WO2003065769A1 - Back sealing member for organic electroluminescence device, glass substrate for organic electroluminescence device, organic electroluminescence device, and methods for manufacturing sealing member and glass substrate - Google Patents

Abstract

A back sealing member for an organic electroluminescence device, capable of prolonging the life of the device, a glass substrate for an organic electroluminescence device, an organic electroluminescence device, and methods for manufacturing the sealing member and glass substrate. An organic EL device (10) comprises a soda-lime glass substrate (11); an organic EL laminate film (12) formed on one side of the glass substrate (11), a pair of organic EL drive pattern formation parts (13) formed on the surface of the glass substrate (11), in the peripheral area of the organic EL laminate film (12), and a back sealing plate (20) made of soda-lime glass, adapted for an organic EL device, and so bonded to the glass substrate (11) through an adhesive layer (14) that the organic EL laminate film (12) is accommodated inside and the organic EL drive pattern formation parts (13) are interposed between the adhesive layer and the back sealing plate. The glass substrate (11) has a dealkalized part (15) subjected to dealkalization on its outermost layer, and the back sealing plate (20) has a dealkalized part (21) subjected to dealkalization on its outermost layer.

Description

 Description: Back sealing member for organic electroluminescent element, glass substrate for organic electroluminescent element, organic electroluminescent element, and sealing member and glass substrate Manufacturing method Technical field

 The present invention relates to a back sealing member for an organic electroluminescence element, a glass substrate for an organic electroluminescence element, an organic electroluminescence element, and a method for manufacturing the sealing member and a glass substrate. Background art

 Organic electroluminescence (EL) devices have an organic multilayer film consisting of a hole transport layer, a light emitting layer, and an electron transport layer interposed between an anode and a cathode. This is a display element that performs charge injection recombination-type light-emitting operation. In addition to lowering the driving voltage, it can realize a wider range of emission colors due to the variety of organic materials. The organic EL device is used as a light source of an organic EL display.

 FIG. 5 is a cross-sectional view showing a schematic structure of a conventional organic EL device.

In FIG. 5, a conventional organic EL element 100 has a glass substrate 101, an organic EL element 102 formed on the surface of the glass substrate 101, and an organic EL element 102 on both sides. A pair of organic EL driving pattern forming portions 103 formed on the surface of the glass substrate 101 and an adhesive layer 104 so that the organic EL element 102 is accommodated inside the organic EL driving pattern forming portion 103. A back sealing plate for organic EL elements (back sealing member) 105 bonded to the surface of the glass substrate 101 via the organic EL drive pattern forming portion 43. The material of the glass substrate 101 is soda glass or non-alkali glass, and the material of the rear sealing plate 105 is glass substrate 101 for metals such as SUS (stainless steel). Since the difference in thermal expansion between the back sealing plate 105 and the glass substrate 101 deteriorates due to a large difference in thermal expansion between them, soda glass or alkali glass is used.

 In addition, as a material for the glass substrate 101 and the rear sealing plate 105, a plurality of matrix-like integratedly arranged organic EL elements 100 are used for mass production. After the sealing plate member composed of the sealing plate 105 is bonded to a glass substrate member composed of a plurality of glass substrates 101 arranged integrally in the same matrix, the individual Glass that can be easily cut as the organic EL element 100 is preferable.

 However, when soda lime glass is used as the material for the glass substrate 101 and the sealing plate 105, the alkaline components elute from the glass over time, and the alkaline components elute from the glass. Accordingly, there is a problem that the organic EL element 102 is deteriorated and the life of the organic EL element 102 is shortened. In addition, alkali-free glass has low moldability compared to soda-lime glass because it has a low softening temperature, although the alkali components are less eluted.

 An object of the present invention is to provide a rear sealing member for an organic EL element capable of extending the life of an organic EL element, a glass substrate for an organic EL element, an organic electroluminescent element, Invention disclosure for providing a method for manufacturing a glass substrate

To achieve the above object, according to a first aspect of the present invention, an organic electroluminescent device sealed on a glass substrate so as to cover an organic electroluminescent element formed on the glass substrate. Back sealing for luminescence element In the member, the back surface sealing member is made of soda lime glass, and has a top surface layer and an inside layer following the top surface layer, and the alkali metal ion concentration of the top surface layer is the inside layer. The present invention provides a back surface sealing member for an organic electroluminescence element, wherein the back surface sealing member has a lower concentration than the metal ion concentration.

 In the first embodiment of the present invention, it is preferable that the thickness of the outermost surface layer is 1 nm or more and 1 m or less.

 In the first aspect of the present invention, it is preferable that the thickness of the outermost surface layer is 10 nm or more and 100 nm or less.

 In the first aspect of the present invention, the average value of the alkaline earth metal ion concentration in the outermost surface layer is larger than the average value of the alkaline earth metal ion concentration in the inner layer. It is preferably at least 80%.

 To achieve the above object, according to a second aspect of the present invention, an organic electroluminescent element is formed on an upper surface, and the organic electroluminescent element covers the organic electroluminescent element. In the glass substrate for an organic electroluminescence element in which the back sealing member is sealed as described above, the glass substrate is made of soda lime glass, and is formed of the outermost surface layer and the second surface layer. And an inner layer, wherein the concentration of the metallic ion of the outermost surface layer is lower than the concentration of the metallic ion of the inner layer. A glass substrate for an element is provided.

 In the second aspect of the present invention, it is preferable that the thickness of the outermost surface layer is 1 nm or more and 1 μm or less.

 In the second aspect of the present invention, it is preferable that the thickness of the outermost surface layer is 10 nm or more and 100 nm or less.

In the second aspect of the present invention, the average value of the alkaline earth metal ion concentration in the outermost surface layer is an alkaline earth metal ion in an inner layer following the outermost surface layer. It is preferable that the concentration is 80% or more with respect to the average value of the ion concentration. To achieve the above object, according to a third aspect of the present invention, there is provided an organic EL device sealed on a glass substrate so as to cover an organic EL device formed on the glass substrate. In the method of manufacturing a back sealing member for manufacturing a back sealing member for an electoru luminescence element by heating and molding a glass substrate made of soda lime glass, the heat molded glass There is provided a method for manufacturing a back surface sealing member, which comprises subjecting a base plate to a dealkalization treatment.

 In the third aspect of the present invention, it is preferable that the dealkalization treatment comprises immersing the glass plate in warm water.

 In the third aspect of the present invention, it is preferable that the temperature of the hot water is 70 ° C. or more and 100 ° C. or less.

 In the third aspect of the present invention, it is preferable to add a polyvalent metal ion to the warm water.

 In the third aspect of the present invention, it is preferable that the polyvalent metal ion is an aluminum ion.

 In the third aspect of the present invention, it is preferable that the hot water has a pH of 3 or more and 10 or less.

 In order to achieve the above object, according to a fourth aspect of the present invention, an organic electroluminescent device is formed on an upper surface, and the organic electroluminescent device covers the organic electroluminescent device. A method of manufacturing a glass substrate for manufacturing an organic electroluminescence element glass substrate having a back sealing member sealed thereto by heating and molding a glass base plate made of soda lime glass. Further, there is provided a method for producing a glass substrate, which comprises subjecting the heat-molded glass base plate to a de-alkaline treatment.

In the fourth aspect of the present invention, the dealkalizing treatment is performed on the glass base plate. Preferably, it consists of immersing it in warm water.

 In the fourth aspect of the present invention, it is preferable that the temperature of the hot water is 70 ° C. or more and 100 I or less.

 In the fourth aspect of the present invention, it is preferable to add a polyvalent metal ion to the warm water.

 In the fourth embodiment of the present invention, it is preferable that the polyvalent metal ion is an aluminum ion.

 In the fourth embodiment of the present invention, it is preferable that the hot water has a pH of 3 or more and 10 or less.

 In order to further achieve the above object, according to a fifth aspect of the present invention, there is provided a back sealing member for an organic electroluminescence element according to the first aspect of the present invention. An organic EL luminescent element is provided.

 In order to further achieve the above object, according to a sixth aspect of the present invention, the glass substrate for an organic electroluminescent element according to the second aspect of the present invention is provided. An organic electroluminescent element is provided.

 To achieve the above object, according to a seventh embodiment of the present invention, a back sealing member for an organic electroluminescence element according to the first aspect of the present invention, And a glass substrate for an organic electroluminescent element according to the above aspect. An organic electroluminescent element is provided. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross-sectional view of an organic EL device including a back sealing member and a glass substrate according to the first embodiment of the present invention. Four

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FIG. 2 is a cross-sectional view of an organic EL device including a back sealing member and a glass substrate according to a modified example of the first embodiment of the present invention.

 FIG. 3 is a cross-sectional view of an organic EL device including a back sealing member and a glass substrate according to a second embodiment of the present invention.

 FIG. 4 is a cross-sectional view of an organic EL device including a back sealing member and a glass substrate according to a third embodiment of the present invention.

 FIG. 5 is a cross-sectional view showing a schematic structure of a conventional organic EL device. BEST MODE FOR CARRYING OUT THE INVENTION

 The present inventor has conducted intensive studies to achieve the above object, and as a result, the back sealing member and the glass substrate of the soda lime glass back sealing member for an organic EL element and the glass substrate are respectively the most preferred. The concentration of alkali metal ions in the surface layer is lower than the concentration of alkali metal ions in the inner layer following the outermost layer, preferably when the thickness of the outermost layer is lnm or more and 1 m or less. More preferably, when the thickness of the outermost surface layer is 1 O nm or more and 100 nm or less, deterioration of the organic EL element due to alkali metal ions can be prevented. It was found that the lifetime of the organic EL element could be extended. Further, the present inventor provides a manufacturing method for manufacturing a back sealing member for an organic EL element and a glass substrate by heating and molding a glass base plate made of soda lime glass. When the plate is subjected to a de-alkaline treatment, preferably, a treatment of immersing the glass base plate in warm water, it is possible to prevent the deterioration of the organic EL element due to the alkali metal ion, and the organic EL element is also used. It has been found that a back sealing member and a glass substrate that can extend the life of the element can be provided at low cost.

 The present invention has been made based on the results of the above research.

Hereinafter, a back sealing member and an organic EL element according to an embodiment of the present invention will be described. An organic EL device having a glass substrate will be described with reference to the drawings.

 FIG. 1 is a cross-sectional view of an organic EL device including a back sealing member for an organic EL device and a glass substrate according to a first embodiment of the present invention.

 In FIG. 1, an organic EL device 10 including a back sealing member for an organic EL device and a glass substrate according to the first embodiment of the present invention is a soda lime glass substrate 11 for an organic EL device, and a glass substrate. An organic EL laminated film 12 formed on one surface of the substrate 11 and a pair of organic EL driving patterns formed on the surface of the glass substrate 11 at the outer peripheral edge of the organic EL laminated film 12 A glass substrate through an organic EL drive pattern forming section 13 by an adhesive layer 14 made of an ultraviolet curable epoxy resin or the like so as to house the organic EL laminated film 12 inside thereof. 11. A back sealing plate (back sealing member) 20 made of soda lime glass adhered on the surface of No. 1. The glass substrate 11 is provided with a dealkalized part 15 on which the outermost layer has been dealkalized, and the rear sealing plate 20 has a dealkalized part on which the outermost layer has been dealkalized. Part 2 1 is provided. The back sealing plate 20 has a concave portion 23 formed in a part thereof, and the concave portion 23 stores a desiccant 24 such as an oxide barrier.

 The thickness of each of the glass substrate 11 and the back sealing plate 20 is 0.7 mm, preferably 0.3 to 1.1 mm. If the thickness of each of the glass substrate 11 and the rear sealing plate 20 is less than 0.3 mm, the strength of each of the glass substrate 11 and the rear sealing plate 20 becomes insufficient, and If the thickness exceeds 1.1 mm, the organic EL element 10 becomes heavy.

The glass substrate 11 is formed by subjecting a soda lime glass substrate of the same shape and the same size as the glass substrate 11 to a dealkaline treatment, and the rear sealing plate 20 is first made of a soda lime glass. The glass base plate is formed by heat molding, and the heat formed glass base plate is subjected to dealkalization treatment. As a result, the alkali metal ion concentration of the dealkalized part 15 of the glass base plate 11 is increased. The alkali metal ion concentration of the inner layer 16 is smaller than the alkali metal ion concentration of the inner layer 16, and the alkali metal ion concentration of the alkali-free portion 21 of the rear sealing plate 20 is changed to the alkali metal ion concentration of the inner portion 22. It becomes smaller than the ion concentration.

 The heat forming is performed by, for example, hot pressing using a forming die. The hot press is carried out by inserting soda lime glass of 80 mm x 80 mm in thickness of 0.9 mm between the upper and lower molds, putting it into a heating furnace at 950 ° C, and molding. After cooling to 200 ° C or less, the molded product is paid out. Since the surface of the hot press forming die has fine irregularities of 1 to 10 m in Ra, the back sealing plate 20 formed by hot pressing has Fine irregularities are transferred to the surface, and the non-glare effect is enhanced.

 The above-mentioned degraving is performed by immersing the glass plate in hot water. This makes it possible to dissolve the alkali metal ions in the outermost surface layer of the glass plate into warm water. In this case, the temperature of the hot water is preferably not less than 70 ° C and not more than 100 ° C (boiling point). If the temperature of the hot water is set to less than 70, the efficiency of the decalcification process is reduced, and boiling exceeds 100 ° C (boiling point). The time of the dealkalization treatment depends on the required performance of the glass substrate 11 and the back sealing plate 20, but is preferably 1 minute or more and 3 hours or less.

 Also, when a polyvalent metal ion is added to the above-mentioned warm water, the polyvalent metal ion is adsorbed on the surface of the glass skeleton, which is the skeletal component of the glass of the glass plate, to prevent the melting of the silica force. Therefore, damage to the outermost surface layer of the glass base plate can be suppressed, and the dealkalizing treatment can be performed efficiently. As the polyvalent metal ion, aluminum nitrate or aluminum ion (trivalent) is preferable. In particular, aluminum ion has high silica dissolution inhibiting effect and high safety. It is inexpensive. The concentration of the polyvalent metal ion is preferably about 10 ppm to about 0.1%.

The pH of the warm water is preferably 3 or more and 10 or less. Hot water If the pH is 3 or less, the alkaline earth metal ion is easily eluted from the glass plate, and if the pH exceeds 10, the alkali metal ion becomes difficult to elute. The dissolution of silica is promoted, and damage is easily generated in the outermost surface layer of the glass plate.

 The thickness and the metal ion concentration of the outermost layer 15 of the outermost layer of the glass substrate 11 and the outermost layer 21 of the outermost layer of the rear sealing plate 20 are as follows. Each is as follows.

 When the alkali metal ion concentration of the alkali-free portion 15 is lower than the alkali metal ion concentration of the inner layer 16 following the alkali-free portion 15, the glass substrate 1 made of soda lime glass is used. Even if it is 1, the alkali metal ion is less likely to elute on the surface of the glass substrate 11. Similarly, the rear sealing plate 20 is also made of soda lime glass, When the alkali metal ion concentration of the metal part 21 is lower than the alkali metal ion concentration of the inner layer 22 following the alkali removal part 21, the alkali metal ion is on the back side. It hardly elutes on the surface of the sealing plate 20, and the deterioration of the organic EL laminated film 12 due to alkali metal ions eluted from the glass substrate 11 and the back sealing plate 20 can be prevented. In addition, the formation of dark spots in the organic EL laminated film 12 is prevented. Since the material of the glass substrate 11 and the material of the back sealing plate 20 are both soda lime glass, the adhesiveness between the back sealing plate 20 and the glass substrate 11 is improved. be able to.

 For this reason, the thickness of the dealkalized parts 15 and 21 is preferably 1 nm or more and 1 nm or less, more preferably 10 nm or more and 100 nm or less. If the thickness of the decalcified portions 15 and 21 is less than 1 nm, the elution of alkali metal ions cannot be sufficiently prevented.If the thickness exceeds 10 m, the glass substrates 11 and 21 cannot be removed. The surface strength of the back sealing plate 20 decreases.

The average of the alkaline earth metal ion concentrations in the dealkalized part 15 is The average value of the alkaline earth metal ion concentration of the removal part 21 is compared with the average value of the alkaline earth metal ion concentration of the inner layer 16. When the average value of the earth metal ion concentration is 80% or less, the surface of each of the dealkalized parts 15 and 21 becomes porous. Alkali metal ions easily accumulate and easily move, so if the concentration of alkaline earth metal ions in the de-alkali parts 15 and 21 drops significantly, Alkali metal ions are easily eluted from the glass substrate 11 and the back sealing plate 20. For this reason, the average value of the alkaline earth metal ion concentration in the dealkalized part 15 is larger than the average value of the alkaline earth metal ion concentration in the inner layer 16. The average value of the alkaline earth metal ion concentration of 1 is preferably 80% or more with respect to the average value of the alkaline earth metal ion concentration of the inner layer 22.

 For this purpose, in the first embodiment of the present invention, it is preferable to adjust the pH of the hot water used for the dealkalization treatment to 3 or more. When the pH of the hot water is lower than 3, not only the alkali metal ions but also the alkaline earth metal ions are easily eluted, and the dealkalized parts 15 and 21 are formed. At the same time, it becomes difficult to maintain the alkaline earth metal ion concentration in the removal parts 15 and 21.

 In the organic EL element 10 according to the first embodiment, the rear sealing member 20 and the glass substrate 11 were both subjected to dealkalizing treatment, but one of the rear sealing member 20 and the glass substrate 11 was used. Only, preferably, only the back surface sealing member 20 may be subjected to a removal treatment.

 FIG. 2 is a cross-sectional view of an organic EL device including a back sealing member for an organic EL device and a glass substrate according to a modification of the first embodiment of the present invention.

In FIG. 2, an organic EL element 30 including a back sealing member for an organic EL element and a glass substrate according to a modification of the first embodiment of the present invention has the same structure. The configuration is basically the same as that of the organic EL element 10 in FIG. 1. The organic EL element 10 is replaced by a glass substrate 11 on a glass substrate 31, and a back sealing plate (back sealing member) 2 0 is replaced with a back sealing plate 32, and the same components are denoted by the same reference numerals, and redundant description will be omitted. Only different portions will be described below.

 The organic EL element 30 shown in Fig. 2 is a sealed structure in which a plurality of soda-lime glass back sealing plates 32 are integrally arranged in a matrix for mass production of the organic EL element 30. A plurality of soda lime glass substrates 31 each comprising an organic EL laminated film 12 and an organic EL driving pattern forming portion 13 were integrally arranged in the same matrix in the plate member. It is formed by bonding to a glass substrate member with an adhesive layer 14 and then cutting into individual organic EL elements 30.

 The glass substrate 31 has, on its outermost surface layer, a dealkalized part 33 similar to the dealkalized part 15 of the glass substrate 11 in FIG. Unlike the glass substrate 11 in that the rear sealing plate 32 is not provided, the rear sealing plate 32 is provided on the outermost surface layer thereof with the same dealkalizing part 21 as the dealkalizing portion 21 of the rear sealing plate 20 in FIG. It is different from the rear sealing plate 20 in that it is provided with a recessed portion 35 but is not provided with a decalcified portion 35 on the cut end surface 36. . In the organic EL element 30, the cut end face 34 of the glass substrate 31 not having the alkali removal part 33 and the cut end face 36 of the back sealing plate 32 not having the alkali removal part 35 are formed. However, since the organic EL element 12 is outside the portion where the organic EL element 12 is sealed, the organic EL element 12 does not deteriorate even if the cut end faces 34 and 36 are not subjected to the removal processing. .

 FIG. 3 is a cross-sectional view of an organic EL device including a back sealing member for an organic EL device and a glass substrate according to a second embodiment of the present invention.

In FIG. 3, a back surface for an organic EL device according to a second embodiment of the present invention is shown. The organic EL element 40 including the sealing member and the glass substrate has basically the same configuration as the organic EL element 10 of FIG. 1, and differs from the first embodiment in that the glass substrate and the back sealing are used. The difference is that the SiO ₂ film is formed on the stop plate. The same components are denoted by the same reference numerals, and redundant description will be omitted. Only different portions will be described below.

In the organic EL element 40 in FIG. 3, the glass substrate 41 is made of soda lime glass, and has the same shape and size as the glass substrate 11 in the organic EL element 10 in FIG. The SiO ₂ film 43 is laminated on the surface. The back sealing plate 42 is made of soda lime glass, has the same shape and the same size as the back sealing plate 20 of the organic EL element 10 of FIG. 1, and has a SiO ₂ film on its surface. 4 4 are stacked.

The S i 0 ₂ film 4 3 does not need to be laminated on the entire surface of the glass substrate 4 1, and in the organic EL element 40, the surface defining the inside 4 5 where the organic EL laminated film 12 is formed rather i as long as is stacked, also, S i 0 ₂ film 4 4 needs to be laminated on the entire surface of the rear seal plate 4 2 rather than, laminated on the surface defining the interior 4 5 Anything can be used.

According to the organic EL element 4 0 in FIG. 3, the glass substrate 4 1, Ri Contact is laminated S i 0 ₂ film 4 3 on its surface, the rear seal plate 4 2, S i 0 ₂ on the surface thereof Since the film 44 is laminated, the alkali metal ions are prevented from being eluted from the glass substrate 41 and the back sealing plate 42 in the inside 45 of the organic EL element 40, and the (4) Deterioration of the organic EL laminated film 12 due to metal ions can be prevented, and thus formation of dark spots in the organic EL laminated film 12 can be prevented.

The organic EL element 4 according to the second embodiment 0, has formed the rear sealing member 4 2 and the glass substrate 4 both 1 'S i 0 ₂ film, the back sealing member 4 2及Pi glass substrate 4 1 only, preferably the back sealing member 4 2 only S i 0 ₂ film may be formed.

 FIG. 4 is a cross-sectional view of an organic EL device including a back sealing member for an organic EL device and a glass substrate according to a third embodiment of the present invention.

 In FIG. 4, an organic EL element 50 including a back surface sealing member for an organic EL element and a glass substrate according to the third embodiment of the present invention has a configuration basically similar to that of the organic EL element 10 of FIG. It is the same, and differs from the first embodiment in that the glass substrate and the back sealing plate are subjected to the chemical strengthening treatment. The same components will be denoted by the same reference numerals, without redundant description, and only different portions will be described below.

 In the organic EL element 50 of FIG. 4, the glass substrate 51 is made of soda lime glass and has the same shape and the same size as the glass substrate 11 of the organic EL element 10 of FIG. In No. 1, a chemical strengthening treatment has been performed, and Na (sodium) atoms on the surface are converted into K (ca) atoms. The back sealing plate 52 is made of soda lime glass, has the same shape and the same size as the back sealing plate 20 of the organic EL element 10 in FIG. 1, and the back sealing plate 52 is A chemical strengthening treatment has been applied, and: Na (Na) atoms on the surface have been converted to K (Ca) atoms.

 The entire surface of the glass substrate 51 does not need to be subjected to the above-mentioned chemical strengthening treatment, and the surface defining the inside 53 of the organic EL element 50 where the organic EL laminated film 12 is formed is not required. The back sealing plate 52 need not have been subjected to the above-described chemical strengthening treatment, and the surface defining the interior 53 may be sufficient. It is only necessary that the steel be subjected to a chemical strengthening treatment.

According to the organic EL element 50 of FIG. 4, the glass substrate 51 is subjected to a chemical strengthening treatment, and the Na on the surface is converted to. The back sealing plate 52 is chemically strengthened. Is applied, and Na on the surface is converted into K. In the inside 53 of the organic EL element 50, the alkali metal ions are prevented from being eluted from the glass substrate 51 and the rear sealing plate 52, and the organic EL laminated film using the alkali metal ions is prevented. 12 can be prevented from being deteriorated, and thus the formation of dark spots in the organic EL layered film 12 can be prevented.

 In the organic EL element 50 according to the fourth embodiment, the back sealing member 52 and the glass substrate 51 are both subjected to the chemical strengthening treatment, but one of the back sealing member 52 and the glass substrate 51 is used. Only, preferably, only the back sealing member 52 may be subjected to chemical strengthening treatment.

 The back sealing plate 20 of the organic EL device 10 in FIG. 1, the back sealing plate 32 of the organic EL device 30 of FIG. 2, the back sealing plate 42 of the organic EL device 40 of FIG. 3, and The back sealing plate 52 of the organic EL element 50 in FIG. 4 has a recess 23 formed in a part thereof, and the recess 23 stores a desiccant 2 such as barium oxide. However, the present invention is not limited to this. For example, the rear sealing plates 20, 32, 42, 52 may be substantially flat, and may be provided with no desiccant 24. Good. When the back sealing plates 20, 32, 42, 52 are almost flat and do not include the desiccant 24, the back sealing plate is used for the organic EL elements 10, 30, 40, 50. Images can be viewed through the stop plates 20, 32, 42, 52.

 Next, examples of the organic EL device including the back sealing member for an organic EL device and the glass substrate according to the present invention will be specifically described.

The present inventor has proposed that the organic EL element 10 of FIG. 1 has nine types of sourcing elements, which differ only in the thickness of the rear part 21 of the outermost surface layer of the rear sealing plate 20 made of soda lime glass. Organic EL element 10 having rear glass sealing plate 20 made of single glass (Example:! ~ 5, Comparative example:! ~ 4, Table 1), and alkaline earth of dealkalized part 21 Nine different types differ only in the ratio of the average value of the alkaline earth metal ion concentration in the inner part 22 of the rear sealing plate 20 to the average value of the similar metal ion concentration. 02 13674

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The organic EL element 10 having a back sealing plate 20 made of soda lime glass (Examples 6 to 10, Comparative Examples 5 to 8, Table 2) and the rear sealing plate 20 were subjected to a de-alkali treatment. An organic EL device 10 (Comparative Example 9) having a back sealing plate 20 made of soda lime glass in which the thickness of the alkali-removed portion 21 was reduced to 0 mm without application was prepared. For these Examples 1 to 10 and Comparative Examples 1 to 9, the amount of precipitated alkali metal salt was evaluated and the dark spot generation time of the organic EL laminated film 12 was evaluated. Back sealing plate strength was evaluated for Comparative Examples 1 to 5 and Comparative Examples 1 to 4 and 9.

 The evaluation of the crystal deposition amount of the alkali metal salt was performed by exposing each of the above Examples 1 to 10 and Comparative Examples 1 to 9 for 120 hours under an environment of an ambient temperature of 60 ° C and a humidity of 80%. After that, by using a dark field observation with an optical microscope (X20.0 magnification), the metal salt deposited on the surface of each back sealing plate 20 of the above Examples 1 to 10 and Comparative Examples 1 to 9 was examined. The number of crystal grains (glass grains) was counted in the field of view, and ranks A to E were used. The evaluation shows that the amount of precipitated alkali metal salt crystals increases from evaluation A to evaluation E. Specifically, the number of crystal grains of the alkali metal salt was 0 to 10 for evaluation A, 10 to 50 per field for evaluation B, and 50 to 200 for evaluation C. Individual / view, evaluation D: 200 to 50,000 / view, evaluation E: 500 or more / view.

 The evaluation of the dark spot generation time of the organic EL laminated film 12 was performed by storing each of the above Examples 1 to 10 and Comparative Examples 1 to 9 in a high temperature environment at an ambient temperature of 100 ° C. in a driving state. The measurement was performed by measuring the time until the occurrence of dark spots.

In the evaluation of the strength of the back sealing plate, a load used for bonding to the glass substrate 11 was applied to the vicinity of the center of the surface of the back sealing plate 20 in each of Examples 1 to 5 and Comparative Examples 1 to 4 and 9 above. The rear sealing plate 20 was checked for damage, and ranks A to C were used. Back sealing plate 20 is organic EL laminated film 1 2 etc. 13674

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When the glass substrate 11 on which is formed is adhered to the adhesive layer 14 with a certain force, a certain force is applied to the rear sealing plate 20. At this time, the rear sealing plate 20 is deformed. May be damaged. For this reason, it is necessary for the back sealing plate 20 to withstand a certain amount of pressurized deformation, and the above evaluation assuming this step is required. In the evaluation, the strength decreased from Evaluation A to Evaluation C.Specifically, Evaluation A was in a state where there was no breakage, and Evaluation B was in a state where there was a risk of breakage in the sealing process considering variation in breakage. Evaluation C indicates a state in which there is a considerable probability of damage during the sealing process.

 Table 1 shows the evaluation of the crystal deposition amount of the alkali metal salt, the evaluation of the dark spot generation time of the organic EL laminated film 12 and the evaluation of the strength of the back sealing plate for Examples 1 to 5 and Comparative Examples 1 to 4 and 9. The result is shown.

表 1 において、 実施例 1 〜 5及び比較例 1 〜 4 ， 9の総合評価は、 脱 アルカリ部 2 ίの厚みと して好ま しい方から、 評価〇、 評価厶、 評価 X と して示されている。 表 1 のアルカリ金属塩の結晶析出量評価、 有機 E L積層膜 1 2のダークスポッ ト発生時間評価、 及び背面封止板強度評価 の結果よ り、 脱アルカリ部 2 1の厚みは 1 n m以上 1 以下であるの が好ま しく、 1 0 n m以上 1 0 0 n m以下であるのがさ らに好ま しいこ とが分かつた。

In Table 1, the overall evaluations of Examples 1 to 5 and Comparative Examples 1 to 4 and 9 are given in order of the thickness of 2 mm of the alkali-free part. It is shown as From the results of the evaluation of the crystal deposition amount of the alkali metal salt, the evaluation of the dark spot generation time of the organic EL laminated film 12, and the evaluation of the strength of the rear sealing plate in Table 1, the thickness of the alkali-free portion 21 is 1 nm or more and 1 or less. It was found that it is more preferable that the thickness be 10 nm or more and 100 nm or less.

 Table 2 shows the results of the evaluation of the crystal deposition amount of the alkali metal salt and the evaluation of the dark spot generation time of the organic EL laminated film 12 for Examples 6 to 10 and Comparative Examples 5 to 9 described above.

Table 2

表 2 において、 実施例 6 〜 1 0及ぴ比較例 5 〜 9の総合評価は、 実施 例 6 〜 1 0及び比較例 5 〜 9 の各々の背面封止板 2 0の脱アルカ リ部 2 1 のアルカ リ土類金属ィォ ン濃度の平均値と、 内側層 2 2 のアルカ リ土 類金属イ オン濃度の平均値に対する比と して好ま しいものを評価〇、 好 ま しく ないものを評価 Xと して示されている。 表 2のアルカリ金属塩の P0213674

In Table 2, the comprehensive evaluation of Examples 6 to 10 and Comparative Examples 5 to 9 is based on the dealkalized part 21 of the rear sealing plate 20 of each of Examples 6 to 10 and Comparative Examples 5 to 9. Of the average value of the alkaline earth metal ion concentration of the inner layer 22 and the average value of the alkaline earth metal ion concentration of the inner layer 22 was evaluated as favorable. Indicated as X. Table 2 of alkali metal salts P0213674

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From the results of the evaluation of the amount of crystal deposition and the evaluation of the dark spot generation time of the organic EL laminated film 12, the inner layer of the alkaline-earth metal ion concentration average value of the alkali-free metal part 21 of the rear sealing plate 20 was found. It has been found that the ratio of 22 to the average value of the alkaline earth metal ion concentration is preferably 80% or more.

In addition, in the deallocation of the rear sealing plate 20, the present inventor has made eight kinds of soda lime glass backs which have been subjected to dealkalization treatment (treatment example 1) with hot water of different temperatures for a predetermined time. The organic EL device 10 having the sealing plate 20 (Examples 11 to: I5, Comparative Examples 10 to: 12 and Table 3). each different temperatures and multivalent gold Shokui on, the example a 1 N 0 predetermined time de-alkali treatment varies with warm water with and without addition of ₃ (processing example 2) six Soviet one Dalai Mugarasu made subjected The organic EL element 10 having the back sealing plate 20 (Examples 16 to 18 and Comparative Examples 13 to 15 and Table 4) was used for de-alkali treatment on the back sealing plate 20. Then, 10 kinds of solutes subjected to dealkalization treatment (treatment example 3) at a predetermined temperature and for a predetermined time with warm water having different pH, respectively. The organic EL device 1 0 with Dara Lee arm glass rear sealing plate 2 0 (Example 1 9-2 3, Comparative Example 1 6-2 0, Table 5) was created.

 For the organic EL devices 10 of the above Examples and Comparative Examples, an evaluation of the efficiency of the dealkalization treatment and an appearance inspection of the surface of the back sealing plate 20 were performed.

 The efficiency of the dealkalization process was evaluated based on the differences in the dealkalization process (differences due to hot ice temperature, differences due to the presence or absence of polyvalent metal ions, and differences due to hot water pH). The evaluation was performed by comparing the thickness of the dealkali part 21 formed.

The appearance inspection of the surface of the back sealing plate 20 is performed by dark field observation with an optical microscope (X200 magnification), and the degree of scratches generated by etching, which is generally called latent scratching, is rated A to C. The relative evaluation was made by attaching the links. Evaluation is evaluation A The evaluation indicates that the number of scratches on the surface of the back sealing plate 20 is large as the evaluation proceeds to C. Specifically, the evaluation A was 0 visual fields, and the evaluation B was 0 to 0.5 visual fields / field. Indicates that the condition is 0.5 or more / field of view.

 Table 3 shows the relationship between the temperature of the hot water for dealkalization treatment in Treatment Example 1 and the thickness of the dealkalized portion 21 of the rear sealing plate 20.

Table 3

表 3から、 脱アルカリ処理用温水の温度は、 7 0 以上であるのが好 ま しいことが分かつた。

Table 3 shows that the temperature of the hot water for the dealkalization treatment is preferably 70 or more.

Table 4 shows the thickness of the dealkalized portion 21 of the back sealing plate 20 and the appearance of the back sealing plate 20 surface with respect to whether or not polyvalent metal ions were added to the hot water for dealkalization treatment in Treatment Example 2. Show the relationship. Table 4

表 4から、 脱アルカ リ処理用温水に多価金属ィォンの添加をするのが 好ま しいことが分つた。

Table 4 shows that it is preferable to add the polyvalent metal ion to the hot water for dealkalization treatment.

Table 5 shows the thickness of the dealkalized part 21 of the rear sealing plate 20 and the alkaline earth metal of the dealkalized part 21 with respect to the pH of the hot water for deallocation by treatment example 3. 2 shows the ratio of the average ion concentration to the average value of the internal 22 of the alkaline earth metal ions, and the relationship between the appearance inspection of the surface of the back sealing plate 20.

Table 5

表 5 において、 実施例 1 9 2 3 '、 比較例 1 6 2 0 の総合評価は、 脱アルカ リ処理用温水の p Hと して好ま しい方から、 評価〇、 評価厶、 評価 X と して示されている。表 5 から、 脱アルカ リ処理用温水の p Hは、 3以上 1 0以下であるのが好ま しいこ とが分かった。

In Table 5, the comprehensive evaluations of Example 1923 'and Comparative Example 1620 were evaluated as evaluation 〇, evaluation 、, and evaluation X, starting with the preferred pH as the de-alkaline treatment hot water. Shown. From Table 5, it was found that it is preferable that the pH of the hot water for dealkalization treatment is 3 or more and 10 or less.

As described above, the evaluation of the crystal deposition amount of the alkali metal salt, the evaluation of the dark spot generation time of the organic EL laminated film 12, the evaluation of the strength of the back sealing plate, the evaluation of the efficiency of the alkali removal treatment, and the evaluation of the back sealing The appearance inspection of the surface of the plate 20 was performed on the organic EL element 10 with the thickness of the rear part 21 of the back sealing plate 20 different from that of the embodiment 1 23 and the comparative example 120. Similarly, the thickness of the dealkalized portion 21 of the glass substrate 11 was different from that of the back sealing plate 20 of Example 123 and Comparative Example 120 in the same manner. In contrast to the above, the evaluation of the crystal deposition amount of the above-mentioned Al metal salt, the evaluation of the dark spot generation time of the organic EL laminated film 12, the evaluation of the strength of the back sealing plate, the evaluation of the efficiency of the dealkalization process, and P leak 2/13674

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(4) The appearance of the surface of the back sealing plate 20 was inspected, and the same results as in Examples 1 to 23 and Comparative Examples 1 to 20 were obtained.

 Therefore, the thickness of the dealkalized portion 15 of the glass substrate 11 is preferably 1 nm or more and 1 / ^ m or less, and more preferably 10 nm or more and 100 nm or less. In particular, the ratio of the average alkaline earth metal ion concentration in the de-alkali zone 15 to the average alkaline earth metal ion concentration in the inner layer 16 is 80% or more. It turns out to be good. In addition, in the de-alkaline treatment of the glass substrate 11, the temperature of the de-alkaline processing hot water is preferably 70 or more, and polyvalent metal ions are added to the de-alcohol processing hot water. It can be seen that the pH of the hot water for dealkalization treatment is preferably 3 or more and 10 or less.

Further, as shown in Table 6, the present inventor made a glass substrate 41 made of soda lime glass and having Sio 2 laminated on the surface thereof, and made of soda lime glass and made of soda lime glass. S i 0 ₂ organic EL element 4 0 in FIG. 3 with a rear seal plate 4 2 are stacked (example 2 4) Contact with and chemical strengthening treatment which is made及Pi Sodarai Mugarasu is applied to And the glass substrate 51 whose surface Na has been converted to K, and which is made of V—Dry glass and has been subjected to a chemical strengthening treatment, and the surface Na has been converted to K. The organic EL device 50 (Example 25) of FIG. 4 including the back surface sealing plate 52 was produced.

Next, for Examples 24 and 25, in the same manner as described above, Examples 24 and 25 were stored in a driving state under a high-temperature environment at an ambient temperature of 100 X until dark spots were generated. The dark spot generation time was evaluated by measuring the time of the dark spot. Table 6 shows the results of the dark spot occurrence time evaluation. Table 6

表 6 から、 有機 E L素子 4 0 , 5 0 において、 ガラス基板 4 1， 5 1 及ぴ背面封止板 4 2， 5 2 が、 ソーダラ イ ム ガラス製であって且つ表面 に S i 0 2が積層されている場合、 及びソ一ダラ イ ムガラス製であって 且つ化学強化処理が施されており 、 表面の N aが Kに変換されている場 合に、 高温環境下でも ガラス基板 4 1 , 5 1 及び背面封止板 4 2 , 5 2 からアルカ リ金属イ オ ンが溶出する こ と を防止でき、 ダークスポッ ト発 生時間を長くする こ とができ るこ とが分かる。 産業上の利用可能性

Table 6 shows that in the organic EL elements 40 and 50, in the organic EL elements 40 and 50, the glass substrates 41 and 51 and the back sealing plates 42 and 52 are made of soda lime glass and have Si 0 2 on the surface. When laminated, and when made of soda lime glass and subjected to chemical strengthening treatment and Na on the surface is converted to K, the glass substrate 41, even in a high temperature environment, It can be seen that alkaline metal ions can be prevented from being eluted from 51 and the rear sealing plates 42, 52, and the dark spot generation time can be prolonged. Industrial applicability

 As described in detail above, according to the back surface sealing member of the present invention, the back surface sealing member is made of soda lime glass, and the alkali metal ion concentration of the outermost surface layer is the inner layer following the outermost surface layer. Since the concentration is lower than the alkali metal ion concentration, the elution of the alkali metal ion from the surface of the back sealing member is suppressed, and the deterioration of the organic EL element due to the alkali metal ion is prevented. Therefore, the lifetime of the organic EL device can be increased.

 According to the back sealing member of the present invention, since the thickness of the outermost surface layer is not less than 1 nm and not more than 1 μm, elution of alkali metal ions from the surface of the back sealing member is further suppressed. can do.

According to the back sealing member of the present invention, the thickness of the outermost surface layer of the back sealing member Is not less than 100 nm and not more than 100 nm, it is possible to further suppress the elution of metal ions from the surface of the back sealing member.

 According to the back sealing member according to the present invention, the average value of the alkaline earth metal ion concentration in the outermost surface layer of the back sealing member is changed to the alkaline earth metal of the inner layer following the outermost surface layer. Since the average value of the metal ion concentration is 80% or more, the elution of alkaline metal ions from the surface of the back sealing member can be further suppressed.

 According to the glass substrate of the present invention, the glass substrate is made of soda lime glass, and the concentration of alkali metal ions in the outermost surface layer is lower than the concentration of alkali metal ions in the inner layer following the uppermost surface layer. Therefore, elution of alkali metal ions from the surface of the glass substrate can be suppressed, and deterioration of the organic EL element due to alkali metal ions can be prevented. Can be increased.

 According to the glass substrate of the present invention, since the thickness of the outermost surface layer is not more than 1 nm, the leaching of alkali metal ions from the surface of the glass substrate can be further suppressed.

 According to the glass substrate of the present invention, the thickness of the outermost surface layer is not less than 100 nm and not more than 100 nm, so that the elution of alkali metal ions from the surface of the glass substrate is further suppressed. be able to.

 According to the glass substrate of the present invention, the average value of the alkaline earth metal ion concentration in the outermost surface layer is different from the average value of the alkaline earth metal ion concentration in the inner layer following the uppermost surface layer. Therefore, the elution of alkali metal ions from the glass substrate surface can be further suppressed.

According to the method for manufacturing a back sealing member according to the present invention, since the soda lime glass plate formed by heating is subjected to dealkalizing treatment, the life of the organic EL element can be increased. Stop members can be provided at low cost. You.

 According to the method of manufacturing the back sealing member according to the present invention, since the deallocation force treatment is a process of immersing the soda lime glass plate in warm water, the dealamination of the soda lime glass plate is performed. Processing can be performed efficiently. According to the method of manufacturing the back sealing member of the present invention, the temperature of the hot water is not less than 70 ° C. and not more than 100 ° C., so that the decalcification of the soda lime glass base plate is more efficient. Can be applied in a targeted manner.

 According to the method for manufacturing the back sealing member according to the present invention, since the polyvalent metal ion is added to the hot water, the polyvalent metal ion is added to the surface of the silica, which is a skeletal component of soda lime glass. Adsorption prevents silica from dissolving, thereby suppressing damage to the outermost surface layer of the back sealing member.

 According to the method of manufacturing the back sealing member according to the present invention, since the polyvalent metal ion is aluminum ion, the polyvalent metal ion can be reduced in price.

 According to the method of manufacturing the back sealing member according to the present invention, since the pH of the hot water is 3 or more and 10 or less, dissolution of silica can be prevented, and thus the outermost surface layer of the back sealing member can be prevented. Damage can be suppressed.

According to the method of manufacturing a glass substrate according to the present invention, the soda lime glass base plate that has been formed by heating is subjected to dealkalizing treatment, so that the life of the organic EL element can be increased. Can be provided at low cost. According to the method for manufacturing a glass substrate according to the present invention, the dealkalizing process is a process of immersing the sodalime glass base plate in warm water. It can be applied efficiently. According to the method of manufacturing a glass substrate of the present invention, the temperature of the hot water is not less than 70 ° C. and not more than 100 ° C., so that the soda lime glass base plate is more efficiently removed. Can be applied in a targeted manner. According to the glass substrate manufacturing method of the present invention, since polyvalent metal ions are added to hot water, polyvalent metal ions are adsorbed on the silica surface, which is a skeleton component of soda lime glass. Dissolution of silica can be prevented, and thus damage to the outermost surface layer of the glass substrate can be suppressed.

 According to the method of manufacturing a glass substrate according to the present invention, since the polyvalent metal ion is an aluminum ion, the price of the polyvalent metal ion can be reduced.

 According to the glass substrate manufacturing method of the present invention, the pH of the hot water is 3 or more and 10 or less, so that the dissolution of silica can be prevented, and thus the damage of the outermost surface layer of the glass substrate can be prevented. Can be suppressed.

 According to the organic EL device of the present invention, since the back sealing member of the present invention is provided, elution of the alkali metal ions from the surface of the back sealing member is suppressed, and the organic EL device is formed of alkali metal ions. The deterioration of the device can be prevented, and the life of the organic EL device can be prolonged.

 According to the organic EL device of the present invention, since the glass substrate of the present invention is provided, elution of alkali metal ions from the surface of the glass substrate is suppressed, and deterioration of the organic EL device due to the alkali metal ions is suppressed. Thus, the lifetime of the organic EL device can be increased.

 According to the organic EL device of the present invention, since the organic EL device includes the back sealing member of the present invention and the glass substrate of the present invention, the back sealing member of the metal ion and the respective surfaces of the glass substrate are provided. It is possible to prevent the organic EL element from deteriorating due to the alkali metal ions by suppressing the elution from the organic EL element, and also to prolong the life of the organic EL element.

Claims

The scope of the claims 1. The back sealing member for an organic electroluminescence element sealed on the glass substrate so as to cover the organic electroluminescence element formed on the glass substrate; The member is made of soda lime glass and has an outermost surface layer and an inner layer following the outermost surface layer. A back sealing member for an organic electroluminescent element, wherein the back sealing member has a lower concentration of metal ions than an inner layer. 2. The back sealing member for an organic electroluminescence element according to claim 1, wherein the thickness of the outermost surface layer is not more than l nm. 3. The back sealing member for an organic electroluminescent element according to claim 2, wherein the thickness of the outermost surface layer is at least 100 nm and at most 100 nm. 4. The average value of the alkaline earth metal ion concentration in the outermost layer is 80% or more of the average value of the alkaline earth metal ion concentration in the inner layer. The rear sealing member for an organic EL port luminescent element according to any one of claims 1 to 3.  5. An organic electroluminescent element in which an organic electroluminescent element is formed on the upper surface and a back sealing member is sealed so as to cover the organic electroluminescent element. In the glass substrate for an element, the glass substrate is made of soda lime glass, and has an outermost surface layer and an inner layer following the outermost surface layer. A glass substrate for an organic electroluminescence element, wherein the concentration is lower than the alkali metal ion concentration of the inner layer. 6. The thickness of the outermost surface layer is 1 nm or more and 1 or less. The glass substrate for an organic electroluminescent element according to claim 5, wherein 7. The glass substrate for an organic electroluminescence device according to claim 6, wherein the thickness of the outermost surface layer is 10 nm or more and 100 nm or less. . 8. The average value of the alkaline earth metal ion concentration in the outermost surface layer is 80% of the average value of the alkaline earth metal ion concentration in the inner layer following the uppermost surface layer. The glass substrate for an organic electroluminescence element according to any one of claims 5 to 7, wherein the content is not less than 10%. 9. A back sealing member for the organic electroluminescent element sealed on the glass substrate so as to cover the organic electroluminescent element formed on the glass substrate, In the method of manufacturing a back sealing member manufactured by heat-molding a glass base plate made of one-piece glass, the heat-molded glass base plate may be subjected to a removing force treatment. A method for manufacturing a back surface sealing member, comprising: 10. The method for manufacturing a back sealing member according to claim 9, wherein the dealkalizing treatment comprises immersing the glass plate in warm water. 11. The method for manufacturing a back sealing member according to claim 10, wherein the temperature of the hot water is 70 ° C. or more and 100 or less.  12. The method for producing a back surface sealing member according to claim 10, wherein a polyvalent metal ion is added to the hot water.  13. The method for manufacturing a back sealing member according to claim 12, wherein the polyvalent metal ion is an aluminum ion.  14. The method for manufacturing a back surface sealing member according to claim 10, wherein ρΗ of the hot water is 3 or more and 10 or less. 15 5. An organic electroluminescent element is formed on the upper surface, and a back sealing member is sealed so as to cover the organic electroluminescent element. The method for producing a glass substrate, wherein the glass substrate for an organic electroluminescence element attached is formed by heating and molding a glass substrate made of soda lime glass. A method for manufacturing a glass substrate, which comprises subjecting a base plate to a removal treatment. 16. The method for manufacturing a glass substrate according to claim 15, wherein the dealkalizing treatment comprises immersing the glass plate in warm water.  17. The method of manufacturing a glass substrate according to claim 16, wherein the temperature of the hot water is 70 ° C. or more and 100 ° C. or less.  18. The method for producing a glass substrate according to claim 16, wherein a polyvalent metal ion is added to the hot water.  19. The method for manufacturing a glass substrate according to claim 18, wherein the polyvalent metal ion is an aluminum ion.  20. The method for producing a glass substrate according to claim 16, wherein the hot water has a pH of 3 or more and 10 or less. 21. An organic electroluminescence element comprising the back sealing member for an organic electroluminescence element according to claim 1. 22. An organic electroluminescent element comprising the glass substrate for an organic electroluminescent element according to claim 5. 23. A back sealing member for an organic electroluminescent element according to claim 1, and a glass substrate for an organic electroluminescent element according to claim 5. Organic light emitting element.