JP2007112956A - Thermosetting composition for sealing organic el element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for sealing an organic EL element that inhibits generation/growth of a dark spot consistently by sealing the EL element without exerting a harmful effect to it and maintains stable light-emitting performance for a long period of time by retaining high permeability. <P>SOLUTION: This composition comprises (A) 100 pts.wt. of a low molecular weight epoxy resin having at least two glycidyl groups and a 200-2,000 molecular weight, (B) 40-150 pts.wt. of a high molecular weight epoxy resin having a bisphenol A or a bisphenol F epoxy backbone and a 20,000-100,000 molecular weight, (C) 0.5-20 pts.wt. of a nitrile group-containing latent imidazole compound based on 100 pts.wt. of the total amount of the (A) and (B) component, and (D) 0.1-10 pts.wt. of a silane coupling agent as main components. The organic EL element is sealed using the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermosetting composition used for sealing an organic EL device that emits light with high brightness by application of an electric field, and more specifically, an organic material formed on a substrate in order to protect the organic EL device from moisture and the like. The present invention relates to a thermosetting composition that is coated on the entire surface of an EL element.

  An organic EL element is a polycrystalline semiconductor device and can be used for a backlight of a liquid crystal because it can emit light with high luminance at a low voltage, and is expected to be a thin flat display device. However, the organic EL element is very sensitive to moisture, and the interface between the metal electrode and the organic EL layer is peeled off due to the influence of moisture, the metal is oxidized to increase resistance, or the organic matter itself is altered by moisture. For this reason, there is a disadvantage that the light is not emitted and the luminance is lowered.

  In order to solve such a problem, a method of molding an organic EL element with an acrylic resin (Japanese Patent Laid-Open No. 3-37991), a method of sealing the organic EL element from outside air by enclosing P2O5 in an airtight case (special (Kaihei 3-261091), a method in which a protective film such as a metal oxide is provided on an organic EL element and then air-tight using a glass plate or the like (JP-A-4-212284), plasma on the organic EL element A method of providing a polymer film and a photocurable resin layer (Japanese Patent Laid-Open No. 5-36475), a method of storing an organic EL element in an inert liquid made of fluorinated carbon (Japanese Patent Laid-Open No. 4-363890), an organic EL A method of bonding a glass plate coated with polyvinyl alcohol on a protective film such as an inorganic oxide provided on an element with an epoxy resin (Japanese Patent Laid-Open No. 5-89959), How to contain EL element in liquid paraffin or silicone oil (JP-A-5-129080), and the like have been proposed. In recent years, a method has been proposed in which a hygroscopic material is added to a sealing resin and this is laminated on the organic EL element to protect the organic EL element from the influence of moisture.

  However, none of the above-mentioned conventional organic EL layer sealing methods are satisfactory. For example, it is not possible to suppress the generation and growth of dark spots only by enclosing the element in an airtight structure together with a hygroscopic agent. The method of storing in carbon or silicone oil not only complicates the sealing process through the process of encapsulating the liquid, but also does not completely prevent the increase of dark spots, but rather the liquid is composed of a cathode and an organic layer. There is also a problem that penetrates into the interface and promotes peeling of the cathode. Even when a hygroscopic material is added to the resin, the resin itself may expand due to moisture absorption and may cause peeling. In addition to this, in order to eliminate the adverse effect of moisture on the organic EL element, a moisture-proof layer is formed by adding a moisture absorbent made of a metal oxide such as barium oxide or calcium oxide to the photocured epoxy layer separately from the sealing layer. Providing separately is also proposed (Japanese Patent Laid-Open No. 2001-237064).

  Further, as described in JP-A-5-182759, an organic EL element is formed on a glass substrate using an ultraviolet curable resin, and a resin composition is laminated so as to cover the entire surface of the organic EL layer. A laminate of permeable glass substrates was developed. However, the resin composition described in the present invention has a problem of deterioration of the organic EL element due to the organic solvent and ultraviolet rays contained in the resin, a problem of peeling of the cathode from the organic layer due to stress strain at the time of curing, There is a problem that uncured occurs where ultraviolet rays do not reach, which is inferior in practicality. In addition, when epoxy resin is used, there is a problem with the moisture permeability of the cured product after curing, although there is less chemical impact on the device than acrylic resin. To improve this, metals such as barium oxide and calcium oxide are used. Although it is conceivable to mix a moisture absorbent composed of an oxide, in this case, since the metal oxide blended in the resin expands due to moisture, there is a problem of destroying the organic EL element itself in some cases. Moreover, when an epoxy resin is cured with an amine curing agent, the organic EL element is corroded from the pinhole of the protective film due to the influence of amine-based gas generated at the time of curing, or the cured product is easily colored, resulting in a decrease in transmittance. There was a possibility.

  On the other hand, JP-A-11-274377 discloses a paste composition composed of a thermoplastic resin, an epoxy resin, a coupling agent, silicon dioxide powder and an organic solvent, and uses an IC or LSI chip for direct sealing. It is described. However, this invention focuses on the stress relaxation property (elasticity) of the cured product, and although there is a description that it is excellent in moisture resistance, no consideration is given to the amount of water contained in the paste composition system. Not. Furthermore, when a two-component curable epoxy resin is used, there is a problem in workability due to the time and effort required for blending and mixing, equipment accompanying it, and usable time.

  Japanese Patent Application Laid-Open No. 9-176413 discloses a method for producing a transparent film using a maleic anhydride copolymer as a curing agent. However, since styrene is contained, bonding cannot be performed. In JP-A-9-235357 and JP-A-10-135255, imidazole is used in combination with an acid anhydride curing agent as a curing accelerator. Also for these, the curing temperature is high and damage to the organic EL device cannot be used. Further, in JP-A-2003-277628, 2,4-diamino-6- [2′-methylimidazole- (1 ′)]-ethyl-S-triazine isocyanuric acid adduct is used, and inertness generated during curing is disclosed. A formulation intended to impart flame retardancy with gas is disclosed. In this compounding system, a transparent cured product cannot be obtained, and it cannot be used as an organic EL panel. In addition, WO02 / 006399 and JP-A-2004-315688 disclose one using a phenoxy resin and a bisphenol-type epoxy resin, but in this system, the visible light transmittance of the cured product is low, or the coloring is strong. There is no practicality.

  JP-A-2004-59718 and JP-A-2004-210901 disclose an adhesive film or thermosetting resin using imidazole as a curing agent or curing accelerator. Both of these have a high curing temperature at the time of curing, and damage to the organic EL element is large. Japanese Patent Application Laid-Open No. 2004-115650 discloses a blend using a liquid imidazole compound. However, in this blend system, thermal stability at the time of coating into a sheet shape cannot be ensured. Furthermore, JP-A-2004-292594 discloses a compounding of an epoxy resin, a phenoxy resin, and a curing agent. However, in this compounding system, there is no mention of a flow start temperature, a moisture content, and an outgas generation amount, and an organic EL element is disclosed. It is not suitable for the entire surface sealing material.

Moreover, in the case of the sealing method using the above-mentioned liquid resin, generation | occurrence | production of a bubble was a big problem in the process of bonding an organic EL element and sealing glass. It was very difficult to attach the entire surface of the display portion without bubbles, and the inclusion of bubbles caused a decrease in the lifetime of the device. In addition, when a liquid resin is used when performing multiple chamfering from the mother glass, masking is required for the non-bonded portion, thus reducing workability.
JP-A-5-182759 JP 2001-237064 A JP 11-274377 A Japanese Patent Laid-Open No. 3-261091 JP-A-4-212284 JP-A-5-36475 JP-A-4-363890 Japanese Patent Laid-Open No. 5-89959 JP-A-5-129080 JP-A-9-176413 JP 9-235357 A Japanese Patent Laid-Open No. 10-135255 JP 2003-277628 A JP 2004-59718 A JP 2004-210901 A Japanese Patent Laid-Open No. 10-273644 JP 2004-59778 A JP 2003-82064 A

  As described above, the deterioration due to the dark spots of the organic EL element is not sufficiently improved, and the unstable emission characteristics are serious defects as light sources for facsimiles, copiers, liquid crystal display backlights, etc. It is not desirable as a display element such as a flat panel display. The present invention solves the above-mentioned problems of the prior art, and by performing sealing without adversely affecting the organic EL element, the generation and growth of dark spots are reliably suppressed, and high transmittance is maintained. It aims at providing the thermosetting composition for organic EL element sealing which can maintain the light emission characteristic stable over a period.

  In order to solve the above problems, in the present invention, (A) 100 parts by weight of a low molecular weight epoxy resin having at least two glycidyl groups in one molecule and having a molecular weight of 200 to 2000, and (B) bisphenol A type Alternatively, 40C to 150 parts by weight of a high molecular weight epoxy resin having a bisphenol F type epoxy skeleton and a molecular weight of 20,000 to 100,000, and a total of 100 parts by weight of the component (A) and the component (B), the (C) nitrile A latent imidazole compound having a group of 0.5 to 20 parts by weight and (D) a silane coupling agent of 0.1 to 10 parts by weight, the composition being non- Using a thermosetting composition for sealing an organic EL element that exhibits fluidity and exhibits fluidity in the range of 50 to 100 ° C. when heated, on a glass or film substrate And it made organic EL elements, and as a seal between the sealing glass or film substrate.

  Specifically, an organic EL layer composed of a transparent electrode, a hole transport layer, an organic EL layer and a back electrode is formed on a glass or film substrate, and the thermosetting composition in the present invention is thermally transferred thereon to make the water impermeable. The film was sealed with heat-resistant glass or film while heating. Or it heat-transfers to water-impermeable glass or a film, and it bonds together and seals to glass or a film in which the organic electroluminescent layer was formed. Moreover, it is preferable that the thermosetting composition which has said (A)-(D) as a main component has a moisture content of 100 ppm or less, and the outgas amount at the time of hardening is 1000 ppm or less.

By using the thermosetting resin composition containing (A) to (D) as a main component as an organic EL element sealant, generation and growth of dark spots can be reliably suppressed, and high transmittance can be achieved. By maintaining the organic EL panel, it is possible to provide an organic EL panel capable of maintaining stable light emission characteristics over a long period of time.
Specifically, the sealing of the organic EL element layer formed on the glass or film, or the filling and sealing of the gap between the organic EL element layer formed on the glass or film and the water-impermeable glass or film substrate layer. By using the thermosetting resin of the present invention for fixing and fixing the entire surface of the organic EL element layer, the progress of the deterioration of the organic EL element can be significantly suppressed. In addition, heat resistance and moisture resistance are improved as compared with sealing by a non-reactive sheet-like pressure-sensitive adhesive or sheet-like thermoplastic resin. Moreover, compared with sealing with an ultraviolet curable resin composition, since there are few uncured portions and large curing shrinkage where ultraviolet rays do not reach, the obtained organic EL device exhibits stable performance.

  The present invention will be described in further detail. The organic EL element sealing structure according to the present invention is manufactured as follows. First, a transparent electrode is formed to a thickness of about 0.1 μm on a glass or film substrate. In forming a transparent electrode, there are methods such as vacuum deposition and sputtering. However, film formation by vacuum deposition may cause crystal grains to grow and reduce the smoothness of the film surface, and when applied to a thin film EL, it needs to be taken care of because it causes a dielectric breakdown film and uneven light emission. . On the other hand, film formation by sputtering has good surface smoothness, and favorable results are obtained when a thin film device is laminated thereon. Subsequently, a hole transport layer and an organic EL layer are sequentially formed to a thickness of 0.05 μm on the transparent electrode. Further, a back electrode is formed to a thickness of 0.1 to 0.3 μm on the organic EL layer.

The thermosetting composition of the present invention is transferred by a roll laminator or the like onto the upper part of the glass or film substrate on which these elements have been formed. At this time, the thermosetting composition of the present invention is previously formed into a base film (release film) and formed into a sheet, and the thermosetting composition formed into the sheet is transferred with a roll laminator. . In addition, when using the method by the said transcription | transfer, a transfer can be smoothly performed if the thickness of the layer of the thermosetting composition extended on the film shall be 10-30 micrometers. Next, a water-impermeable glass or film substrate is superimposed on the transferred thermosetting composition. This is heat-pressed using a vacuum laminator device to temporarily fix the upper and lower substrates. Thereafter, the thermosetting resin is completely cured at a temperature of heating (120 ° C. or lower). In addition, when making it heat-harden, it is desirable to carry out at 120 degrees C or less so that an organic EL element may not be damaged. It is also possible to transfer the thermosetting composition of the present invention to a water-impermeable glass or film substrate and then superimpose it on the organic EL element substrate. For the purpose of improving the reliability of the organic EL element, it is also possible to superimpose the organic EL element substrate in a state where the element has been protected with an inorganic film and the water-impermeable glass or film with the thermosetting composition of the present invention. . Examples of the inorganic film include silicon oxide, silicon nitride, and silicon oxynitride.
Moreover, it is desirable that the thermosetting composition has storability for 7 days or more at room temperature in consideration of workability.

The cured product layer of the thermosetting composition of the present invention formed as described above is 1000 g / m ² × 24 hours or less in an atmosphere having a moisture permeability of 60 μC and a humidity of 95% at a thickness of 150 μm. In addition, the transmittance of 405 nm light is 90% or more with respect to a 20 μm thick cured product layer, and further has an adhesive strength of 1.0 MPa or more in a peel-to-glass adhesion test. It is desired to cure at a relatively low temperature (120 ° C. or lower).

  In particular, in the invention described in claim 6 of the present invention, it is suitable that the thickness of the cured product layer of the thermosetting composition is 1 to 100 μm, and more preferably 10 to 30 μm. When the thickness is less than 1 μm, it becomes difficult to absorb the unevenness of the formed organic EL element and to bond two plates (glass or film). Further, the thickness of the cured product layer of the thermosetting composition in the invention described in claim 8 is substantially the same as that of the invention of claim 6 described above, but the organic EL element layer is formed only by the thermosetting composition. In order to seal, a film thickness (200 μm or more) may be secured within a range where 90% light transmittance of 405 nm can be secured.

  In the thermosetting resin composition of the present invention, (A) the compound having a glycidyl group in the molecule specifically includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, phenol novolac. An epoxy resin such as a mold resin is preferably mentioned. Among these, those having a low chloride ion content, specifically, those having a hydrolyzable chlorine content of 500 ppm or less are preferred. Preferable specific examples of the component (A) include Epicron EXA-835LV (manufactured by Dainippon Ink Industries) and Epicoat 152 (manufactured by Japan Epoxy Resin Co., Ltd.) having a low concentration of chlorine ions.

The high molecular weight epoxy resin having (B) bisphenol A type or bisphenol F type epoxy skeleton and having a molecular weight of 2000 to 70000 used in the present invention is specifically solid bisphenol A type epoxy resin or solid bisphenol F type. An epoxy resin such as an epoxy resin or a phenoxy resin is preferably used. Among these, a phenoxy resin having film strength is preferable when the thermosetting composition is formed into a sheet. Further, these high molecular weight epoxy resins often have better physical properties of the cured product when they do not contain glycidyl groups (epoxy groups) remaining in the system.
As specific examples of the component (B), Epicoat 1256 (manufactured by Japan Epoxy Resin Co., Ltd.) and PKHH (manufactured by INCHEM Co.) can be preferably used. Component (B) is preferably added in an amount of 40 to 150 parts by weight, more preferably 50 to 100 parts by weight, per 100 parts by weight of component (A). When it is less than 40 parts by weight, it cannot impart non-fluidity (a film cannot be formed when formed into a sheet), and when it exceeds 150 parts by weight, for example, the film becomes hard and brittle when formed into a sheet, Workability becomes worse. In addition, the crosslink density is low and reliability cannot be maintained.

Specific examples of the latent imidazole compound having a nitrile group used in the present invention include 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- Imidazole compounds such as 2-phenylimidazolium trimellitate are preferably mentioned, and C11Z-CNS and 2PZ-CNS-PW (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) are mentioned as commercial products.
The component (C) functions as a curing agent for the components (A) and (B) (when the component (B) has an epoxy group), and the amount of the component (C) added is an epoxy equivalent, storage stability, Although it should be arbitrarily determined in consideration of curability and transmittance, it is preferable to add 0.5 to 20 parts by weight with respect to a total of 100 parts by weight of component (A) and component (B), More preferred is 1.5 to 10 parts by weight. When the amount is less than 0.5 part by weight, the components (A) and (B) cannot be sufficiently cured, and when the amount exceeds 20 parts by weight, the coloring becomes intense and the stability as a composition is increased. Becomes worse.

  Specific examples of (D) silane coupling agents that can be used in the present invention include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride Salt, 3-methacryloxyp Pills trimethoxysilane silane coupling agent, and the like. Two or more of these silane coupling agents may be mixed. Among these, 3-glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) is preferable because it has good compatibility with the component (A) and the component (B) and is excellent in stability. It is preferable that the addition amount of this (D) component is 0.1-10 weight part with respect to a total of 100 weight part of (A) and (B) component. More preferably, it is 0.3-2 weight part. If the amount is less than 0.1 parts by weight, the effect cannot be confirmed, and if it exceeds 10 parts by weight, there is an adverse effect in terms of outgassing.

  The thermosetting composition of the present invention comprises a base film (solution) prepared by dissolving a solution obtained by dissolving and mixing the components (A) to (D) in an organic solvent such as methyl ethyl ketone or toluene with a coating machine. It is desirable to apply it onto a release film), volatilize the organic solvent, and form it into a solid sheet (film, tape) in the normal temperature range (about 25 ° C.). Thus, if it forms in a sheet form beforehand, thermal transfer can be easily performed with respect to the organic EL element surface. Further, the thermosetting composition of the present invention may be directly formed on a substrate on which an organic EL element is formed, or a non-water-permeable sealing glass or a sealing film having gas barrier properties. In this way, it can be stored for a long time at a low temperature by forming it in a solid state at room temperature, but it is preferable to store it together with a desiccant such as silica gel in order to keep the moisture content below a certain level.

  Furthermore, it is desirable for the thermosetting composition of the present invention to exhibit fluidity in the range of 50 to 100 ° C. This is because when the organic EL device is sealed, the heat-cured thermosetting composition is smoothly filled into the irregularities on the surface of the device to eliminate bubbles, and if the flow temperature is less than 50 ° C., thermal transfer is performed. During thermosetting or sealing by thermosetting, the fluidity of the thermosetting composition is too high, and it tends to sag, and it becomes difficult to manage the film thickness of the cured product, and storage stability before curing May be damaged. On the other hand, when the temperature exceeds 100 ° C., workability at the time of thermal transfer is deteriorated so that bubbles are likely to be included, or it is heated more than necessary, which may affect the organic EL element.

  In the present invention, as long as the object of the present invention can be achieved, other components such as a storage stabilizer, a plasticizer, a tack adjuster and the like can be added. Care must be taken with impurities.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples.
Each composition is prepared as shown in Tables 1 and 2, and various evaluation tests are performed. The results are shown in Tables 1 and 2. In addition, each component used is as follows. Further, the blending ratio is based on weight unless otherwise specified.
(A) Component Epicron EXA-835LV: Bisphenol A type and F type mixed epoxy resin low chlorine type molecular weight 300 to 350 (Dainippon Ink Chemical Co., Ltd.)
Epicoat 152: Phenol novolac type epoxy resin Molecular weight: about 530 (made by Japan Epoxy Resin Co., Ltd.)
Epicoat 1001: Solid bisphenol type epoxy resin Molecular weight: about 900 (made by Japan Epoxy Resin Co., Ltd.)
(B) Component PKHH: Phenoxy resin Molecular weight 52000 (made by INCEM)
YP-70: Phenoxy resin Molecular weight 45000-55000 (manufactured by Toto Kasei)
Epicoat 1256: Phenoxy resin Molecular weight: about 50000 (manufactured by Japan Epoxy Resin Co., Ltd.)
(C) Component C11Z-CNS: 1-cyanoethyl-2-undecylimidazolium trimellitate Melting point: 123-129 ° C. (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2PZ-CNS-PW: ground product of 1-cyanoethyl-2-phenylimidazolium trimellitate Melting point 105 to 111 ° C. (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
(Other curing agents)
2MAOK-PW: 2,4-diamino-6- [2′-methylimidazoline- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct pulverized decomposition temperature 260 ° C. (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole Melting point: about 41 ° C. (manufactured by Shikoku Chemicals)
Amicure PN-23: amine-epoxy adduct solid dispersion type latent curing agent (manufactured by Ajinomoto Co.)
Fuji Cure FXE-1000: urea adduct solid dispersion type latent curing agent (Fuji Kasei Kogyo Co., Ltd.)
(D) Component KBM403: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)

Each thermosetting composition was prepared at the blending ratios shown in Table 1 as Examples 1-8. Moreover, the numerical value which shows the mixture ratio in a table | surface is a basis of weight unless there is particular notice.
The specific adjustment means is as follows.
(1) A ground product of 1-cyanoethyl-2-phenylimidazolium trimellitate (2PZ-CNS-PW) and / or 1-cyanoethyl-2-undecyl imidazolium trimethyl on epoxy resin (835LV, Epicoat 152) A master batch in which meritate (C11Z-CNS) is uniformly dispersed is prepared.
(2) Phenoxy resin (PKHH, Epicoat 1256) is dissolved in methyl ethyl ketone by stirring at room temperature.
Said (1) and (2) and the silane coupling agent (KBM403) were mix | blended with the predetermined quantity, and each composition was obtained by normal temperature stirring. Next, each composition is coated on a PET film which has been subjected to mold release treatment using a coating machine so as to have a thickness of about 20 μm, and is laminated on each mold release film and is a solid sheet in a normal temperature range (about 25 ° C.). A sample was obtained.

Moreover, also about Comparative Examples 1-9, each thermosetting composition was adjusted with the compounding ratio shown in Table 2 similarly to the Example. In particular,
(1) 2MA-OK-PW, 2PZ-CNS-PW, 2E4MZ, PN-23, and FXE1000 are added to epoxy resin (835LV, Epicoat 152), respectively, and two rolls are performed with three ceramic rolls. Prepare a masterbatch that is uniformly mixed.
(2) Phenoxy resin (YP-70, Epicoat 1256) is dissolved in methyl ethyl ketone by stirring at room temperature. Said (1) and (2) and the silane coupling agent (KBM403) were mix | blended with the predetermined quantity, and each composition was obtained by normal temperature stirring. Next, each composition is coated on a PET film that has been release-treated using a coating machine so that the thickness is about 20 μm, and is laminated on each release film and is a solid sheet in a normal temperature range (about 25 ° C.). A sample was obtained.

The various evaluation tests are as follows.
Evaluation Test 1: Measurement of Flow Start Temperature Each sample formed in the form of a sheet is degassed by stacking five sheets so that the thickness is about 100 μm even if it is peeled off from the release paper (using a vacuum laminator). This was heated to 25 ° C. to 150 ° C. using a rheometer, and the flow start temperature at that time was measured (device used: DAR-100 viscoelasticity measurement manufactured by Reologica).
Evaluation result 2: About 0.1 g of each sample formed in a moisture amount measurement sheet was weighed and heated to 150 ° C. using a Karl Fischer moisture meter, and the amount of moisture generated at that time was measured. (Solid vaporization method)
Evaluation test 3: About 5 mg of each sample formed in an outgas measurement sheet is weighed, and 120 ° C. × 15 minutes by a dynamic space method using a double shot pyrolyzer and a glass chromatograph / mass spectrometer (GC-MS). The amount of outgas generated when heated was measured. The total amount of outgas generated was quantified using n-decane as a standard substance.
Evaluation Test 3: A glass substrate for a visible light transmittance measurement panel was cut by 25 mm × 50 mm, each sample formed in a sheet shape was transferred and cured under curing conditions of 100 ° C. × 3 hours. The transmittance of each sample piece was measured with a glass spectrophotometer.
Evaluation Test 4: Dark Spot Evaluation A transparent electrode by sputtering was formed on a glass substrate with a thickness of 0.1 μm. Subsequently, a hole transport layer and an organic EL layer were sequentially formed in a thickness of 0.05 μm on the transparent electrode. In addition, a film having a back electrode thickness of 0.2 μm is formed on the organic EL layer. After film formation of these elements was completed, each sample formed in a sheet shape on the glass substrate 1 was transferred using a roll laminator. A non-permeable glass substrate was stacked on the transferred glass substrate 1 and heat-pressed using a vacuum laminator. Thereafter, each sample was completely cured by a heat dryer at 100 ° C. for 3 hours. Panels were prepared in this way, and dark spot growth was observed in an environment of 60 ° C. × 90% with continuous lighting. The case where no dark spot having a diameter of 100 μm or more after 1000 hours had occurred was indicated as “◯”, the case where a dark spot was slightly observed was indicated as “Δ”, and the case where a dark spot was clearly observed was indicated as “X”.
Moreover, as a comprehensive judgment, those that can be used as a sealing agent for organic EL elements without problems are indicated by ◯, those that can be used by Δ, and those that cannot be used by ×.

表中の−は未測定を表す。

-In the table represents unmeasured.

  In Examples 1 to 8, excellent results were obtained in all evaluations. Moreover, in the comparative example 1, the flow start temperature was low and became 50 degrees C or less. In addition, it has been difficult to form a uniform film during coating to form a sheet. In addition, in the evaluation of dark spots, it was not a good result due to the influence of many low molecular weight components. In Comparative Example 2, there were many high molecular weight components and there was no problem with the flow start temperature, but the film became hard and brittle, and the workability was also poor. Moreover, the dry state of ethyl methyl ketone at the time of sheet formation deteriorated, and the outgas generation amount increased.

  In Comparative Example 3, the amount of the curing agent component was large and the water content exceeded 0.50% by weight, and the visible light transmittance was 90% or less due to the influence of the curing agent.

  In Comparative Example 4, curing was insufficient, and the amount of outgas generation during curing far exceeded 1000 ppm. Further, since the curing is insufficient, sufficient reliability cannot be ensured, and good results cannot be obtained in the dark spot evaluation.

  In Comparative Example 5, 2E4MZ having a melting point of 50 ° C. or lower (about 41 ° C.) was used as the curing agent. For this reason, the curing reaction started at the time of coating to form a sheet, which has no storage and no practicality. Moreover, since it was a semi-hardened state, the fluidity start temperature could not be measured clearly.

  In Comparative Examples 6 and 7, the curing agent was evaluated using a curing agent other than imidazole. As a result, in all cases, the visible light transmittance was 80% or less, and the reaction started at the time of coating, which was impractical.

  In Comparative Example 8, no coupling agent was added. As a result, reliability could not be ensured, and good results could not be obtained by dark spot evaluation. In Comparative Example 9, a large amount of coupling agent is added. The liquid component increased, and the flow start temperature became 50 ° C. or lower. Moreover, the stickiness of the sheet-like adhesive surface became severe, and workability was also lowered.

  The thermosetting composition of the present invention can be applied not only to organic EL device sealing but also to sealing applications for the purpose of improving the moisture resistance, weather resistance, and impact resistance of other electronic components.

Claims (6)

  (A) having at least two glycidyl groups in one molecule, 100 parts by weight of a low molecular weight epoxy resin having a molecular weight of 200 to 2000, and (B) a bisphenol A type or bisphenol F type epoxy skeleton, A latent imidazole compound having a (C) nitrile group is 0.5 to 100 parts by weight based on 40 to 150 parts by weight of a high molecular weight epoxy resin having a molecular weight of 20000 to 100,000 and (A) component and (B) component. A composition comprising 20 parts by weight and (D) 0.1 to 10 parts by weight of a silane coupling agent as a main component, wherein the composition exhibits non-fluidity at 25 ° C. and 50 to 50 when heated. A thermosetting composition for sealing an organic EL element that exhibits fluidity in a range of 100 ° C.   The thermosetting composition for sealing an organic EL device according to claim 1, wherein the thermosetting composition is formed in a sheet shape in advance.   The thermosetting composition for sealing an organic EL element according to claim 2, wherein the thermosetting composition formed in the sheet form has a flow start temperature of 50 to 100 ° C.   The thermosetting composition for sealing an organic EL device according to claim 1, wherein the amount of outgas generated during curing of the thermosetting composition is 1000 ppm or less.   The thermosetting composition for sealing an organic EL device according to claim 1, wherein the moisture content of the thermosetting composition is 100 ppm or less.   The thermosetting composition for sealing an organic EL element according to claim 1, wherein a transmittance of 405 nm in the cured product of the thermosetting composition is 90% or more.