KR20210146279A - Peripheral encapsulant for resin composition and organic EL display device - Google Patents

Abstract

An object of the present invention is to provide a resin composition that is excellent in applicability, adhesiveness, and moisture permeability prevention, and can obtain an organic EL display element excellent in display performance by using it as a peripheral encapsulant for an organic EL display element. do. Moreover, this invention aims at providing the peripheral sealing agent for organic electroluminescent display elements which uses this resin composition.
The present invention contains polyisobutylene, a curable resin, a polymerization initiator, and fumed silica, the polyisobutylene has a weight average molecular weight of 5000 or more and 100,000 or less, and the curable resin is a urethane (meth ) containing acrylate, the content of the urethane (meth)acrylate is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene, the content of the fumed silica is the polyisobutyl It is a resin composition of 1 weight part or more and 30 weight part or less with respect to 100 weight part of ren.

Description

Peripheral encapsulant for resin composition and organic EL display device

This invention is excellent in applicability|paintability, adhesiveness, and moisture permeation prevention property, and also relates to the resin composition which can obtain the organic electroluminescent display element excellent in display performance by using it as a peripheral sealing agent for organic electroluminescent display elements. Moreover, this invention relates to the peripheral sealing agent for organic electroluminescent display elements formed using this resin composition.

An organic electroluminescent display element (organic electroluminescent display element) has the thin film structure by which the organic light emitting material layer was pinched|interposed between a pair of mutually opposing electrodes. Electrons are injected into this organic light emitting material layer from one electrode and holes are injected from the other electrode, so that electrons and holes are combined in the organic light emitting material layer to emit light. Compared with a liquid crystal display element requiring a backlight, etc., visibility is good, thickness reduction is possible, and it has the advantage that DC low voltage drive is possible.

However, such an organic EL display element has a problem that, when an organic light emitting material layer or an electrode is exposed to the outside air, the light emitting characteristic deteriorates rapidly, and the lifespan becomes short. Therefore, for the purpose of improving the stability and durability of an organic electroluminescent display element, in an organic electroluminescent display element, the sealing technique which blocks|blocks an organic light emitting material layer and an electrode from moisture and oxygen in air|atmosphere became indispensable.

In patent document 1, an organic electroluminescent display element is sealed by the structure which has an organic filling layer which coat|covers and seals the laminated body which has an organic light emitting material layer, and the moisture absorption sealing layer (sealing wall) which covers the side surface of the organic filling layer. A method is disclosed. In general, as an encapsulant for an organic EL display device, an in-plane encapsulant is used for the organic filling layer, and a peripheral encapsulant having a composition different from that of the in-plane encapsulant is used for the encapsulation wall. However, even when the organic EL display element is sealed using such an in-plane encapsulant and a peripheral encapsulant, display defects may occur in the organic EL display element when exposed to a harsh high temperature, high humidity environment.

Japanese Patent Laid-Open No. 2014-67598

An object of the present invention is to provide a resin composition that is excellent in applicability, adhesiveness, and moisture permeability prevention properties, and can obtain an organic EL display element excellent in display performance by using it as a peripheral encapsulant for an organic EL display element. do. Moreover, this invention aims at providing the peripheral sealing agent for organic electroluminescent display elements which uses this resin composition.

The present invention contains polyisobutylene, a curable resin, a polymerization initiator, and fumed silica, the polyisobutylene has a weight average molecular weight of 5000 or more and 100,000 or less, and the curable resin is a urethane (meth ) acrylate, the content of the urethane (meth)acrylate is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene, the content of the fumed silica is the polyisobutyl It is a resin composition of 1 weight part or more and 30 weight part or less with respect to 100 weight part of ren.

Hereinafter, the present invention will be described in detail.

The present inventors examined mix|blending polyisobutylene in order to improve the moisture permeation prevention property of the resin composition used as a peripheral sealing agent for organic electroluminescent display elements. However, the obtained resin composition may cause liquid dripping at the time of application|coating. Then, in order to prevent the liquid dripping at the time of application|coating, the present inventors examined mixing|blending fumed silica with a resin composition. However, when fumed silica is mix|blended in a large amount in order to fully prevent liquid dripping at the time of application|coating, the adhesiveness and moisture permeability prevention property after exposure of the resin composition obtained to a high-temperature, high-humidity environment may become inferior. Then, the present inventors examined mixing|blending urethane (meth)acrylate and a fumed silica so that it might become each specific content ratio with respect to polyisobutylene. As a result, an organic EL display element excellent in applicability, adhesiveness (including adhesiveness after exposure to high temperature and high humidity environment), and moisture permeability prevention, and excellent in display performance when used as a peripheral encapsulant for organic EL display elements found that a resin composition capable of obtaining

In addition, in this specification, the "(meth)acrylate" means an acrylate or a methacrylate, and the "urethane (meth)acrylate" means a compound having a urethane bond and a (meth)acryloyl group . In addition, the said "(meth)acryloyl" means acryloyl or methacryloyl.

The resin composition of this invention contains polyisobutylene.

By containing the said polyisobutylene, the resin composition of this invention becomes a thing excellent in moisture permeation prevention property, and when it uses as a peripheral sealing agent for organic electroluminescent display elements, it becomes a thing difficult to be compatible with an in-plane sealing agent.

The lower limit of the weight average molecular weight of the polyisobutylene is 5000, and the upper limit is 100,000. When the weight average molecular weight of the said polyisobutylene is this range, the resin composition obtained becomes more excellent in applicability|paintability, adhesiveness, and moisture permeation prevention property. A preferable lower limit of the weight average molecular weight of the polyisobutylene is 20,000, a preferable upper limit of 80,000, a more preferable lower limit of 30,000, a more preferable upper limit of 60,000, a still more preferable lower limit of 35,000, and a still more preferable upper limit of 40,000 It is 5000.

In addition, in this specification, the said "weight average molecular weight" is a value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Corporation) etc. are mentioned, for example.

The minimum with preferable content of the said polyisobutylene in a total of 100 weight part of the said polyisobutylene and curable resin mentioned later is 10 weight part, and a preferable upper limit is 80 weight part. When content of the said polyisobutylene is 10 weight part or more, the resin composition obtained becomes a thing more excellent in moisture permeation prevention property. When content of the said polyisobutylene is 80 weight part or less, the resin composition obtained becomes a thing more excellent in applicability|paintability and adhesiveness. A more preferable minimum of content of the said polyisobutylene is 20 weight part, and a more preferable upper limit is 60 weight part.

The resin composition of this invention contains curable resin.

The said curable resin contains urethane (meth)acrylate. By containing the urethane (meth)acrylate in combination with fumed silica to have a content to be described later, respectively, the dispersibility of the fumed silica can be improved, and as a result, the resin composition of the present invention prevents liquid dripping during application be something that can be prevented. Moreover, by containing the said urethane (meth)acrylate, the resin composition of this invention becomes a thing excellent in the adhesiveness after exposure to a high-temperature, high-humidity environment.

It is preferable that the said urethane (meth)acrylate has polybutadiene skeleton. When the said urethane (meth)acrylate has the said polybutadiene skeleton, the effect of improving the dispersibility of a fumed silica becomes more excellent.

The minimum with preferable weight average molecular weight of the said urethane (meth)acrylate is 2000, and a preferable upper limit is 20,000. When the weight average molecular weight of the said urethane (meth)acrylate is this range, it becomes the thing excellent in compatibility with the said isobutylene, and it becomes the thing excellent in the effect of improving the dispersibility of a fumed silica. The minimum with a more preferable weight average molecular weight of the said urethane (meth)acrylate is 5000, and a more preferable upper limit is 10,000.

The lower limit of the content of the urethane (meth)acrylate is 1 part by weight and the upper limit is 30 parts by weight with respect to 100 parts by weight of the polyisobutylene. When content of the said urethane (meth)acrylate is 1 weight part or more, it becomes the thing excellent in compatibility with the said polyisobutylene, and it becomes the thing excellent in the effect of improving the dispersibility of a fumed silica. Moreover, it becomes the thing excellent in the adhesiveness after the resin composition obtained is exposed to a high-temperature, high-humidity environment. When content of the said urethane (meth)acrylate is 30 weight part or less, the resin composition obtained becomes the thing excellent in moisture permeation prevention property. A preferable lower limit of the content of the urethane (meth)acrylate is 3 parts by weight, a preferable upper limit is 25 parts by weight, a more preferable lower limit is 5 parts by weight, and a more preferable upper limit is 20 parts by weight.

From a viewpoint of adhesiveness etc., it is preferable that the said curable resin contains other curable resin other than the said urethane (meth)acrylate.

As said other curable resin, the (meth)acrylic compound which does not have a urethane bond, an epoxy compound, an oxetane compound, the urethane compound etc. which do not have a (meth)acryloyl group are mentioned. Especially, it is preferable that the (meth)acryl compound which does not have the said urethane bond is included.

In addition, in this specification, the said "(meth)acryl" means acryl or methacryl, and the said "(meth)acryl compound" means a compound having a (meth)acryloyl group.

As (meth)acrylic compound which does not have the said urethane bond, For example, isobornyl (meth)acrylate, adamantyl (meth)acrylate, methylcyclohexyl (meth)acrylate, norbornylmethyl ( Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclodecyl (meth) acrylate, 4-t-butylcyclo Hexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, tricyclodecane dimethanol di (meth)acrylate, etc. are mentioned. Especially, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate are preferable.

As said epoxy compound, a glycidyl ether compound, an alicyclic epoxy compound, etc. are mentioned, for example.

As said glycidyl ether compound, diethylene glycol diglycidyl ether etc. are mentioned, for example.

Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 1 of 2,2-bis(hydroxymethyl)-1-butanol; 2-epoxy-4-(2-oxylanyl)cyclohexane adduct, etc. are mentioned.

Examples of the oxetane compound include 1,4-bisb[(3-ethyl-3-oxetanyl)methoxy]methylbbenzene, di[2-(3-oxetanyl)butyl]ether. and 3-ethyl-3-hydroxymethyloxetane.

As a urethane compound which does not have the said (meth)acryloyl group, the reaction product of an isocyanate compound and arbitrary polyol compounds, etc. are mentioned, for example.

As said isocyanate compound, a toluene diisocyanate compound, a diphenylmethane diisocyanate compound, etc. are mentioned, for example.

Examples of the toluene diisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate, or a mixture thereof.

As the diphenylmethane diisocyanate compound, for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) ), or a mixture thereof.

As for content of said other curable resin, with respect to 100 weight part of said polyisobutylene, a preferable minimum is 20 weight part, and a preferable upper limit is 150 weight part. When content of said other curable resin is this range, the resin composition obtained becomes a thing more excellent in adhesiveness and moisture permeation prevention property. A more preferable lower limit of content of said other curable resin is 30 weight part, a more preferable upper limit is 120 weight part, A more preferable minimum is 40 weight part, and a still more preferable upper limit is 100 weight part.

The resin composition of this invention contains a polymerization initiator.

As said polymerization initiator, a radical polymerization initiator and a cationic polymerization initiator can be used. Especially, a radical polymerization initiator is preferable.

As said radical polymerization initiator, an optical radical polymerization initiator and a thermal radical polymerization initiator can be used.

As said radical photopolymerization initiator, a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, a thioxanthone compound, etc. are mentioned, for example.

Specific examples of the radical photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 1,2- (dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-2-phenylacetophenone, bis (2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyl) Ethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione2-(O-benzoyloxime) , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned. Among them, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one is preferable.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.

As said azo compound, 2,2'- azobis (2, 4- dimethylvaleronitrile), azobisisobutyronitrile, etc. are mentioned, for example.

Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, peroxyester, diacylperoxide, peroxydicarbonate, and the like.

Among the thermal radical polymerization initiators, commercially available ones include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, V-501 (all manufactured by FUJIFILM Wako Pure Pharmaceutical Co., Ltd.). can be heard

As said cationic polymerization initiator, a photocationic polymerization initiator and a thermal cationic polymerization initiator are mentioned.

The said photocationic polymerization initiator will not be specifically limited if it generate|occur|produces a protonic acid or a Lewis acid by light irradiation, An ionic photo-acid generating type may be sufficient, and a nonionic photo-acid generating type may be sufficient as it.

As the anion moiety of the ionic photoacid generating type photocationic polymerization initiator, for example, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (provided that X is at least 2 represents the phenyl group substituted with the above fluorine or trifluoromethyl group) etc. are mentioned.

As said ionic photo-acid generating type photocationic polymerization initiator, For example, the aromatic sulfonium salt, aromatic iodonium salt, aromatic diazonium salt, aromatic ammonium salt, (2,4-cyclopentadiene which has the said anion moiety) -1-yl)((1-methylethyl)benzene)-Fe salt and the like.

Examples of the aromatic sulfonium salt include bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluoro Rhoantimonate, bis(4-(diphenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate , Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetra Fluoroborate, diphenyl-4-(phenylthio)phenylsulfoniumtetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium Tetrafluoroborate, triphenylsulfoniumtetrakis(pentafluorophenyl)borate, triarylsulfoniumtetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy) )phenylsulfonio)phenyl)sulfidebishexafluorophosphate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoroantimonate , bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy) )) phenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)thiophenyl)sulfoniumtetrakis(pentafluorophenyl)borate, and the like. .

Examples of the aromatic iodonium salt include diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrakis (pentafluoro Phenyl) borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodoniumtetrafluoroborate, bis(dodecylphenyl) ) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoro Roantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetrakis(pentafluorophenyl)borate, etc. can be heard

Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate. and the like.

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, and 1-benzyl-2-cyano. Pyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naph Tylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, etc. are mentioned.

As the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl)((1- Methylethyl)benzene)-Fe(II)hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II)hexafluoroantimonate, ( 2,4-Cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II)tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl )benzene)-Fe(II)tetrakis(pentafluorophenyl)borate, and the like.

Examples of the nonionic photoacid generating type photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonate. .

As what is marketed among the said photocationic polymerization initiators, For example, the photocationic polymerization initiator by the Midori Chemical company, the photocationic polymerization initiator by the Union Carbide company, the photocationic polymerization initiator by the ADEKA company, 3M The photocationic polymerization initiator by the company make, the photocationic polymerization initiator by the BASF company, the photocationic polymerization initiator by the Rhodia company, etc. are mentioned.

As a photocationic polymerization initiator by the said Midori Chemical company, DTS-200 etc. are mentioned, for example.

UVI6990, UVI6974 etc. are mentioned as said Union Carbide photocationic polymerization initiator, for example.

As a photocationic polymerization initiator by the said ADEKA company, SP-150, SP-170, etc. are mentioned, for example.

As a photocationic polymerization initiator by the said 3M company, FC-508, FC-512, etc. are mentioned, for example.

As said BASF photocationic polymerization initiator, IRGACURE261, IRGACURE290, etc. are mentioned, for example.

As a photocationic polymerization initiator by the said Rhodia company, PI2074 etc. are mentioned, for example.

As the thermal cationic polymerization initiator, the anion moiety is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (provided that X is at least two or more fluorine or trifluoromethyl groups substituted phenyl group), sulfonium salts, phosphonium salts, ammonium salts, etc. are mentioned. Among them, sulfonium salts and ammonium salts are preferable.

As said sulfonium salt, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, etc. are mentioned.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl)ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) Ammoniumtetrakis(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium Hexafluorotetrakis(pentafluorophenyl)borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammoniumhexafluoroantimonate, methylphenyldibenzylammoniumtetrakis(pentafluorophenyl)borate, phenyltribenzyl Ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridinium trifluoro Methanesulfonic acid etc. are mentioned.

As what is marketed among the said thermal cationic polymerization initiators, the thermal cationic polymerization initiator by Sanshin Chemical Industries, Ltd., the thermal cationic polymerization initiator by King Industries, etc. are mentioned, for example.

Examples of the thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4. can

As a thermal cationic polymerization initiator by the said King Industries, CXC-1612, CXC-1821, etc. are mentioned, for example.

As for content of the said polymerization initiator, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable minimum is 0.05 weight part, and a preferable upper limit is 10 weight part. When content of the said polymerization initiator is 0.05 weight part or more, the resin composition obtained becomes a thing excellent in sclerosis|hardenability. When content of the said polymerization initiator is 10 weight part or less, hardening reaction of the resin composition obtained does not become quick too much, workability|operativity becomes a more excellent thing, and hardened|cured material can be made into a more uniform thing. A more preferable lower limit of content of the said polymerization initiator is 1 weight part, and a more preferable upper limit is 5 weight part.

The resin composition of the present invention contains fumed silica. By containing the fumed silica in combination with the urethane (meth)acrylate having the above content so as to have a content to be described later, the resin composition of the present invention can prevent liquid dripping at the time of application.

As for the said fumed silica, a preferable lower limit of a specific surface area is 80 m<2>/g, and a preferable upper limit is 400 m<2>/g. When the specific surface area of the said fumed silica is this range, the effect which prevents the liquid dripping at the time of application|coating of the resin composition obtained becomes more excellent. A more preferable lower limit of the specific surface area of the fumed silica is 120 m2/g, a more preferable upper limit is 350 m2/g, a more preferable lower limit is 180 m2/g, and a more preferable upper limit is 330 m2/g.

In addition, the said "specific surface area" can be measured by the BET method using nitrogen gas as a specific surface area measuring apparatus. As said specific surface area measuring apparatus, ASAP-2000 (made by Shimadzu Corporation) etc. are mentioned, for example.

A preferable lower limit of the average primary particle diameter of the fumed silica is 2 nm, and a preferable upper limit thereof is 30 nm. When the average primary particle diameter of the fumed silica according to the present invention is within this range, the effect of preventing liquid dripping at the time of application of the obtained resin composition becomes more excellent. A more preferable lower limit of the average primary particle diameter of the fumed silica is 5 nm, and a more preferable upper limit is 10 nm.

In addition, the said "average primary particle diameter" can be measured by a dynamic light scattering type particle diameter measuring apparatus etc. As said dynamic light scattering type particle diameter measuring apparatus, ELSZ-1000S (made by Otsuka Electronics Co., Ltd.) etc. are mentioned, for example.

The lower limit of the content of the fumed silica is 1 part by weight and the upper limit is 30 parts by weight with respect to 100 parts by weight of the polyisobutylene. When content of the said fumed silica is 1 weight part or more, the effect which prevents liquid dripping at the time of application|coating of the resin composition obtained becomes more excellent. When content of the said fumed silica is 30 weight part or less, the resin composition obtained becomes the thing excellent in adhesiveness and moisture permeation prevention property. A preferable lower limit of the content of the fumed silica is 1.5 parts by weight, a preferable upper limit is 15 parts by weight, a more preferable lower limit is 2 parts by weight, and a more preferable upper limit is 10 parts by weight.

In addition, the ratio of the content of the fumed silica and the content of the urethane (meth) acrylate is preferably 0.1 parts by weight or more and 10 parts by weight or less of the urethane (meth) acrylate with respect to 1 part by weight of the fumed silica.

It is preferable that the resin composition of this invention contains a water absorbing filler. By containing the said water absorbent filler, the resin composition of this invention becomes a thing excellent in moisture permeation prevention property.

Examples of the absorptive filler include alkaline earth metal oxides, magnesium oxide, and molecular sieves.

As an oxide of the said alkaline-earth metal, calcium oxide, strontium oxide, barium oxide, etc. are mentioned, for example.

Especially, from a viewpoint of water absorption, the oxide of an alkaline-earth metal is preferable, and calcium oxide is more preferable.

These water absorbent fillers may be used independently and may be used in combination of 2 or more type.

As for content of the said water absorbing filler, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable minimum is 10 weight part, and a preferable upper limit is 300 weight part. When content of the said water absorbent filler is this range, the resin composition obtained becomes a thing more excellent in moisture permeation prevention property. A more preferable lower limit of the content of the water-absorbent filler is 30 parts by weight, and a more preferable upper limit thereof is 250 parts by weight.

The resin composition of this invention is the range which does not impair the objective of this invention for the purpose of improving adhesiveness, etc. WHEREIN: You may contain other fillers other than the said fumed silica and a water absorbing filler.

As said other filler, an inorganic filler or an organic filler can be used.

As said inorganic filler, silica other than fumed silica, a talc, alumina, etc. are mentioned, for example.

As said organic filler, polyester microparticles|fine-particles, polyurethane microparticles|fine-particles, vinyl polymer microparticles|fine-particles, acrylic polymer microparticles|fine-particles, etc. are mentioned, for example. Especially, talc is preferable.

The resin composition of this invention may contain a thermosetting agent.

Examples of the thermal curing agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.

Examples of the hydrazide compound include 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, dihydrazide sebacate, dihydrazide isophthalate, dihydrazide adipic acid, and malon. acid dihydrazide; and the like.

Examples of the imidazole derivative include 1-cyanoethyl-2-phenylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, 2,4-diamino -6-(2'-Methylimidazolyl-(1'))-ethyl-s-triazine, N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'- (2-methyl-1-imidazolylethyl)-adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. can be heard

As said acid anhydride, tetrahydrophthalic anhydride, ethylene glycol bis(anhydro trimellitate), etc. are mentioned, for example.

These thermosetting agents may be used independently and may be used in combination of 2 or more type.

Among the above-mentioned thermosetting agents, commercially available ones include, for example, SDH (manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine Techno). and the like.

As for content of the said thermosetting agent, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable lower limit is 0.01 weight part, and a preferable upper limit is 10 weight part. When content of the said thermosetting agent is 0.01 weight part or more, the resin composition obtained becomes a thing excellent in thermosetting property. When content of the said thermosetting agent is 10 weight part or less, the resin composition obtained becomes a thing excellent in storage stability. A more preferable lower limit of the content of the thermosetting agent is 0.5 parts by weight, a more preferable upper limit is 5 parts by weight, a more preferable lower limit is 1 part by weight, and a more preferable upper limit is 3 parts by weight.

The resin composition of this invention may contain tackifying resin for the purpose of improving adhesiveness further, etc.

As said tackifying resin, a terpene resin, modified terpene resin, a coumarone resin, an indene resin, petroleum resin etc. are mentioned, for example.

As said modified terpene resin, hydrogenated terpene resin, a terpene phenol copolymer resin, aromatic modified terpene resin etc. are mentioned, for example.

Examples of the petroleum resin include aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins, and hydrides thereof. and the like.

Especially, as said tackifying resin, from viewpoints of adhesiveness of a resin composition, moisture permeability resistance, compatibility, etc., a terpene resin, an aromatic modified terpene resin, a terpene phenol copolymer resin, a hydrogenated alicyclic petroleum resin, an aromatic petroleum resin , aliphatic aromatic copolymer petroleum resin and alicyclic petroleum resin are preferable, alicyclic petroleum resin is more preferable, alicyclic saturated hydrocarbon resin and alicyclic unsaturated hydrocarbon resin are still more preferable, cyclohexyl ring-containing saturated hydrocarbon resin, dish Chlopentadiene-modified hydrocarbon resins are particularly preferred.

These tackifying resins may be used independently and may be used in combination of 2 or more type.

A minimum with a preferable content of the said tackifying resin is 0.01 weight part with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, and a preferable upper limit is 100 weight part. When content of the said tackifying resin is this range, the effect of improving adhesiveness can be exhibited more, maintaining moisture permeation prevention property. A more preferable minimum of content of the said tackifying resin is 10 weight part, and a more preferable upper limit is 40 weight part.

The resin composition of this invention may contain a sensitizer. The said sensitizer improves the polymerization initiation efficiency of the said polymerization initiator more, and has a role which accelerates|stimulates the hardening reaction of the resin composition of this invention more.

Examples of the sensitizer include anthracene-based compounds, thioxanthone-based compounds, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2,4-dichlorobenzophenone, o -Methyl benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc. are mentioned.

Examples of the anthracene-based compound include 9,10-dibutoxyanthracene.

As said thioxanthone type compound, 2, 4- diethyl thioxanthone etc. are mentioned, for example.

These sensitizers may be used independently and may be used in combination of 2 or more type.

As for content of the said sensitizer, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable minimum is 0.05 weight part, and a preferable upper limit is 3 weight part. When content of the said sensitizer is 0.05 weight part or more, a sensitizing effect is exhibited more. When content of the said sensitizer is 3 weight part or less, light can be transmitted to a deep part, without absorption becoming large too much. A more preferable minimum of content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.

The resin composition of this invention may contain a stabilizer. By containing the said stabilizer, the resin composition of this invention becomes the thing excellent in storage stability more.

As said stabilizer, an aromatic amine compound, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc. are mentioned, for example.

As said aromatic amine compound, benzylamine, an aminophenol type epoxy resin, etc. are mentioned, for example.

Especially, an aromatic amine compound is preferable and benzylamine is more preferable.

These stabilizers may be used independently and may be used in combination of 2 or more type.

As for content of the said stabilizer, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable minimum is 0.001 weight part, and a preferable upper limit is 2 weight part. When content of the said stabilizer is this range, storage stability becomes more excellent, maintaining sclerosis|hardenability which was excellent in the resin composition obtained. A more preferable lower limit of the content of the stabilizer is 0.005 parts by weight, and a more preferable upper limit thereof is 1 part by weight.

The resin composition of this invention may contain a silane coupling agent. The said silane coupling agent has a role of improving the adhesiveness of the resin composition of this invention, a board|substrate, etc.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, etc. are mentioned. Especially, 3-acryloxypropyl trimethoxysilane is preferable.

These silane coupling agents may be used independently and may be used in combination of 2 or more type.

As for content of the said silane coupling agent, with respect to a total of 100 weight part of the said polyisobutylene and the said curable resin, a preferable minimum is 0.1 weight part, and a preferable upper limit is 10 weight part. When content of the said silane coupling agent is this range, the effect of improving the adhesiveness of the resin composition obtained becomes more excellent, preventing the bleed-out of an excess silane coupling agent. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight.

The resin composition of this invention may contain a surface modifier in the range which does not impair the objective of this invention. By containing the said surface modifier, the flatness of the coating film of the resin composition of this invention can be improved.

As said surface modifier, surfactant, a leveling agent, etc. are mentioned, for example.

As said surface modifier, things, such as a silicone type, an acryl type, a fluorine type, are mentioned, for example.

As what is marketed among the said surface modifiers, the surface modifier by the Bick Chemie Japan company, the surface modifier by the Kusumoto Chemical company, the surface modifier by the AGC Semi-Chemical company, etc. are mentioned, for example.

As said surface modifier by the said Bick Chemie Japan company, BYK-300, BYK-302, BYK-331 etc. are mentioned, for example.

UVX-272 etc. are mentioned as said surface modifier by the said Kusumoto Chemicals company, for example.

As a surface modifier by the said AGC Semi-Chemical company, Suflon S-611 etc. are mentioned, for example.

The resin composition of this invention may contain the compound which reacts with the acid which generate|occur|produced in the resin composition, and/or ion exchange resin in the range which does not impair the objective of this invention.

Examples of the compound reacting with the generated acid include a substance neutralizing acid and, for example, a carbonate or hydrogen carbonate of an alkali metal, or a carbonate or hydrogen carbonate of an alkaline earth metal. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used, and a cation exchange type or amphoteric ion exchange type capable of adsorbing chloride ions is particularly preferable.

The resin composition of the present invention may contain various known additives, such as curing retarders, reinforcing agents, softeners, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants, if necessary, within the scope not impairing the object of the present invention. .

It is preferable that the resin composition of this invention does not contain a solvent from a viewpoint of suppressing generation|occurrence|production of an outgas more. Even if the resin composition of this invention does not contain a solvent, it can be made into the thing excellent in applicability|paintability.

In addition, in this specification, "a solvent is not contained" means that content of a solvent is less than 1000 ppm.

As a method for producing the resin composition of the present invention, for example, using a mixer, polyisobutylene, a curable resin, a polymerization initiator, fumed silica, and a water absorbent filler to be added as needed are mixed. method and the like.

As said mixer, a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, three rolls etc. are mentioned, for example.

The resin composition of the present invention is a value obtained by dividing the viscosity measured at 25°C and 0.5 rpm using the E-type viscometer by the viscosity measured at 25°C and 5 rpm using the E-type viscometer (hereinafter, “ A preferable lower limit of the thixotropic index”) is 2.0, and a preferable upper limit thereof is 5.0. When the said thixotropic index is this range, the resin composition of this invention becomes a thing excellent in applicability|paintability. A more preferable upper limit of the thixotropic index is 3.5.

It is preferable that the resin composition of this invention is used as a peripheral sealing agent for organic electroluminescent display elements for forming sealing walls around the laminated body which has an organic light emitting material layer. The said peripheral sealing agent for organic electroluminescent display elements is used in combination with the in-plane sealing agent for organic electroluminescent display elements which coat|covers the laminated body normally.

The peripheral sealing agent for organic electroluminescent display elements which uses the resin composition of this invention is also one of this invention.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in applicability|paintability, adhesiveness, and moisture permeation prevention property, and also can provide the resin composition which can obtain the organic electroluminescent display element excellent in display performance by using it as a peripheral sealing agent for organic electroluminescent display elements. . Moreover, according to this invention, the peripheral sealing agent for organic electroluminescent display elements which uses this resin composition can be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1 to 10, Comparative Examples 1 to 6)

According to the compounding ratios shown in Tables 1 and 2, each material was stirred and mixed for 3 minutes at a stirring speed of 2000 rpm using a stirring mixer, and the resin composition of Examples 1-10 and Comparative Examples 1-6 was produced. As the stirring mixer, ARV-310 (manufactured by Thinkki) was used.

About each obtained resin composition, using the E-type viscometer, the viscosity in the conditions of 25 degreeC, 0.5 rpm, and the viscosity in the conditions of 25 degreeC, 5 rpm were measured, and 25 degreeC and the conditions of 0.5 rpm The thixotropic index was derived as the value obtained by dividing the measured viscosity by the viscosity measured under the conditions of 25°C and 5 rpm. As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Industries, Ltd.) was used.

<Evaluation>

The following evaluation was performed about each resin composition obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(1) Coatability

Each resin composition obtained in Examples and Comparative Examples is filled in a syringe and mounted on the discharge adapter of the dispenser, the resin composition is discharged for 10 seconds by making the discharge pressure of the dispenser positive pressure, and then the syringe tip when the negative pressure is set for 1 minute Liquid dripping was confirmed. As a syringe, a UV block syringe (manufactured by Musashi Engineering) with a capacity of 10 mL was used, and as a dispenser, a tabletop application robot SHOTMASTER SX series (manufactured by Musashi Engineering) was used. A case in which a droplet did not form at the tip of the syringe in 1 minute was “◎”, a case in which a droplet was generated at the tip of the syringe in 1 minute but did not fall is “○”, and a case in which a droplet fell from the tip of the syringe in 1 minute was “ △", the case where 2 or more drops fell from the tip of a syringe in 1 minute was made into "x", and applicability|paintability was evaluated.

(2) Adhesiveness

To 10 g of each resin composition obtained in Examples and Comparative Examples, 0.03 g of spacer particles having a diameter of 10 μm were added and uniformly dispersed using a stirring mixer. Micropearl SP-210 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used as the spacer particles, and ARV-310 (manufactured by Thinkki Corporation) was used as the stirring mixer. After apply|coating the resin composition which disperse|distributed the spacer particle|grains to the center part on the glass substrate A, the glass substrate B was crossed so that it might be crossed, and it was affixed, and it pressurized and made thickness uniform. The application amount of the resin composition in which the spacer particles were dispersed was adjusted so that the resin composition in which the spacer particles were dispersed after being pressurized to have a uniform thickness became a circular shape having a diameter of 5.0 to 7.0 mm. The said glass substrates A and B were dried, after wash|cleaning the surface of the glass of length 60mm, width 30mm, and thickness 5mm with acetone. Next, the glass substrate A and the glass substrate B were adhere|attached and the test piece for initial stage adhesive evaluation was obtained by irradiating 3000 mJ/cm<2> of ultraviolet-rays with a wavelength of 365 nm with a UV-LED irradiation apparatus, and hardening the resin composition. In addition, after bonding glass substrate A and glass substrate B in the same manner as the test piece for initial adhesive evaluation, exposure to high temperature and high humidity conditions of 85 ° C. and 85 % RH for 500 hours. Adhesive evaluation after exposure to high temperature and high humidity environment A dragon test piece was obtained.

For each test piece, the both ends of the glass substrate A are fixed from the bottom by placing the glass substrate B down, and the both ends of the glass substrate B are compressed from above with a precision universal testing machine at 23° C. and a speed of 5 mm/min. By doing so, the adhesive force of the glass substrate A and the glass substrate B was measured. The point to compress was made into the range of 20 mm in length and 5 mm in width centering on the position of 7.25 mm from the both ends of the glass substrate B. Autograph AG-Xplus (manufactured by Shimadzu Corporation) was used as the precision universal testing machine.

Adhesive force made the maximum load from the start of compression by a precision universal testing machine until glass substrate A and glass substrate B peel completely by the value which divided by the area of the resin composition of a test piece. When the adhesive strength was 300 N/cm2 or more, "◎", less than 300 N/cm2 and 250 N/cm2 or more, "○", less than 250 N/cm2 and 200 N/cm2 or more, "△", 200 N The case of less than /cm<2> was made into "x", and initial adhesiveness and adhesiveness after exposure to a high-temperature, high-humidity environment were evaluated.

(3) moisture permeability prevention

The following Ca-TEST was implemented about each resin composition obtained by the Example and the comparative example.

First, to 10 g of each resin composition obtained in Examples and Comparative Examples, 0.03 g of spacer particles having a diameter of 10 μm were added and uniformly dispersed using a stirring mixer. Micropearl SP-210 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used as the spacer particles, and ARV-310 (manufactured by Sinki Corporation) was used as the stirring mixer. Next, the resin composition in which the spacer particle|grains were disperse|distributed was apply|coated to the surface of a glass substrate.

Next, a mask having a plurality of openings of 2 mm × 2 mm was covered on another glass substrate having a size of 30 mm × 30 mm, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions of vapor deposition were that the inside of the vapor deposition machine of a vacuum vapor deposition apparatus ^{was pressure-reduced to 2x10 -3} Pa, and 2000 angstrom Ca was formed into a film by the vapor deposition rate of 5.0 angstrom/s. The glass substrate on which Ca was deposited was moved in a glove box managed at a dew point (-60 ° C. or higher), and the glass substrate coated with the resin composition on the surface and the glass substrate on which Ca was deposited were placed, the resin composition was placed on the deposition pattern of Ca. It was glued to become . After pressurizing and making the thickness of the resin composition layer uniform, 3000 mJ/cm<2> of ultraviolet rays with a wavelength of 365 nm were irradiated with a UV-LED irradiation apparatus, the resin composition was hardened, and the Ca-TEST board|substrate was produced.

The obtained Ca-TEST board|substrate was exposed to 85 degreeC, 85 %RH high-temperature, high-humidity conditions, and the penetration distance of the water|moisture content from the glass substrate cross section into the layer which consists of a hardened|cured material of a resin composition was observed from loss|disappearance of Ca.

As a result, when the exposure time under high-temperature, high-humidity conditions was 1000 hours, when the penetration distance of moisture was less than 3.0 mm, "double-circle", when 3.0 mm or more and less than 3.5 mm, "○", 3.5 mm or more and less than 4.0 mm The case where it was "(triangle|delta)" and the case where it was 4.0 mm or more was made into "x", and moisture permeation prevention property was evaluated.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in applicability|paintability, adhesiveness, and moisture permeation prevention property, and also can provide the resin composition which can obtain the organic electroluminescent display element excellent in display performance by using it as a peripheral sealing agent for organic electroluminescent display elements. . Moreover, according to this invention, the peripheral sealing agent for organic electroluminescent display elements which uses this resin composition can be provided.

Claims (7)

It contains polyisobutylene, a curable resin, a polymerization initiator, and fumed silica,
The polyisobutylene has a weight average molecular weight of 5000 or more and 100,000 or less,
The curable resin includes urethane (meth) acrylate,
The content of the urethane (meth) acrylate is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene,
The resin composition, characterized in that the content of the fumed silica is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene. The method of claim 1,
The urethane (meth)acrylate is a resin composition having a polybutadiene skeleton. 3. The method of claim 1 or 2,
The said urethane (meth)acrylate is a resin composition whose weight average molecular weights are 2000 or more and 20,000 or less. 4. The method of claim 1, 2 or 3,
The resin composition in which the said curable resin contains the (meth)acrylic compound which does not have a urethane bond further. 5. The method of claim 1, 2, 3 or 4,
The fumed silica is a resin composition having a specific surface area of 80 m 2 /g or more and 400 m 2 /g or less. 6. The method of claim 1, 2, 3, 4 or 5, wherein
A value obtained by dividing the viscosity measured at 25°C and 0.5 rpm using the E-type viscometer by the viscosity measured at 25°C and 5 rpm using the E-type viscometer is 2.0 or more and 5.0 or less. The peripheral sealing agent for organic electroluminescent display elements formed using the resin composition of Claim 1, 2, 3, 4, 5, or 6.