TW201022358A - Sealant, sealing member, organic electroluminescent device, organic electroluminescent display panel and method of fabricating organic electroluminescent device - Google Patents

Abstract

The present invention is directed to a sealing member of an organic electroluminescent (EL) device containing siloxane compounds, such that degradation of the element in the organic EL device can be suppressed and longevity of the organic EL device can be achieved. A sealing member of an organic EL device is provided, including cured material or polymer of a resin composition for a sealant that contains organic siloxane compounds. Concentration of primary alcohol in the foregoing cured material or polymer is less than or equal to 10 ppm measured by headspace GC-MS analysis. In addition, a resin composition for a sealant is provided, which is directed to a resin composition for a sealant of an organic EL device containing siloxane compounds. The content of primary alcohol contained therein is less than or equal to 50 ppm.

Description

201022358 32598pif VI. Description of the invention: [Technical field to which the invention pertains] $暇About-type-tightness_and sealing materials and organic electroluminescence using these=readings_fine_mines_e, [prior art] Gan_, known in recent years The organic electroluminescent device that has been extensively developed is extremely degraded by moisture. For example, _ is generated between the electrode layers of the light-emitting layer due to moisture, and the luminescent material is deteriorated to be called a dark spot. The non-light-emitting area or the inability to maintain illumination. Therefore, a technique is known in which the organic EL member is smashed by the fixing of the airtight cover or the sealing member on the substrate (for example, Japanese Patent Laid-Open No. Hei 5-36475, Japanese Patent Laid-Open No. Hei 5 89959 Japanese Patent Laid-Open Publication No. Hei 7-169567. However, there is still a case where the luminance of the organic EL member is lowered or a dark spot is generated as the driving time elapses, and the function cannot be fully functioned as a member. The material of the (4) component itself generates a gas which deteriorates the member. Therefore, a sealing member for suppressing generation of a hydrocarbon gas or a siloxane gas or the like has been proposed (refer to Japanese Laid-Open Patent Publication No. Hei 11-74074). On the other hand, with the development of the market for organic electroluminescence members, the sealing member is required to have high heat resistance, low shrinkage at the time of curing, transparency, and moisture permeability. In order to meet these requirements, a sealant to which a filler (11 alcohol) or a silane coupling agent is added has been developed. SUMMARY OF THE INVENTION The object of the present invention is to suppress deterioration of an organic electroluminescent member with time and maintain its initial performance. The inventors have found that one of the main causes of deterioration of organic electroluminescence over time is the primary alcohol in the gas generated inside the member. Further, it has been found that the main source of the primary alcohol is the sealing member of the organic electroluminescent member. Further, it has been found to be particularly due to the decane coupling agent contained in the sealant. Therefore, the present invention provides a sealing member in which the concentration of the primary alcohol is extremely low even in the sealing member of the organic EL element, even if it contains the organic oxy-oxygen compound. Thus, the object is to suppress deterioration of the organic electroluminescent member having the sealing member, and to have a long life of the device. Further, the present invention provides a sealant for providing a sealing member as described above, that is, a sealant which suppresses generation of a primary alcohol, or an absorbable one-stage alcohol, or which can react with a primary alcohol A sealant for substances other than primary alcohols. That is, the first part of the invention relates to a sealant. ® [U One Sealant] 1 g of this sealant is heated in a loot for 6 Torr to produce a primary alcohol in an amount of 10 #g or less. [2] The sealant according to [1], which comprises a reactant of a decane coupling agent or/and an anthraquinone coupling agent. [3] The sealant according to [1], wherein the primary alcohol has a boiling point of 120 or less at 1 atm. [4] The sealant according to [2], wherein the above decane coupling agent is represented by the following formula (1), (1,) or (1"): 5 201022358 32598pif [Chemical 1] r2

Rr〇

0 1 , Si-O-hR 3 • · · (1) r4 ?4, n

RrO^-Si-O 十-R • · · (1,) n r4 R“O—S 卜 I r4 r4" • · • a") (in general formula (l), (r) or (Γ) R1 to R3 each independently represent a group represented by the following formula (2), and 1U'RV and RV' each represent a monovalent organic group other than the oxy group, and η represents an integer of 1 or more, and η is 2 or more. In the case, two or more R2, IU, and RV may be the same or different from each other. [Chem. 2] 201022358 32598pif r5 • ••(2)

I - Re Re (In the formula (2), 'R5 represents a hydrogen atom or a hydrocarbon group, and R6 and R7 each independently represent a hydrocarbon group). [5] The sealant according to [4], which further comprises an epoxy resin, and R4, RV or W each independently has an epoxy group, an amino group, an acryl group (acryl) Group), any of the isocyanate groups. [6] The sealant according to [2], which further comprises a compound which adsorbs alcohol or reacts with an alcohol, and the above decane coupling agent is represented by the following general formula (3), (3,) or (3,,): 3]

Rl2 〇

Si Ο I Rl4 _

R 14

Rii*-〇-Si-0 Rl4,

•R 13 • · ·(3) n

R 13 • · · (3’) n 7 201022358 32598pif R”-. One Si—~*Rl4" · · ·()

Rl4 (In the formula (3), (3') or (3n), Rii to R13 are each independently a monovalent organic group, but one or more of Rii to Ri3 are represented by the formula (4) The group, r14, R14' and Rh" respectively represent a monovalent organic group other than the oxy group, and η represents an integer of 1 or more. When η is greater than or equal to 2, 2 or more of Ri2, rh and rh exist. 'can be the same or different from each other' [Chemical 4]

R1 I HICIH (4) (In the formula (4), Ri5 represents a hydrogen atom or a nicotine group). [7] The sealant as described in [6] wherein the compound which adsorbs alcohol or reacts with an alcohol is an isocyanate compound. [8] The sealant according to [1], which further comprises a curable resin or/and a thermoplastic resin. [9] The sealant according to [8], which contains 0.1 part by weight to 1 part by weight of the above decane coupling agent and/or 1 part by weight of the above-mentioned curable resin or/and thermoplastic resin. Or the reactant of a decane coupling agent. 201022358 32598pif [10] The seal according to [9] wherein the above-mentioned hard-recording resin is a thermosetting resin. [11] The sealant of the above, wherein the thermosetting resin is an epoxy resin. [12] The sealing crucible according to [11], which further comprises an acid anhydride and a hardening accelerator. [13] The sealant according to [12], which comprises ο. 1 part by weight to 1 part by weight of the above-mentioned Wei coupling agent and/or Wei even with respect to 1 part by weight of the above-mentioned epoxy resin. The reactant of the mixture. The equivalent ratio of the acid anhydride group to the epoxy group of the above acid anhydride and the above-mentioned hardening accelerator is from 08 to 12, and the equivalent functional ratio of the functional group of the hardening accelerator to the epoxy group is from 0008 to 0152. A second part of the invention relates to a sealing member. [14] A type of sealing member's; a sealing member comprising a polymer or cured product containing a sealant of a dreamer coupling agent and/or a bite of a bottle of the coupling agent, and heating the above-mentioned sealant at 100t. The amount of the primary alcohol produced in minutes is less than or equal to 10 eg. [15] The sealing member according to [14], wherein the above-mentioned alcohol is in! The boiling point in atmospheric pressure is less than or equal to 12 〇. Hey. The second part of the invention relates to an organic EL element and a method for manufacturing the same, which comprises the steps of forming an organic a member on a substrate; the second step is The EL member is adhered to the denseness as described in (1); and in the third step, the sealant is hardened to form a sealing member. The method for producing an organic EL device according to the above [16], wherein the second step is carried out by thermal lamination. [18] An organic EL element </ RTI> comprising: an organic EL member, and a cured product of the sealant as described in [n item] connected to the above-described organic EL member. [19] An organic EL element comprising the sealing material as described in [14]. [20] An organic EL display panel comprising the organic EL element according to [18] or [19]. [Effect of the Invention] The organic EL device having high sealing property and high life can be provided by the sealing agent of the present invention. The above described features and advantages of the present invention will be more apparent from the following description. [Embodiment] 1. Sealant of the present invention The sealant of the present invention is characterized in that the amount of the alcohol to be heated is lowered. In the case of Zhao, it is preferred that the ig of the present invention is heated by the shoe for 60 minutes to produce a primary alcohol in an amount less than: more preferably less than or equal to 5 states. The amount of alcohol produced by heating can be utilized at the top. Space (h she (four) gas chromatography mass spectrometry 3 chromatograph-mass spectrometry, GC-MS) the empty method of dip" is based on a fixed temperature test

St: The volatile component is brought to equilibrium from the sample, and then the volatile component of the sample is introduced to a gas chromatography mass spectrometer 201022358 32598pif (GC-MS ) ' to analyze the target component. In the headspace sampler, the temperature of the measured sample is heated at 60 °C for 60 minutes, and the out gas component is characterized by the method of (}(:/)^8. The amount of gas generated can be quantified by toluene using a gas chromatograph 'GC method. More specifically, 'for example, the following conditions can be used. (1) Headspace sampler measurement conditions (Machine type: HP7694) Vial capacity: 1〇mi loop capacity: 丨ml bake

Box temperature: 100 °C Loop temperature (LoopTemp): 150 °C Transfer line temperature (TR LINE Temp): 150 °C Gas chromatograph working time (Gc Cycle Time): 50 minutes vial heating equilibration time (VIALEQ Time) : 30 minutes pressurization time (Pressuriz Time): 0.13 minutes Loop Fill Time: 0.15 minutes Loop EQ Time: 0.15 minutes Injection time (InjectTime): 1〇·3 Minute vial pressure: 69Kpa (AUX5) (2) GC measurement conditions (machine type: HP6890 (FID)) Column: DB, WAX 122-7063 Inner diameter: 0.25 mm Length: 60 m film thickness · · 0.5 from m Temperature: tube Column 4 〇 °c Hold for 1 minute - 23 (TC (l (TC / min) hold 15 minutes 201022358 32598pif injection inlet 250 ° C detector 250 ° C carrier gas: 氦 initial flow 1.81 ml / min set pressure 202

Kpa average linear velocity 3 0 cm/sec split ratio 10 : 1 Detector: hydrogen 40 ml/min air 450 ml/min supplement (makeup) + tube total 50 ml/min (3) GC-MS determination Conditions (Machine type: HP6890-HP5973 (MSD)) ❹ Column, temperature conditions: Basically the same as the GC method of the previous paragraph Total ion chromatogram (TIC): m/z = 10 ~ 550 Library search data : NBS 75000 pieces, and the concentration of the primary alcohol in the sealant of the present invention is preferably less than or equal to 5 〇 11 ^ 1) spleen 'better is less than or equal to 1 〇 8 卯 111. The concentration of the primary alcohol in the sealant can be measured by UC-NMR. As described above, the sealant of the present invention is characterized in that the amount of the primary alcohol or the primary alcohol concentration due to the heat of the twisting can be reduced, and the primary alcohol can be the boiling point (bp) in the 1st milk pressure. It is less than 〗, C), 1-propanol (97 ° C), butanol (ii 7 ° C), and the like. The sealant of the present invention contains one or both of a reaction of a decane coupling agent and a decane coupling agent. The decane coupling agent is preferably an alkoxy silane. The reactant of the decane coupling agent means a hydrolyzate or a dehydrated polymer of alkoxy fluorene 12 201022358 32598 pif alkane. In the following, the reactants of the decane coupling agent and the decane coupling agent are collectively referred to as a decane coupling agent. The decane coupling agent improves the adhesion of the substrate to be sealed to the sealant. In order to improve the adhesion, it is preferred to set the content of the decane coupling agent contained in the sealant to 〇1 part by weight to 10 parts by weight based on 100 parts by weight of the resin constituting the sealing agent. It is preferred to bond an organic group other than one, two or three oxy groups to the Si element constituting the alkoxy oxime of the decane coupling agent. It is preferred that the organic group other than the oxy group contains an epoxy group, an amine group, an acrylonitrile group or an isocyanate group. These organic groups can be reacted with other components (resin components) contained in the sealant. The alkoxy group of the alkoxydecane of the decane coupling agent contained in the sealant of the present invention may be a primary alkoxy group, a secondary alkoxy group, or a tertiary alkoxy group but having a primary alkane. The oxane decane coupling agent will be the source of the primary alcohol. Therefore, the first form of the decane coupling agent contained in the sealant of the present invention is a oxyalkylene having no primary alkoxy group and a secondary alkoxy group or a tertiary alkoxy group. On the other hand, the second form of the decane coupling agent contained in the sealant of the present invention is an alkoxy decane having a primary alkoxy group, but in this case, it is preferably in the sealant of the present invention. Contains components that absorb alcohol or react with alcohol to form other substances. As described above, the first aspect of the decane coupling agent contained in the sealing agent of the present invention is an alkoxy decane having no primary alkoxy group, and is represented, for example, by the following formula or d"). 13 201022358 32598pif [Chemical 5 ] Ο

FtpO·

Si—〇Λα —r3 (1) η

Ri~0. 'Si 一·〇—R3 (1,) ψ (1,,)

Ri—o—Si—R/ . R4 [6] ·?—Re • · · (2) The following 231), 0,) or (1))*, Rl to R3 independently represent the following general formula (2) The formula is shown in the formula: Nicotinyl. The formula (2), wherein, and 1 respectively represent a C 7 hydrogen atom or a mercapto group, preferably a carbon number of ~4 alkyl group. R5 to R7 201022358 32598pif The decane coupling agent represented by the formula U), (r) or (Γ') may be hydrolyzed to produce R1〇H, R2〇H or R3〇H, but both are secondary or tertiary alcohols. It is not a primary alcohol. ^4, RV and RV' respectively represent a monovalent organic group, but are not an oxy group, and there is no phenomenon of alcohol production due to hydrolysis. In addition, 1, oxime, and &lt;, respectively, may also have an organic Functional group. The functional group referred to herein is preferably a functional group capable of reacting with a resin component contained in the sealant. The reason is that the φ ☆··Wei coupling agent reacts with the resin component contained in the sealing material. The bonding can further improve the adhesion between the substrate and the sealing material, and by the above bonding, the decane coupling agent can be prevented from being precipitated from the sealing agent. In the case of an epoxy resin, it is preferably an epoxy group, an amine group, an acryl group, an isocyanate group or a hydroxyl group, etc. In addition, the vinyl group contains a vinyl group (vinyl) In the case of the resin, R4, R4 or RV preferably has a vinyl group. η represents an integer of 1 or more, and is usually preferably 丨~5 (when η is greater than or equal to 2, 2 The two or more of r2, ^ and ® may be the same or different from each other. Examples of the alkoxydecane having no first-stage alkoxy group include: 3-glycidyl/oxypropyl-isopropoxy group 3-glycidoxypropyl trusopropoxy silane, 3-glycidoxypropyl tris(2-butoxy)decane, 3·glycidoxypropyl tri-tert-butoxydecane, 3 glycidyloxypropane Methyl diisopropoxylated, 3-glycidoxypropylmethyl bis(2-butoxy)decane, 3-glycidoxypropyl decyl di-t-butoxydecane, 2- (3,4-epoxycyclohexyl)ethyltriisopropoxy silane 15 201022358 32598pif (2-(3,4-epoxycyclohexyl)ethyl triisopropoxy silane ), 2- (3, 4-epoxycyclohexyl)ethyltris(2-butoxy)-infraline, 2-(3,4-epoxycyclohexyl)ethyltri-tert-butoxydecane, N-phenylamine Ν-phenyl- τ -aminopropyl triisopropoxy silane, N-phenyl-7-aminopropyltris(2-butoxy) calcined, N-phenyl·r- N-(aminoethyl)-3-aminopropyl methyldiisopropoxy silane N-(2-aminoethyl)-3-aminopropylmethyl diisopropoxy silane , N-(2-Aminoethyl)-3-aminopropyl-decylbis(2-butoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyl Di-tert-butoxy decane, N-(2-aminoethyl)-3-aminopropyl decyl triisopropoxy decane, Ν-(2·aminoethyl)-3-aminopropyl Base bis(2-butoxy)decane, N-(2-aminoethyl)-3-aminopropyl decyl tri-tert-butoxydecane, 3-aminopropyltriisopropyloxide 3-aminopropyl triisopropoxy silane, 3-aminopropyltris(2-butoxy)decane, 3-aminopropyltris-tert-butoxydecane, 3-mercaptopropyltriisopropyloxide 3-mercaptopropyl triisopropoxy silane , 3-mercaptopropyltris(2-butoxy)decane, 3-mercaptopropyltridecyloxybutane, vinyl triisopropoxy silane, ethylene-based (2-butoxy)decane, vinyl tri-tert-butoxydecane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltriisopropoxylate salt N-(2-(vinylbenzylaminoethyl)-3-aminopropyl triisopropoxy silane hydrochloride ), N-(2-(vinylheptylamino)ethyl)-3-aminopropyltris(2-butyl) Oxy) decane hydrochloride, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyl tri-tert-butoxy decane hydrochloride, 3-201022358 32598pif methacryl oxime 3-methacryloxypropyl triisopropoxy silane, 3-mercaptopropenyloxypropyltris(2-butoxy)decane, 3-methylpropenyloxypropyl tri Dibutyloxy calcined and other dream compound coupling agents. These crushing couplers may be used in two or more types. &amp; ° ❹ Ο The second form of the decane coupling agent contained in the sealant of the present invention has an alkoxy group-cut alkoxy group, for example, represented by the following formula (3) or (3") ] State is, (3,) ^12 0

Ri 1_0_ -Si—Ο—R R14 η , 13 • ••(3) R14 Si—Ο I _Rl4

—R 13 (3,) n

Ria

Ri 1_0—Si—R14&quot; • · · (3,,)

Ri [化8] 17 201022358 32598pif Η

I ?~R15 · · · (4) Η The price has "2" (1) &lt; (3") 'Rll~Rl3 respectively represent one (one or more of - levels is a furnace base represented by the general formula (4), ιΤ^ Γ). Preferably, in the formula (4), Ri5 is a hydrogen atom. The hydrocarbon group represented by 51 15 is a fluorenyl group having a carbon number of 1 to 4.

Dragon? The hydrocarbon group represented by 3^11 to 1113 and not represented by the formula (4) has a hydrocarbon number of 1 to 4. &amp;# I The decane coupling agent represented by the formula (3), (3') or (3") is hydrolyzed by the production of RiiOH, r^oh or R^OH', at least any one of which is a first order, therefore, in order to seal In the agent, the amount of the primary alcohol or the primary alcohol/degree is lowered, and it is preferred that the decane coupling agent is contained in the sealant in combination with the component which absorbs the alcohol or reacts with the alcohol to become another substance. It is the same as I in the general formula (1), and represents a valence organic group, but is not an oxy group, and is a group which does not generate an alcohol due to hydrolysis. Further, 'RH, 〜' and 〜" are the same as R4, and may have Organic functional

η in the formula (3) or (3') represents an integer of 1 or more, and is usually preferably 1 to 5. In the case where η is greater than or equal to 2, Ri2, Rh, and RiV present on two or two turns may be identical to each other or different from each other. Examples of the dioxin-oxygen stone ceremonies having a first-stage alkoxy group include: 3-glycidoxypropyl dimethoxy dream, 3-glycidoxypropyl decyl dimethoxy zebra, 2- (3,4-Epoxycyclohexyl)ethyltrimethoxydecane, N_stupyl 18 201022358 32598pif aminopropyldimethoxyoxy, N-(2-aminoethyl)&gt;3_ Aminopropyl fluorenyl dimethoxy, Ν·(2·aminoethyl)_3·aminopropyl decyl trimethoxy calcination, 3-aminopropyl triethoxy zebra, 3 Benzylpropyltrimethoxy-Xi Xing, Ethylene-Based Dioxane-based Shishi-6, Fan (2-(Ethyl-based arylamino)ethyl)·3·Aminopropyltrimethoxy-Wei Hydrochloride 3, mercapto propylene methoxy propyl dimethoxy; granule oxy Wei. This _ lang can be mixed 2 or more. φ The sealant of the present invention may also contain alcohol, especially It is a primary alcohol or a component which reacts to form other substances. 4 In the case where the sealant contains a burntoxy group having a primary alkoxy group, it is preferred that the sealant also contains the component. Examples of ingredients include isocyanate compounds The isocyanate compound is easily reacted with an alcohol, particularly a primary alcohol, to form a urethane. The isocyanate compound may be an alkyl isocyanate or an aryl isocyanate. The isocyanate compound contained in the resin composition for a sealant is preferably highly reactive with an alcohol, and therefore an aromatic isocyanate compound is used as compared with the aliphatic isocyanate compound (for example). 2,6_toluene-isocyanate S (tolylenediisocyanate, TDI) or methylene bis(4,1-extension base)-isocyanuric acid (methylene bis(4,l-plienylene)=diisocyanate,MDI Further, it is preferable that the isocyanate compound is not volatilized, and therefore it is preferred to use a high molecular weight isocyanate compound. The isocyanate compound contained in the resin composition for a sealant Including 19 201022358 32598pif amount 'in the case of the amount of one-stage alcohol contained in the known sealing material (mole), adding 1 to 2 times equivalent of the isocyanate of the primary alcohol. When the agent produces a primary alcohol, it is preferred to add the isocyanate in such a manner that the decane coupling agent may produce a maximum amount of the primary alcohol in an amount of from 1 to 2 equivalents. It is preferred that the sealing agent of the present invention contains a resin component. The resin may be The curable resin may be a thermoplastic resin or both. The curable resin is a resin which forms a three-dimensional crosslinked structure by bonding a polymer chain to each other by a crosslinking reaction. Examples of the resin include a phenol resin, an epoxy resin, a urearesin, a melamine resin, an unsaturated polyester resin, a polyurethane, and the like. The curable resin contained in the sealant of the present invention is preferably an epoxy resin. The epoxy resin contains a compound having one or more epoxy groups in the molecule. The epoxy group-containing compound may be a monofunctional epoxy compound, a bifunctional epoxy compound, or a polyfunctional epoxy compound of 3 or more. Examples of the 1-functional epoxy compound include phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, and ethyl diethylene glycol. Glycidyl ether), dicyclopentadienyl glycidol ((^&gt;^1〇卩61^(如116吕1}^(1)4 61;1^〇, 2-transethylethyl glycidyl bond ( 2-hydroxyethylglycidylether), etc. Examples of 2-functional epoxy compounds include: p-phenylene diglycidyl 201022358 32598pif hydrazine, m-diphenol diglycidyl ether 'ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Ether, 1,4-butanediol diglycidyl ether, iota, 6-hexanediol diglycidyl ether, cyclohexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, dicyclopentadiene Glycol diglycidyl ether, naphthalenediol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether 'hydrogenated bisphenol A diglycidyl ether, deuterated bisphenol F diglycidyl ether. Etc. Examples of polyfunctional epoxy compounds of 3 or more include: trimethylpropane tricondensate Glycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac epoxy, acetal varnish type epoxy, etc. Also, the epoxy resin may also contain an epoxy group-containing polymer or oligo. Oligomer. The polymer or oligomer having an epoxy group is not particularly limited, and can be obtained by polymerizing a vinyl monomer having an epoxy group. Examples of the monomer are preferably glycidyl (meth)acrylate, _3,4-epoxycyclohexylmethyl (meth)acrylate, decyl glycidyl (meth) acrylate. A (meth) acrylate-based monomer such as an ester. The epoxy resin may be a copolymer or oligomer of an ethylene-based monoterpene having an epoxy group and another vinyl monomer. Examples thereof include (meth) acrylates. Preferably, the ester group of the (meth) acrylate is methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2 -ethylhexyl, cyclohexyl, benzyl, isobomyl, lauryl, myristyl, etc. On the non-functional alkyl vinegar of the linear structure and the branched structure 21 201022358 32598pif. In addition, the epoxy resin may also be a vinyl monomer having an epoxy group and styrene or α-mercaptophenylene. Copolymer of α-methylstyrene, ethyl acetate, etc. Thermoplastic resin The resin contained in the sealant of the present invention may also be a thermoplastic resin. The thermoplastic resin contained in the sealant is, for example, polyethylene terephthalate or polytrifluoroethylene (p〇lychl〇r〇 trifluoroethylene). A sealant containing a thermoplastic resin can also be used in combination with a glass membrane or a glass sheet. For example, as described in Japanese Laid-Open Patent Publication No. 2002-299041, a film containing a layer of the resin composition for a sealant of the present invention may be formed on both surfaces of a glass film as a sealing member. The sealant of the present invention may also contain an acid anhydride. In particular, a sealing material having high transparency can be obtained from a resin composition containing a sealing agent for an epoxy resin and an acid anhydride as a curable resin. Since the aromatic acid anhydride is mostly colored, it is preferably an aliphatic acid (aromatic hydrogenated product) acid anhydride. Examples of the acid anhydride contained in the sealant include: phthalic anhydride, tetrahydrophthalic acid needle, methoxytetrahydrophthalic acid, trimellitic anhydride, and six Intramethylene methylene tetraphthalic anhydride, benzophenone tetraphthalic acid dianhydride, and the like. The highly transparent one is an aliphatic acid anhydride, and hexahydrophthalic anhydride or mercaptohexahydrophthalic anhydride can be used. The sealant containing a curable resin may also contain a hardening accelerator. The type of the hardening accelerator is not particularly limited, and may be appropriately selected depending on the type of the curable resin 22 201022358 32598pif. In the case where the curable resin is an epoxy resin, the hardening accelerator may be a taste-based compound or an amine compound. Examples of the α-salt compound include 2-ethyl-4-methyl-miso. Examples of the amine compound include tris (dimethylaminomethyl) pheiiol and the like. An example of a preferred composition of the sealant of the present invention is that it contains 1 part by weight of an epoxy resin and 0.1 part by weight to 10 parts by weight of an anti-coupling agent, and further becomes an equivalent ratio of an acid anhydride group to an epoxy group. The method of .8 to 1.2 contains an acid sulfonate, and contains a hardening accelerator in such a manner that the equivalent ratio of the reactive functional group/epoxy group is from 0.008 to 0.152. The active functional group of the hardening accelerator means an amine group, an imidazolyl group or the like. The sealant of the present invention may also contain any filler. Examples of the optional filler include glass beads, styrene polymer particles, methyl acrylate polymer particles, ethylene polymer particles, and propylene polymer particles. The sealant of the present invention may also be in the form of a film. In the case of being used as a sealant for an organic EL device, a W film-like sealant having a thickness of several micrometers to several tens of micrometers is generally used. The sealant of the present invention may be formed into a film on the surface of a carrier such as another film or a glass plate or a metal foil, in addition to being formed into a film shape by itself. 2. Organic EL device The organic EL device of the present invention is characterized in that it is sealed by using the sealing agent of the present invention. The organic EL device is generally a laminated light-emitting device having at least one pair of electrode layers (anode electrode layer and cathode electrode layer) and an organic light-emitting layer disposed between a pair of electrode layers. The sealing method of the organic EL element is not particularly limited. Organic EL 23 23 201022358 32598pif The method of sealing the money is called the "frame (four)" method and the method called "face seal". The frame sealing means a method in which the organic EL member disposed on the substrate is covered with a sealing cover and the peripheral portion of the sealing cover is sealed (and subsequently) with a sealing member. (4) The sealing member of (4) hemp of the present invention can also be produced. On the other hand, the term "surface seal" means a method in which a sealing plate is placed on an organic EL member disposed on a substrate, and a sealing member is filled between the sealing plate and the substrate and between the organic crucible member and the sealing plate. The sealing member can also be produced using the sealant of the present invention. In other words, the sealing member of the present invention can be used to seal only the light-emitting surface side or the non-light-emitting surface side of the organic EL element, and the sealing member of the present invention can be used to seal both the light-emitting surface side and the non-light-emitting surface side. Further, in the organic EL device of the present invention, the sealing agent may be applied to a desired position to be cured or polymerized to form a sealing member, or a sealing agent having a predetermined shape (for example, a film shape) may be disposed at a desired portion. And it is made to be 'hardened or polymerized to make a sealing member. When the film is placed in close contact, it may be thermally laminated or adhered using an adhesive. In general, the organic EL device is known to be easily deteriorated by moisture or the like, and it is also known that it is easily deteriorated even for an organic gas. The present inventors have found that the alcohol gas easily deteriorates the organic EL element, for example, to cause a dark spot or to cause it to become non-emitting. On the other hand, it has been found that an alcohol gas other than the primary alcohol, that is, a secondary alcohol gas or a secondary alcohol gas, is extremely difficult to make the organic EL element 24 compared with the primary alcohol (see Reference Example described later). The term "primary alcohol" as used herein means that the current boiling point (bp) ▲ is less than or equal to 12 于 in the atmosphere J. . Alcohol. The alcohol is less than or equal to 12 ,, including methanol (65 ° C), ethanol (78 ° C), 1-propanol (97. hydrazine, 1-butanol (117t:), etc.. The sealing agent of the present invention is polymerized or The sealing member obtained by hardening is characterized in that it contains a hardened material or a polymer of a tree and an organic Weixuan compound and can greatly reduce the concentration of the primary alcohol. The so-called organic stone oxide composition refers to the content thereof. The Si atom is bonded to an organic group other than the oxy group. It is preferred that the carbon atom of the organic group other than the oxy group is bonded to the Si atom. It is preferred that the (IV) member of the organic EL device of the present invention is extremely large. The concentration of the primary alcohol is reduced to a certain extent, specifically, the concentration measured by the headspace GC_MS method is less than or equal to 1 〇 ppn. The so-called headspace GC_MS method is as described above. [Examples] @ 3-glycidoxypropyl·three different Synthesis of propoxy decane Trichlorosilane (4 67 g, 31 mm 〇1) was dissolved in 80 mL of toluene'. Isoproxol (is〇pr〇pyl alcohol) was slowly added dropwise under ice cooling (10.4 g, 170 mmol). After the addition, the mixture was stirred at room temperature for 19 hours. 2 g of sodium carbonate was suspended in 5 〇mL of diisopropyl ether (diiS〇propyi ether), and the reaction liquid was gradually added dropwise thereto. After stirring at room temperature for 3 hours, the solid was separated by filtration, 1 〇. The mL hydrazine is washed to obtain a triisopropoxy decane solution. This solution is not purified and used in the subsequent reaction. 25 201022358 32598pif In the obtained triisopropoxy zephyr solution, the force σ starts. The chloroplatinic acid isopropanol solution has 20 mg of diglycidyl ether (1.65 g' 14.5 mmol), and the reaction solution is concentrated under reduced pressure with 18 〇 ° and ally, and further heated for reflux for $ hours. L3;) glycidoxypropyl-triisopropoxy group by 1 this 25^ boiling point: 106 ° C / 4 mmHg yield: 13%

Hz) 0.69 (dd^lH^J=3Hz&gt;llH.x P. 3H 3.15~3.1 (m, lH), 2.79 (dd, ih, w: 3 3 (m'3H), (dd, 1H, J= 3 Hz, 5 Hz), 175 Z, 5HZ), 2.61 /5 i.65 (m, ; 2H), 1 18 (d, 18H, J=6Hz), 〇.6~0.55 (m, 2H); 118 Purity: 94.8% (determined by GC) [Chemistry 9]

26 201022358 32598pif [Table 1] Formulation A Formulation B Formulation C Epoxy Resin (EPICLON 830S) 100 100 100 Anhydride (RIKACIDMH-700) 93 93 93 Tertiary Amine (JER CURE 3010) 3 3 3 Decane Coupler 3 - glycidoxypropyl trimethoxycycloalkane 2-monoglycidoxypropyl triisopropoxy montane - 5 - EPICLON 830S : Dainippon Ink and Dainippon Ink and

Chemicals Inc) RIKACID MH-700 : JE CURE 3010 : Nippon Epoxy Resins Co., Ltd. 3-glycidoxypropyltrimethoxy ketone: KBM403 (Shin-Etsu Chemical Co., Ltd.) 3-shrinkage Glyceroxypropyl triisopropoxy octamane: The above synthesis example [gassing analysis] 1.0 g of each of Formulation A and Formulation B of Table 1 was accurately weighed and sealed in a vial. The encapsulated formulation was heated for 60 minutes using TC. The gas in the vial was introduced into the GC-MS to detect the gas composition. The gas detected was shown in Table 2.

[Table 2] Acetone DPA Acetone MffiK Hexahydrophthalic acid (hexahydro phthalide) A 15 β% 3 β% 2 β% 1 Formulation B ----- 20 3 β% 2 fig 1 β% : Isopropanol MIBK: methyl isobutyl 2 η As described above, sterol was detected from the formulation A, and isopropanol was detected from the formulation B t . The decane coupling agent can be considered as a source of production, respectively. [Next test] 27 201022358 32598pif Prepare two glass plates with a thickness of 5 mm. The formulation A, the formulation oxime or the formulation C shown in Table 1 was sealed between two glass plates. The gap between the two glass plates is 12 em. The obtained laminated glass plate was heated at 1 ° C for 30 minutes to harden the encapsulated formulation. The resulting glass plate was stored at 60 ° C, 90% RH for a fixed period of time. Thereafter, the ruptoe strength at the time of peeling the glass plate at a stretching speed of 2 mm/min was measured. The measured breaking strength is divided by the subsequent area to obtain the subsequent strength. In the graph of Fig. 1, 'in the case where the formulation A to the formulation C are used, the relationship between the strength and the storage time is followed. As shown in Fig. 1, when the formulation C to which the decane coupling agent was not added was used, the initial strength (the storage time was 0 hours) was also low, and the strength was lowered as the storage time elapsed. On the other hand, when the formulation A and the formulation B to which the decane coupling agent was added were used, the initial adhesion strength was high, and the strength did not decrease even if the storage time elapsed. And Formulation A has the same adhesive properties as Formulation b. [Deterioration test] 玻璃 A glass substrate (formed by Tokyo Sanrong Vacuum Co., Ltd. with sodium ITO, 1500 Α 'SLR product) with an indium tin oxide (ITO) film was prepared, and the ΙΤ0 film was patterned into an electrode. shape. Ultrasonic water, neutral detergent, propylene and hydrazine for uitrasonic cleaning' Further extraction of the glass substrate from the boiled IPA for drying and UV/ozone on the surface (ultra-violet/ozone, After UV/O3) cleaning, the glass substrate is fixed on the substrate 28 201022358 32598pif holder holder of the vacuum evaporation apparatus. The pressure in the tank was reduced to less than or equal to 1×1 (T8 Pa. The pressure was continuously maintained to form the following film. On the ITO electrode surface, a copper phthalocyanine (CuPC) vapor-deposited film was formed (thickness of 100 phantoms as electricity). A hole injection layer is formed on the hole injection layer to form 4,4,-bis(N-(l-naphthyl)-N-phenylamino)biphenyl (4,4-bis(N-(l-naphthyl) )-N-phenylamino)biphenyl » NPD)

The deposited film (thickness 500A) was used as a hole transport layer. On the hole transport layer, a tris (8-quinolinolato aluminum, Alq3) vaporized film (thickness: 650 A) was formed as an electron injecting and emitting layer. On the electron-injecting and transporting layer, a lithium fluoride (Lih) film (5 persons) as an electron injecting electrode was formed. On the surface of the electron injecting electrode, a vapor film (A1) was formed as a protective electrode. The organic electroluminescent member of the fabricated element was not brought into contact with air, but was transferred from the evaporation apparatus to a gl〇ve box under a nitrogen atmosphere. In the handle box, the organic electroluminescent member 1 g &amp; was placed inside the molding container H 2 in the manner shown in Fig. 2, and the container was sealed. The organic electroluminescent member disposed in the IS container 2 is electrically connected! Each of the contact terminals can be externally controlled to be energized. The sealed inlaid container 2 is then removed from the glove box. 1 g of formulation A or formulation B of Table 1 was injected from the separator of the container. The injected formulation is hardened by heating. Thereafter, the organic electroluminescence member disposed in the container (125 mA/cm) was driven at a constant current for 300 hours, and the light-emitting state of the light-emitting portion was observed by the brightness detecting unit 4. Confirmation 29 201022358 32598pif The case where the dark spot is generated is recorded as χ, and the case where the dark spot is not confirmed is recorded as 〇 for evaluation. Fig. 3A shows the light-emitting state of the organic electroluminescence member when the preparation A is injected, and Fig. 3B shows the light-emitting state of the organic electroluminescence member when the preparation B is injected. Example 1 Example 2 Injection formulation formulation A luminescent state after formulation BU 〇〇 X 〇 [Reference example] An organic electroluminescent member was produced in the same manner as the above-described deterioration test, and was placed. Inside the aluminum container 2 (see Fig. 2), the container is sealed. The separator from the bar is infused with various alcohols (30 //1) using a microsyringe 3 . Immediately after the injection of the alcohol, the organic electroluminescence member disposed in the container (125 mA/cm2) was driven at a constant current for 48 hours, and the light-emitting state of the light-emitting portion was observed by the brightness detecting unit 4. The case where the dark spot is generated is recorded as X, and the case where the dark spot is not confirmed is recorded as 〇 φ for evaluation. [Table 4] Reference Example 1 Reference Example 2 Reference Example 3 Injecting component 2-propanyl 2-butanol The third luminescent state after 48 hours 〇 〇 〇 [Table 5] 30 201022358 32598pif

- Reference Comparative Example 1 Comparative Example y _ Ethanol-Injection Component Methanol ~ Comparative Example 3 Reference Comparative Example 4 Luminescence state after 48 hours _____正丙酵正丁酵 XX —-— XX As shown in Table 4 The second alcohol of the second alcohol, 2-propanol or 2-butanol, and the third butanol of the tertiary alcohol were confirmed to be out of order, and did not cause deterioration of the luminescent state. Another-side' as shown in Table 5, in the injection of human-grade alcohol

In the case of alcohol, ethanol, n-propanol or n-butanol, deterioration of the luminescence state was observed. Therefore, it has been found that the life of the organic EL device having the sealing member capable of suppressing the generation of the -first alcohol gas becomes long. [Industrial Applicability] The organic EL element having a high life can be provided by the sealing member of the present invention. This application claims priority based on the application number JP2_-250598 filed on Sep. 29, 2008. All of the application specification and drawings are hereby incorporated by reference. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Ben, the protection of the Ming (four) when the rear view of the towel, please define the Wei _ defined. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing changes with time in the subsequent strength of a sealant containing a decane coupling agent. Fig. 2 is a view for explaining the method of evaluating the illuminating state of the organic electroluminescent member in the embodiment, 2010 2010 358 32 598 pif. 3A and 3B are photographs showing the light-emitting state of the organic electroluminescence member. [Description of main components] 1 : Organic electroluminescent member 2: Aluminum container 3: Micro syringe 4: Brightness detection unit

32

Claims (1)

201022358 32598pif VII. Patent Application Range·· I A sealant that heats lg of the sealant at 100 ° C for 60 minutes to produce a primary alcohol of less than or equal to 10 #g. 2. The sealant as described in claim 1 which comprises a reaction product of a sinter coupling agent and/or a decane coupling agent. 3. The sealant of claim 1, wherein the primary alcohol has a boiling point of less than or equal to 12 Torr at 1 atm. Hey. 4. The sealant of claim 2, wherein the above-mentioned hair coupling agent is represented by the following formula (1), (1,) or (1"): [Chemical Formula 1] ο I R1 R2lolsi-lR4 ο Π R3._ί_Jn II Io R4—-si丨R4 _—I—0 1 R1 R4lsi-丨r4 I 0 1 R1 R4H 33 201022358 32598pif in the general formula (i), (r) or (i”) R1 to R3 each independently represent a group represented by the following formula (2), and ^4, RV and RV' each represent a monovalent organic group other than the oxy group, and η represents an integer of 1 or more, and n is 2 or more.悴2 or more, R4 and RV may be mutually fifiable and different; J mutually [Chemical 2] I ~C-R6 · · · (2) In the general formula (2), R5 represents a hydrogen atom or The hydrocarbon group, hydrazine and r7 each independently represent a hydrocarbon group. 5. The sealant of claim 4, further comprising an epoxy resin, and 仏, ^, or &, respectively, each having an epoxy group, an acryl group, an isocyanate group Any organic group. 6. The sealant of claim 2, further comprising a compound that adsorbs alcohol or reacts with an alcohol, and the above decane coupling agent is represented by the following formula (3), (3,) or (3,,) : [Chem. 3] 34 201022358 32598ptf Reference R12 0 1 Si-0 I ^14 Rii-〇T~Si 一Οι—R Rii_0· R14 Si 一OR ^13 (3) n •R 13 • · · (3,) 14 J n R14 (3,,) • · · Rn-0—Si—R14&quot; r14 In the general formula (3), (3') or (3”), Rli~Rl3 are each independently a monovalent organic group, but Ru One or more of R13 are a group represented by the formula (4), Rl4, Rl4' and Rl4" each represent a monovalent organic group other than the oxy group, and η represents an integer of 1 or more, and η is greater than or equal to In the case of 2, two or more R12, R14 and R14' may be the same or different from each other; [Chemical 4] 35 201022358 32598pif 5 R1 I Η丨C丨Η (4) In the general formula (4) 'R15 represents a hydrogen atom or a hydrocarbon group. 7. The sealant of claim 6, wherein the adsorbing alcohol or the compound reacting with the alcohol is an isocyanate compound. 8. The sealant as described in claim 1 further comprising a curable resin or/and a thermoplastic resin. 9. The sealant according to claim 8, wherein the above-mentioned decane coupling agent or/and decane is contained in an amount of from 10 parts by weight to 10 parts by weight based on 100 parts by weight of the above-mentioned curable resin or/and thermoplastic resin. The reactant of the coupling agent. 10. The sealant of claim 9, wherein the curable resin is a thermosetting resin. 11. The sealant of claim 1, wherein the thermosetting resin is an epoxy resin.密封 12. The sealant of claim 11, further comprising an acid anhydride and a hardening accelerator. 13. The sealant according to claim 12, which comprises, by weight of the above-mentioned epoxy resin, 1 to 10 parts by weight of the above-mentioned decane coupling agent or/and a decane coupling agent. The ratio of the respective acid anhydride groups/epoxy groups of the above acid anhydride and the above-mentioned hardening accelerator is 0.8 to 1.2 'the active functional group/epoxy group of the hardening accelerator 36 201022358 32598ptf The ratio of the amount is 0.008 to 0.152 . A sealing member which is a sealing member comprising a polymer or a cured product containing a sealant of a breaker coupling agent and/or a catalyst of a catalyst, and lg of the above sealing agent is 1 Torr. (1) The sealing member according to claim 14, wherein the primary alcohol has a boiling point of less than or equal to Hot at 1 atm. ❹ 16. — A method for producing an organic EL device, comprising: a first step of forming an organic EL member on a substrate; and a second step of: adhering to the above-mentioned organic EL member with a sealant as described in claim 1; In the third step, the sealing agent is cured to form a sealing member. The manufacturing method I7, the organic rainbow element described in the sixteenth patent range, and the second step are performed by a thermal lamination method. The EL element 'is composed of: an organic EL member, a ❹ ❹ == member connection, as in the scope of the patent application, item 1: the stipulation of the item, the EL7^', which is included in the patent application.