] In addition to the above components, a diaminosiloxane compound may be included in the sealing material in order to improve the sealing property of the sealing layer. When diaminosiloxane is used in combination, it is preferable that the polyimide compound and the polyamic acid compound are those in the above formulas 1 to 3 or formulas 27 to 29, where X is any one of formulas 4 to 7. Masle. The diaminosiloxane is preferably used in an amount of 0.10 mol or less with respect to 1 mol of the polyimide compound having the structure of Formula 1 to Formula 3 or the polyamic acid compound of Formula 27 to Formula 29. . If the amount of diaminosiloxane compound is 0.1 mol or less, the heat resistance inherent in the sealing layer will not be impaired, and storage stability such as phase separation of the sealing material will also be a problem. Will not occur.

[0078] Logarithmic viscosity is generally used as an index of the molecular weight of a polyimide compound. The polyimide compound of the present invention has a logarithmic viscosity of 0.5 g / dL in a mixed solvent (90:10) of p_chlorophenol and phenol, 35. C is preferably 0.01 to 5.0, and more preferably 0.10 to 0.50. The molecular weight of the polyamic acid compound can be measured by gel permeation chromatography (GPC), and the mass average molecular weight of the polyamic acid compound of the present invention is preferred. It is 4000-30000, More preferably, it is 5000-15000.

[0079] (II) Inorganic oxide filler contained in the sealing layer

 The sealing layer in the present invention contains at least one inorganic oxide filler selected from the group consisting of glass, silica, alumina and titania. Of these, glass having a low alkali content called non-alkali glass is preferable, and non-alkali glass fiber (fiber) is particularly preferable.

[0080] As an inorganic oxide filler, the thermal expansion coefficient is smaller than that of a polyimide resin formed from at least one compound selected from the above-mentioned polyimide compounds and polyamic acid compounds that form a sealing material. It has a coefficient of expansion, preferably 38 X 10- ⁶ / ° C or less, particularly good Mashiku is preferably those having the 20 X 10- ⁶ / ° C. When the thermal expansion coefficient of the inorganic oxide filler exceeds 38 ^× 10 ^_6 / ° C, the effect of suppressing the above-described decrease in the strength of the sealing portion and the decrease in the degree of vacuum is reduced, which is preferable. The lower limit of the thermal expansion coefficient of the inorganic oxide filler is not particularly limited, but is preferably 1 ^× 10 ^_6 / ° C or more. When the thermal expansion coefficient of the inorganic oxide filler is 1 X 10 ^_6 / ° C or more, the difference between the thermal expansion coefficient of at least one compound selected from the polyimide compounds and polyimide acid compounds used for the sealing material is different. It is preferable because it does not become too large and inconveniences such as peeling at the interface between the resin and the film hardly occur when the temperature changes.

The thermal expansion coefficient of the sealing layer containing the inorganic oxide filler is preferably 38 × 10− ° C. or less, and particularly preferably 20 ^× 10 ⁻⁶ / ° C. or less. If the Netsu膨expansion coefficient of the sealing layer is more than 38 X 10- ⁶ / ° C, since the effect of suppressing the decrease in the degradation or the degree of vacuum strength of the sealing portion as described above it is reduced unfavorably. The lower limit of the thermal expansion coefficient of the sealing layer, in particular limited, such les, but the thermal expansion coefficient is preferably suitable when Ru der ⁶ X 10_ 6 / ° C or more. If the coefficient of thermal expansion is 6 X 10_ ⁶ Z ° C or higher, the difference between the coefficient of thermal expansion of the glass envelope components will not be too large, and the sealing layer and envelope will change when the temperature changes. This is preferable because inconveniences such as peeling at the interfaces with the constituent members hardly occur. What is important as the inorganic oxide filler used in the present invention is that the content of the alkali metal oxide in the inorganic oxide filler is 1% by mass or less, preferably 0.8% by mass or less, particularly preferably 0. 6% by mass or less. Where alkali metal oxide content Means the total amount of alkali metal oxides such as lithium, sodium and potassium. The content of alkali metal oxide here is the content calculated as the equivalent amount of alkali metal oxide when the alkali metal is present in a form other than oxide in the inorganic oxide filler. means.

 [0081] When the content power of the alkali metal oxide in the inorganic oxide filler exceeds 1% by mass, bubbles are generated in the sealing material layer at the stage of firing the sealing material, and the sealing strength is reduced. It will cause a decrease in sealing performance. The amount of the alkali metal oxide contained in the inorganic oxide filler in the present invention is determined according to JISM8852, 8853 or 8856.

 [0082] The form of the inorganic oxide filler is preferably granular or fibrous. The average maximum length of the inorganic oxide filler is preferably 0.5 to 500 × m, particularly preferably:! To 200 μm.

 Among them, an elongated shape having an aspect ratio of preferably 2 to 100, particularly preferably 4 to 20, particularly a fiber is preferable. When the aspect ratio is less than 2, the effect of adding the inorganic oxide filler is not significant. When the aspect ratio exceeds 100, the fluidity of the sealing material liquid containing the inorganic oxide filler decreases, and the This is not preferable because workability is lowered. The inorganic oxide filler is preferably contained in an amount of 10 to 60% by mass, particularly preferably 20 to 50% by mass, based on the sealing layer. When the content of the inorganic oxide filler is less than 10% by mass, the effect of including the inorganic oxide filler is poor, and conversely, when the content exceeds 60% by mass, the seal containing the inorganic oxide filler is included. Neither is preferred because the fluidity of the dressing liquid or the like decreases.

[0083] In the present invention, the inorganic oxide filler is preferably treated with a silane coupling agent in order to improve compatibility with the polyimide resin constituting the sealing material. In this case, the silane coupling agent is preferably a silane having an amino group, and the amino group is preferably a primary or secondary amino group. Specifically, _Ί— Aminopropyltriethoxysilane, N _ j3 — (Aminoethyl) γ-Aminopropyltrimethoxysilane, Ν— / 3— (Aminoethyl) ONE N '— j3— (Aminoethyl) ) Γ-Aminopropyltrimethoxysilane, γ-

[0084] The treatment of the inorganic oxide filler with the silane coupling agent is usually performed by silane coupling. It is preferably carried out by immersing the inorganic oxide filler in an aqueous liquid or liquid in which the agent is dissolved or dispersed, preferably with stirring. Preferably, the silane coupling agent is attached to the surface of the inorganic oxide filler with respect to 100 parts by mass of the inorganic oxide filler, preferably from 0.5 to 5 parts by mass, particularly preferably from 0.5 to 2 parts by mass. It is processed.

 [0085] In the present invention, in addition to the above inorganic oxide filler, other additives can be contained for the purpose of adjusting the viscosity of the sealing material solution, reducing the thermal stress of the fired body, and the like. These additives are not particularly limited, and examples include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, and aluminum silicate.

 Furthermore, in the present invention, a lead-free inorganic sealing material such as a phosphoric acid-based or bismuth-based material is used in combination with a sealing material composed of at least one compound selected from the above-mentioned polyimide compounds and polyamic acid compounds. Also good. Such inorganic sealing materials are used when the display device needs to be sealed at a higher temperature, specifically 400 ° C or higher, or when it is necessary to match characteristics. Preferably used.

 [0086] (III) Primer layer

 In the present invention, when sealing the display envelope using the sealing material, it is preferable to place a primer layer on at least one side of the sealing layer. The primer layer includes a fired body of one or more compounds selected from an organometallic compound represented by the following formula (A) and a hydrolyzate thereof.

R ² MR ¹ (A)

n (4-n) In the formula (A), M represents at least one element selected from the group consisting of Si, Ti and Zr, R ¹ represents a hydrolyzable group, and R ² has 1 to 4 carbon atoms. An alkyl group or a phenyl group, and n represents an integer of 0 to 2.

[0087] R ¹ in the formula (A) usually represents a group capable of forming a hydroxyl group or a siloxane bond by hydrolysis at 25 to 100 ° C in the presence of no catalyst and excess water. n is an integer of 0 to 2, preferably an integer of 0 to 1, particularly preferably 0. Since the number power of n increases as the number of hydroxyl groups increases, the envelope constituent member made of glass, and the sealing layer The number of bonds increases, and good adhesion at the interface is developed. In the hydrolyzate of the organometallic compound represented by the formula (A), some unhydrolyzed R ¹ groups may remain.

[0088] Preferable examples of R ¹ include a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and an isocyanate group. Specific examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In the case of having an alkoxy group, hydrolysis is promoted when an acid is used as a catalyst, which is preferable. In the case of having an alkoxy group, it is possible to generate a large number of hydroxyl groups depending on the hydrolysis and the condensation reaction conditions, so that the adhesion at the interface can be improved. Also, compounds in which some alkoxy groups are substituted with acetylylacetonate groups can be used.

[0089] Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Since a compound having an isocyanate group or a halogen atom has a high hydrolysis rate, hydrolysis proceeds with moisture in the air even if the compound is applied as it is. For this reason, the probability of reacting the envelope component with the sealing material is higher than the condensation reaction of the hydrolyzable compound itself, so that the adhesion at the interface can be increased.

 Preferred hydrolyzable groups include alkoxy groups or isocyanate groups from the viewpoint of ease of handling and safety.

 [0090] M in the formula (A) is at least one element selected from the group force consisting of Si, Ti, and Zr, and any compound containing these elements generates a hydroxyl group or has an adhesive property at the interface. Can be increased. From the point of availability, Si has a more favorable reaction control and is easy to handle and has high storage stability.

[0091] R ² in the formula (A) is an alkyl group or phenyl group having carbon numbers:! Preferably, a methyl group, an ethyl group, a butyl group, and a phenyl group are used. If the number of carbons increases excessively, its function is impaired due to its hydrophobicity and steric hindrance. A methyl group or an ethyl group is preferable.

[0092] As a preferable specific example of the compound represented by the formula (A), a silicon compound is tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxyoxysilane, tetrabutoxysilane, tetraisocyanatesilane, methyltrichlorosilane. , Methyltrimethoxysila , Methyl triisocyanate silane, ethyltrimethoxysilane, butyltrimethoxysilane phenyltrichlorosilane, and phenyltrimethoxysilane.

 [0093] Further, examples of the titanium compound include tetrachloro titanium, tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tripropoxy monoacetyl cetato titanium, and dipropoxy bis acetyl cetato titanium. It is done.

 Examples of the zirconium compound include tetrapropoxyzirconium, tetrabutoxyzinoleconium, and tributoxymonoacetylacetonatozirconium.

 [0094] One or more compounds selected from the organometallic compound represented by the above formula (A) and a hydrolyzate thereof are preferably contained in a medium such as alcohol, preferably in a range of 0.5 to 10% by mass. The primer layer-forming material is in the form of a solution or a dispersion.

 [0095] In proceeding with the hydrolysis-condensation reaction, a hydrolysis-condensable compound containing an aluminum element may be added. Specific examples include aluminum alkoxy compounds, and aluminum isopropoxide.

 [0096] (IV) Display envelope

 The display device according to the present invention is typically a light source that emits light from a cathode (force sword) under high vacuum and collides with a phosphor to excite and emit light. Sword luminescence type. Such power sword luminescence type display devices are represented by field emission type cold cathode display devices (FED), cathode ray tubes (CRT), and the like.

 [0097] Such a display device is provided with a vacuum envelope made of glass with a high vacuum inside in order to realize force-sword luminescence. The glass forming the envelope in the present invention is preferably SiO-SrO-BaO-QO-AlO system, SiO-TO-QO1 AlO

 2 2 2 3 2 2 2 system, SiO 2 -TO-Q O—Al 0 -ZrO system, etc. are used. In these equations, T

3 2 2 2 3 2

 O represents an oxide of an alkaline earth metal, and Q O represents an alkali metal oxide. Above all, SiO

 2

 -TO-Q O-AlO glass is preferred. Inside the vacuum envelope, a high-speed electron beam

2 2 2 3

Is excited when the electron beam collides with a drive circuit for emitting light, and generates fluorescence. And a display panel portion coated with a phosphor.

 [0098] The vacuum envelope after sealing is evacuated at a high temperature in order to make the inside high vacuum. This high-temperature evacuation process has been conventionally performed at 250 to 380 ° C. However, as described in the prior art, it is preferable that the heat treatment at the time of manufacturing the display device is performed at the lowest possible temperature. Therefore, it is expected that the high-temperature evacuation process will be carried out at a temperature of 200 to 330 ° C in the future. During the high-temperature evacuation process, vacuum stress and thermal stress are applied to the sealing portion of the vacuum envelope.

 [0099] The display device according to the present invention will be described below using the conventional CRT and FED configurations as examples. However, the display device in the present invention is not limited to CRT and FED. Including CRT and FED, which is not an envelope in which the inside is in a vacuum in the final product state, a display device having an envelope that temporarily undergoes a vacuum state for gas replacement or the like is also included. For example, plasma display (PDP) is also included.

 FIG. 1 is a partially cutaway side view of an embodiment of a display device according to the present invention, and the display device 1 is configured as a CRT. In Fig. 1, the right side of the drawing is the front side and the left side is the rear side.

 In FIG. 1, a display device 1 includes a vacuum envelope (glass bulb) 11 including a display panel unit 2 and a glass funnel unit 3. The display panel part 2 constituting the front side of the vacuum envelope 11 is located in front of the vacuum envelope 11 and has a substantially planar display area 21 for displaying an image and a rear side from the side of the face part including the display area 21. It consists of a skirt portion 22 that extends in the direction. A neck 31 for storing the electron gun 16 is provided at the rear end of the glass channel portion 3 constituting the rear side of the vacuum envelope 11. The display panel part 2 and the glass funnel part 3 constituting the vacuum envelope 11 are usually made of glass. However, the display region 21 of the display panel unit 2 may be a multilayer material made of a light-transmitting resin in its front side portion that is not entirely made of glass. Further, the constituent members of the vacuum envelope 11 may be made of an inorganic material other than glass, specifically, for example, ceramic or metal.

[0101] The display device 1 shown in Fig. 1 also has an explosion-proof reinforcement band 17 for maintaining strength. A phosphor 13 that emits fluorescence by interaction with an electron beam emitted from the electron gun 16; an aluminum film 14 that reflects the fluorescence to the display surface 21 side; and the electron beam landing on a predetermined position of the phosphor 13 A shadow mask 15 for making the shadow mask 15, a stud pin 18 for fixing the shadow mask to the inner wall of the skirt portion 22, and the like.

In the display device 1 according to the present invention, the display panel portion 2 and the glass funnel portion 3 which are constituent members of the vacuum envelope 11 are sealed via the sealing layer 5. The sealing layer 5 is formed by applying a sealing material to the sealing surface of the vacuum envelope constituent member by the method described later, that is, after applying the sealing material in a liquid state, or using the sealing material as a film. It is a layer of a fired body of a sealing material obtained by firing under desired conditions after being attached. In the display device 1 shown in FIG. 1, the sealing surface of the vacuum envelope 11 components, specifically, the rear end surface of the skirt portion 22 of the display panel portion 2 and the front end surface of the glass funnel portion 3 are sealed. It is sealed through the attachment layer 5.

 [0103] In the display device of the present invention, the bending strength of the sealing portion of the vacuum envelope is preferably 30 MPa or more at 220 ° C. Here, the sealing portion of the envelope refers to a portion of the sealing layer 5 and the component constituting the envelope that is in the immediate vicinity of the sealing layer 5, and when the bending mode is loaded, The strength at the time of breaking as the starting point was defined as the bending strength of the sealing portion. Taking the display device 1 of FIG. 1 as an example, it is the bending strength of the sealing portion composed of the rear end portion of the skirt portion 22 and the front end portion of the funnel portion 3.

 In the present invention, the bending strength can be determined, for example, as a measured value of a four-point bending test performed by a method according to JIS R1601, as described in the examples described later.

FIG. 2 is a partially cutaway side view of another embodiment of a display device according to the present invention, and the display device is configured as a typical FED. In Fig. 2, the upper side of the drawing is the front side and the lower side is the rear side. In the display device 1 ′ in FIG. 2, a front panel portion (display panel portion) ₂ ′ located on the front side thereof, and a rear panel portion 3 ′ disposed on the rear side thereof facing the front panel portion 2 ′, the front panel portion. A vacuum envelope 11 ′ is composed of the outer frame 4 disposed between the panel portion 2 ′ and the rear panel portion 3 ′. The front panel part 2 ', the rear panel part 3' and the outer frame 4 which are constituent members of the vacuum envelope 11 'are usually made of glass. However, it may be made of an inorganic material other than glass, for example, ceramic or metal. . Here, the joint surfaces of the constituent members of the vacuum envelope 11 ′ are sealed through the sealing layer 5. Therefore, the joint surface between the front panel portion 2 ′ and the outer frame 4 and the joint surface between the rear panel portion 3 ′ and the outer frame 4 are sealed via the sealing layer 5.

 In the display device 1 ′, the rear panel portion 3 ′ is a field emission type electron source substrate. On the inner side surface thereof, that is, the surface facing the front panel portion 2 ′, the cathode 61 and the negative electrode 61 are provided. The field emission cold cathode 62 is formed. Further, on the surface of the rear panel portion 3 ′ that faces the front panel portion 2 ′, a Goto electrode 63 that controls the electron flow is formed across the insulating layer 64. On the other hand, an anode 65 and a phosphor pixel 66 paired with the field emission cold cathode 62 are provided on the surface of the front panel portion 2 ′ facing the rear panel portion 3 ′.

 Also in this FED display device, the sealing layer 5, that is, the sealing material of the present invention, is required to have the same characteristics as the display device 1 of the first embodiment.

[0105] (V) Sealing method

 When sealing the envelope component of the display device in the present invention, it is preferably performed as follows. That is, for the sealing surface of the envelope constituent member for the display device to be sealed, preferably one kind selected from the organometallic compound represented by the formula (A) and the hydrolyzate thereof. A primer single layer forming material comprising a solution or dispersion containing the above compound is applied. Application may be either spraying or brushing. A layer of primer layer forming material having a thickness of preferably 1 to: OOOnm is preferably formed on the sealing surface after drying. The drying is performed at room temperature in a short time, but the conditions vary depending on the type of primer layer forming material.

[0106] After forming the primer layer forming material layer, the primer layer forming material layer contains, as a main component, one or more compounds selected from polyimide compounds and polyamic acids containing an inorganic oxide filler. A sealing material or a liquid thereof is applied, or a sealing material film mainly composed of a polyimide compound containing an inorganic oxide filler is applied. The coated surface is preferably dried or pre-baked at 150 to 200 ° C. to form a sealing material layer. The layer of the primer layer forming material and the layer of the sealing material are preferably formed on both the sealing surfaces of the envelope constituent member to be sealed as described above. Piece of wear Alternatively, only the primer layer forming material layer may be formed.

 [0107] Next, the sealing surface of the envelope constituting member having the primer layer forming material layer and the sealing material layer is preferably 250 to 400 ° C, and preferably 500 to 10 It is sealed by firing for about 10 minutes, preferably at 330 to 400 ° C for 300 to 10 minutes, more preferably at 330 to 400 ° C for 60 to 10 minutes. After that, the envelope components are evacuated at a high temperature of 200 to 330 ° C. so that the inside of the envelope component is placed in a high vacuum, and the envelope of the display device is manufactured.

 [0108] The firing of the sealing surface in the present invention may be performed in an inert gas atmosphere such as a nitrogen atmosphere or an argon gas atmosphere, or may be performed in the air. In the sealing in the present invention, since the firing temperature is less than 400 ° C, problems such as thermal deformation related to the metal member in the display device when the conventional frit glass is used as the sealing material are eliminated. The

 [0109] In the above description, the primer layer forming material and the sealing material are applied separately in this order. However, in the present invention, the primer layer forming material and the sealing material are The sealing composition to be included can be applied simultaneously to the sealing surface of the envelope constituent member. Examples of the sealing composition include a primer layer forming material containing one or more compounds selected from an organometallic compound represented by the following formula (A) and a hydrolyzate thereof, an inorganic oxide filler, and a polyimide compound. And a sealing material containing at least one compound selected from polyamic acid compounds.

R ² MR ¹ (A)

 n (4-n)

(Wherein, M represents at least one element selected from the group consisting of Si, Ti and Zr, R ¹ represents a hydrolyzable group, R ² represents an alkyl group or a phenyl group having 1 to 4 carbon atoms. N represents an integer of 0 to 2.)

The ratio of the primer layer forming material and the sealing material in the sealing composition is preferably from 0.5 to 10 parts by weight, particularly preferably 1 to 100 parts by weight of the sealing material. ˜5 parts by mass is preferred. Example

 [0110] The present invention will be specifically described below with reference to Examples and Comparative Examples, but should not be construed as being limited thereto.

 In Examples and Comparative Examples, the unit without particular notice is based on mass. Examples 1 to 3 are examples, and examples 4 to 6 are comparative examples.

 (Synthesis of polyimide (1))

 In a vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube, 4, 4 'Bis (3-aminophenoxy) biphenol 55 · 26g (0.15 monole), 3, 4, 3, 4'- Biphenylenotetracarboxylic Norebon dianhydride 15.0 g (0.051 monole), pyromellitic anhydride 16.69 g (0.0765 monole), 4-phenol ethynyl phthalic anhydride 11 · 17 g (0.045 mol) ), 290 g of Crezo Monore were added and stirred at room temperature for 20 hours. Thereafter, the mixture was reacted at 200 ° C for 3 hours and cooled to room temperature. Next, 600 g of methanol was added, followed by filtration to obtain polyimide (1).

[0111] (Synthesis of polyimide (2))

 In a vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube, 35.08g (0.12 monole) of 1,3-bis (3-aminophenoxy) benzene, 6.37g of 3,3 diaminobenzozoenone (0. 93 Monore), 3, 4, 3 ', 4, Ibi, Phenyloretol Norebonic dianhydride 39. 72g (0. 135 Monore), 4_ Phenylethylphthalic anhydride 7.44g (0.03) Mol), m_Talesol 275 g was added and stirred at room temperature for 20 hours. Thereafter, the mixture was reacted at 200 ° C for 3 hours and cooled to room temperature. Next, 550 g of methanol was added, followed by filtration to obtain polyimide (2).

[0112] [Example 1]

Polyimide (1) is 28 mass%, glass fiber filler A (average fiber diameter 10 mu m, average fiber length 70 μ πι, aspect ratio: 7) is 12 mass _^0/0, and Jihidorota one Bineoru 60 mass _^0/0 Each material was weighed so as to have a ratio of 5 and mixed into a paste-like material while being ground using a mortar.

 The content of alkali metal oxide in the above glass fiber filler 繊 維 is Na ○: 0.3%

 2

, K 0: 0.2% and Li 0: 0%. The glass fiber filler A is as follows.

twenty two

And treated with a silane coupling agent. Add glass fiber filler AlOg to a container charged with 100 g of water and 3-aminopropyltrimethoxysilane lg and stir at room temperature for 4 hours. Interprocessed, filtered and dried.

 The paste-like material is used as a sealing material for glass envelopes. The thermal expansion coefficient (ii) of the sealing layer when this paste-like material is used as a sealing material was measured by the following method. Next, using this paste-like material, using the glass plate used in the glass envelope, the state of bubbles generated in the sealing layer is defined as the area ratio by the method described in (2) below. It was measured. These results are shown in Table 1. The content of the glass fiber filler A in the obtained sealing layer is the same as the ratio of the glass fiber filler A to the total of the polyimide (1) and the glass fiber filler A at the time of the paste-like preparation. %.

[0113] (1) Thermal expansion coefficient of sealing layer

 The paste was cast on a glass plate with a coater with a predetermined gap, pre-baked at 160 ° C for 30 minutes and 220 ° C for 2 hours, and then fired at 350 ° C for 2 hours. Thereafter, the film was peeled off from the glass by dipping in warm water at 80 ° C and dried at 150 ° C for 3 hours to obtain a film. This film is cut to a size of 5mm x 17mm, heated at 5 ° C / min from 30 ° C to 150 ° C using TMA60 manufactured by Shimadzu Corporation, and the coefficient of thermal expansion (ct) is measured by tensile measurement. It was measured.

 (2) Generated bubble area ratio

 Paste-like material is made up of two 60 mm square plate-like soda-lime glasses (glass composition Si〇: 71

 2

%, Ca 0: 10%, Na 0: 13%, Al 2 O: 2%, Mg 0: 4%. (Both sides are mirror surfaces)

 2 2 3

About 0.13g each was weighed, dried at 150 ° C for 30 minutes, and heat treated at 220 ° C for 120 minutes. After cooling, the two glass pieces were superposed on the joint surface, and baked at 350 ° C for 120 minutes with a load of about 100 g / cm ² , and a sample of the bonded portion was obtained. The bonded surface was observed through the mirror glass, and the state of bubbles was photographed with a digital camera.

 The resulting image is binarized to separate the bubble part from the likely part, and the area of the bubble part (A) and the area of the observed adhesion part (B) are calculated. The area ratio (%) was defined. From experience, when this area ratio is 10 or more, there is a high possibility that there is a problem in maintaining airtightness and mechanical reliability.

[0114] [Example 2]

In Example 1, polyimide (2) is used instead of polyimide (1) and glass fiber filler Instead of A, glass fiber filler B (average fiber diameter 10 μΐη, average fiber length 100 / m, aspect ratio: 10) made of the same glass is used, and the content of glass fiber filler B in the sealing layer A pasty material was produced in the same manner as in Example 1 except that the content was 20% by mass, and a sealing layer was produced.

 For the sealing layer using this paste-like material, the thermal expansion coefficient (ii) was measured in the same manner as in Example 1, and the area ratio of the generated bubbles was determined. The results are shown in Table 1.

[0115] [Example 3]

 In Example 1, glass fiber filler C made of the same glass (average fiber diameter 10 μm, average fiber length 40 μm, aspect ratio: 4) was used instead of glass fiber filler A. A pasty material was produced in the same manner as in Example 1 except that the content of C was 40% by mass in the sealing layer to prepare a sealing layer.

 For the sealing layer using this paste-like material, the thermal expansion coefficient (ii) was measured in the same manner as in Example 1, and the area ratio of the generated bubbles was determined. The results are shown in Table 1.

[0116] [Table 1]

[Example 4-6

 In Example 1, as shown in Table 2, as a filler, Example 4 (no addition), Example 5 (Kaolin: average minor axis about 4 μm, average major axis about 24 μm, aspect ratio: 6 ), Example 6 (My power: scale-like particles, average minor axis about 0.24 xm, average major axis about 12 xm, aspect ratio: 50) And a sealing layer was produced.

For the sealing layer using this paste-like material, the coefficient of thermal expansion ( And the area ratio of the generated bubbles was determined. The results are shown in Table 2.

[0118] [Table 2]

As is apparent from Tables 1 and 2, in any of the examples of the present invention, the thermal expansion coefficient of the sealing layer is small, and the generated bubbles in the sealing layer are small. On the other hand, in Examples 4 to 6, which are comparative examples, the filler does not contain any additive (Example 4), and the thermal expansion coefficient of the sealing layer is large. In the case of the product added, the bubbles generated in the sealing layer were large.

[0120] The display envelope provided by the present invention is used as a display device such as a display (FED), a plasma display (PDP), and a cathode ray tube (CRT) having a field emission cold cathode. It should be noted that the entire contents of the description, patent claims, drawings and abstract of Japanese Patent Application No. 2006-55573 filed on March 1, 2006 are incorporated herein by reference. And that is what we take in.

Claims

The scope of the claims

 [1] Two or more display envelope components made of glass are display envelopes sealed with a sealing layer,

 The sealing layer is made of a fired body of a sealing material mainly containing at least one compound selected from a polyimide compound and a polyamide oxide compound containing an inorganic oxide filler, and the inorganic oxide filler is And at least one filler selected from the group consisting of glass, silica, alumina, and titaure, and an alkali metal oxide is contained in an amount of 1% by mass or less based on the inorganic oxide filler. Envelope.

[2] The ^display envelope according to [1], wherein the sealing layer has a thermal expansion coefficient of 38 ^× 10 ^_6 / ° C. or less.

 [3] The envelope for display according to claim 1 or 2, wherein the inorganic oxide filler is glass fiber.

 [4] The envelope for display according to any one of claims 1 to 3, wherein the inorganic oxide filler has an aspect ratio of 2 to 100.

[5] The envelope for display according to any one of [5] to [4], wherein the inorganic oxide filler is contained in the sealing layer in an amount of 10 to 60% by mass.

6. The display envelope according to any one of claims 1 to 5, wherein the inorganic oxide filler is treated with a silane coupling agent.

[7] The primer layer according to any one of claims 1 to 6, wherein a primer layer containing a fired body of at least one compound selected from an organometallic compound and a hydrolyzate thereof is present on at least one side of the sealing layer. Envelope for display.

8. The display envelope according to claim 7, wherein the organometallic compound is a compound represented by the following formula (A).

R ² MR ¹ ---(A)

 n (4— n)

(Wherein, M represents at least one element selected from the group consisting of Si, Ti and Zr, R ¹ represents a hydrolyzable group, R ² represents an alkyl group or a phenyl group having 1 to 4 carbon atoms. Where n is Represents an integer of 0-2. )

 [9] The display envelope according to any one of [1] to [8], wherein the envelope is a vacuum envelope.

 [10] At least one compound selected from a polyimide compound and a polyamic acid compound as a main component and an inorganic oxide filler on the sealing surface of two or more display envelope components made of glass A step of forming a sealing material layer containing 1% by mass or less of an alkali metal oxide in the inorganic oxide filler,

 A step in which the sealing surfaces of the two or more display envelope constituent members are joined together via the sealing material layer;

 Next, a step of solidifying the sealing material by heating to a temperature of 250 to 400 ° C,

 A method for sealing an envelope constituting member for display, comprising:

[11] Before forming the sealing material layer, on the sealing surface of the envelope component member, at least one selected from the organometallic compound represented by the formula (A) and a hydrolyzate thereof. The method for sealing an envelope constituent member for a display according to claim 10, comprising a step of applying a primer layer-forming material containing a compound.

R ² MR ¹ ---(A)

 n (4-n)

(Wherein, M represents at least one element selected from the group consisting of Si, Ti and Zr, R ¹ represents a hydrolyzable group, R ² represents an alkyl group or a phenyl group having 1 to 4 carbon atoms. N represents an integer of 0 to 2.)

 [12] It comprises an inorganic oxide filler comprising at least one compound selected from a polyimide compound and a polyamic acid compound as a main component and an alkali metal oxide content of 1% by mass or less. A composition for sealing an envelope constituting member for display.