JP2005129520A - Transparent sealant for organic el element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent sealant for an organic EL element excellent in flexibility, capable of sufficiently sealing the EL element and suppressing generation of a dark spot to enhance visibility of an image in the case of use for an organic EL display. <P>SOLUTION: A transparent sealant for an organic EL element 2 is formed of flexible polymer compounds, and disposed between the light emitting surface of a light emitting element 3 and the sealing member 4 of an EL display panel 1 comprising the element 3; sequentially including a substrate 31, a positive electrode layer 32, a light emitting layer 33 and a negative electrode layer 34; and the sealing member 4 disposed on a side of the light emitting surface of the element 3. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a transparent sealing material for organic EL elements. More specifically, the present invention relates to a transparent sealing material for organic EL elements used to fill a gap on the light emitting surface side of a light emitting element constituting an electroluminescence display panel (hereinafter simply referred to as “EL display panel”). The transparent sealing material for organic EL elements of the present invention is used in EL display panels for mobile phones, personal digital assistants, desktop computers, notebook computers, televisions, in-vehicle information devices, watches, and other various display devices. It can be used suitably.

Since the EL element emits light by itself, a display device including the EL element has high visibility. A high-performance display device including an organic EL element that can reduce the applied voltage as compared with an inorganic EL element by utilizing such properties, that is, an organic EL display has been studied.
The organic EL element basically has a configuration in which an anode layer, a light emitting layer, and a cathode layer are sequentially formed on a substrate made of glass or the like. In order to improve performance, a functional layer may be provided between each layer.
The organic EL element having the above-described configuration can emit light by energizing between the anode layer and the cathode layer. However, if moisture, impurities, etc. are present around the element, the material constituting the element is eroded, leading to deterioration. When a display device including a deteriorated organic EL element is used, a light emission defect, that is, a dark spot is generated, leading to deterioration of visibility.

  In addition, a display device including an organic EL element is usually provided with a transparent substrate (may be a sealing can) made of glass or the like in order to cover and seal the organic EL element. As a method for solving the above problems, a method of disposing a dehydrating agent in a space formed between an organic EL element and a transparent substrate, a method of using a transparent sealing material made of an ultraviolet curable resin, a non-adsorbent-containing method A method of filling an active liquid (see Patent Document 1) and the like are disclosed. However, the suppression of the occurrence of dark spots is insufficient. In addition, when a hard transparent sealing material obtained using an ultraviolet curable resin is used, it is not easy to fix the transparent substrate or the sealing can in the manufacturing stage of the display device, and the element is not sufficiently fixed. Sealing may be insufficient.

JP-A-9-35868

  INDUSTRIAL APPLICABILITY The present invention is excellent in flexibility, can sufficiently seal an organic EL element, and, when an organic EL display is used, can suppress the occurrence of dark spots and increase the visibility of an image. An object is to provide a transparent sealing material.

The present invention is shown below.
[1] Organic EL used for an electroluminescence display panel including a light emitting element sequentially including a substrate, an anode layer, a light emitting layer, and a cathode layer, and a sealing member disposed on the light emitting surface side of the light emitting element A transparent sealing material for an element, which is formed from a flexible polymer composition, and is disposed between a light emitting surface of the light emitting element and the sealing member. Transparent encapsulant.
[2] The transparent sealing material for organic EL elements according to [1], wherein the total light transmittance is 90% or more when the thickness of the transparent sealing material for organic EL elements is 0.5 mm.
[3] The transparent sealing material for organic EL elements according to [1] or [2], wherein the flexible polymer composition is an elastomer composition.
[4] The flexible polymer composition includes a diene polymer, an olefin polymer, an acrylic polymer, a urethane polymer, a polyamide polymer, a polyester polymer, a vinyl chloride polymer, and a fluorine polymer. The transparent sealing material for organic EL elements according to any one of the above [1] to [3], comprising at least one polymer selected from a polymer and a silicone-based polymer.
[5] The diene polymer includes a styrene / butadiene copolymer and a hydride thereof, a styrene / isoprene copolymer and a hydride thereof, a butadiene block copolymer and a hydride thereof, and a styrene / butadiene / styrene block copolymer. The transparent sealing material for organic EL devices according to the above [4], which is at least one selected from a coalescence and a hydride thereof, and a styrene / isoprene / styrene block copolymer and a hydride thereof.
[6] The diene polymer has a butadiene polymer block (I) having a vinyl bond content of less than 25%, a mass ratio of the conjugated diene unit (a1) and the other monomer unit (a2) [(a1 ) / (A2)] is (100 to 50) / (0 to 50), and each of the conjugated dienes has at least one polymer block (II) in the molecule having a vinyl bond content of 25 to 95%. The transparent sealing material for organic EL devices according to the above [4] or [5], which is a hydride of a conjugated diene block polymer obtained by hydrogenating a system block polymer.
[7] In the diene polymer, the mass ratio [(b1) / (b2)] of the conjugated diene unit (b1) and the aromatic vinyl compound (b2) is (99-50) / (1-50). [4] or [5] above, wherein the diene polymer having at least one polymer block in the molecule having a vinyl bond content of 65 to 95% is a hydrogenated diene polymer obtained by hydrogenation Transparent sealing material for organic EL elements.
[8] The organic EL device according to [4], wherein the olefin polymer is at least one selected from an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer. Transparent sealing material.
[9] The ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer are a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, and The transparent sealing material for organic EL elements according to the above [8], which has a functional group selected from nitrile groups.
[10] The transparent sealing material for organic EL elements according to [8], further comprising metal ions and / or metal compounds.
[11] The transparent sealing material for organic EL elements according to [1] to [10], wherein the flexible polymer composition contains a liquid substance.
[12] The transparent sealing material for organic EL elements according to [11], wherein the liquid substance has a kinematic viscosity at 40 ° C. of 800 mm ² / s or less.
[13] The content of the liquid substance is 50 to 5000 parts by mass with respect to a total of 100 parts by mass of the polymer contained in the flexible polymer composition. Transparent encapsulant for organic EL elements.
[14] The transparent sealing material for organic EL elements according to any one of [1] to [13], wherein the transparent sealing material for organic EL elements is a thin-walled body having a thinnest portion having a thickness of 0.1 to 1000 μm. Sealing material.

The transparent sealing material for organic EL elements of the present invention is formed from a flexible polymer composition. The transparent sealing material for organic EL elements of the present invention is excellent in flexibility and can be sufficiently sealed without deteriorating the light emitting elements. As a result, the occurrence of dark spots can be suppressed, and the visibility of the image is stabilized.
Since the transparent sealing material for organic EL elements of the present invention is also excellent in transparency, even when it is in close contact with a transparent member such as a sealing member constituting the EL display panel, the transparency does not decrease. As a result, the visibility of the image is stabilized.
When the flexible polymer composition is an elastomer composition, the flexible polymer composition has sufficient flexibility even when formed into a desired shape. As a result, the space inside the EL display panel can be filled without a gap.
In addition, the flexible polymer composition includes a diene polymer, an olefin polymer, an acrylic polymer, a urethane polymer, a polyamide polymer, a polyester polymer, a vinyl chloride polymer, a fluorine polymer. When a polymer selected from a polymer and a silicone polymer is included, and when a specific diene polymer or olefin polymer is included, a transparent encapsulant for organic EL elements having a particularly high transparency should be used. Can do. Furthermore, when the flexible polymer composition contains a liquid substance having a kinematic viscosity in a predetermined range, it is possible to obtain a molded article with more flexibility without reducing transparency.
The transparent sealing material for organic EL elements of the present invention can be a thin-walled body. Even in such a form, it is not easily broken and easily damaged.

The present invention will be described in detail below.
The transparent sealing material for organic EL elements of the present invention is disposed on a light emitting element (organic EL element) including a substrate, an anode layer, a light emitting layer, and a cathode layer in this order, and on the light emitting surface side of the light emitting element. It is used for an EL display panel including a sealing member, is formed from a flexible polymer composition, and is disposed between the light emitting surface of the light emitting element and the sealing member.

The transparent sealing material for organic EL elements of the present invention is formed from a flexible polymer composition described below. In the present invention, the “flexible polymer composition” may include a polymer described below and other components, or may be a polymer alone. Therefore, the transparent sealing material for organic EL elements of the present invention may be formed from a flexible polymer composition containing the polymer described below and other components, or only the polymer. It may be formed from a flexible polymer composition comprising
The flexible polymer composition preferably contains a polymer that has flexibility and gives a transparent molded body. The polymer to be contained may be a resin or an elastomer (including rubber). Furthermore, you may combine resin and an elastomer. In the present invention, the flexible polymer composition is preferably an elastomer composition. Examples of the polymer contained include olefin polymers, diene polymers, acrylic polymers, urethane polymers, polyamide polymers, polyester polymers, vinyl chloride polymers, fluorine polymers, silicones. System polymers and the like. These can be used alone or in combination of two or more.

The diene polymer is preferably a polymer using a conjugated diene. For example, the diene polymer may be a conjugated diene homopolymer or copolymer, or a copolymer of a conjugated diene and another monomer. Further, the diene polymer may be used in combination of a homopolymer and a copolymer. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4, Examples include 5-diethyl-1,3-octadiene and chloroprene. Of these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are particularly preferable. In addition, the compound illustrated above can be used individually by 1 type or in combination of 2 or more types.
As other monomers in the case of a copolymer, styrene, t-butylstyrene, α-methylstyrene, α-chlorostyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p- Examples thereof include aromatic vinyl compounds such as aminostyrene; vinyl cyanide compounds such as (meth) acrylonitrile; nitrogen atom-containing vinyl compounds such as vinylpyridine. Of these, styrene and α-methylstyrene are preferred. In addition, the compound illustrated above can be used individually by 1 type or in combination of 2 or more types. When the diene polymer is a copolymer of a conjugated diene and another monomer, the conjugated diene unit is random, tapered (in which the monomer increases or decreases along the molecular chain), and part It may be a distribution selected from blocks.

Examples of the diene polymer include polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, isobutylene / isoprene polymer, acrylonitrile / butadiene copolymer, and the like. In addition, conjugated diene block copolymers such as styrene / butadiene / styrene block copolymers and styrene / isoprene / styrene block copolymers may be used. This conjugated diene block copolymer may be a copolymer of conjugated diene, or a copolymer of conjugated diene and one or more other monomers such as an aromatic vinyl compound as described above. It may be a coalescence. Therefore, examples of the block structure of this block copolymer include (AB) _mA , (BA) _m B, (ABA) _m , and (BABB) _m. . Furthermore, as the block structure of this block copolymer, (A-B) _m X, (B-A) _m X, (A-B-A) _m X, (B-A-B) _m X, etc. In this way, the polymer molecular chain may be extended or branched via the coupling agent residue X. In each general formula, “A” is a block mainly composed of conjugated diene units, “B” is a block mainly composed of other conjugated diene units or other monomer units, and m is an integer of 1 or more. The diene polymer according to the present invention may be a hydride (hydrogenated polymer) of the above polymer. In the case of using a hydride, the hydrogenation rate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The higher the hydrogenation rate, the better the light resistance, shape retention and mechanical properties when formed into a molded body.

  As the diene polymer, a hydride of a conjugated diene block polymer or a hydride of a diene polymer composed of a conjugated diene and an aromatic vinyl compound can be preferably used.

  The conjugated diene block polymer includes a butadiene polymer block (I) having a vinyl bond content of less than 25%, and a mass ratio of the conjugated diene unit (a1) and the other monomer unit (a2) [(a1 ) / (A2)] is (100 to 50) / (0 to 50) and the polymer block (II) having a vinyl bond content of 25 to 95%, each having at least one polymer in the molecule A block polymer (hereinafter referred to as “polymer (P)”) is preferred.

  In the butadiene polymer block (I), the content of vinyl bonds (1,2-vinyl bonds) is preferably less than 25%, more preferably 5 to 20%, still more preferably 7 to 19%. Therefore, the butadiene polymer block (I) becomes a crystalline block showing a structure similar to an ethylene / butene copolymer by hydrogenation. By setting the vinyl bond content within the above range, the mechanical properties and shape retention of the molded product can be improved.

The polymer block (II) may be a block composed only of a conjugated diene unit, or may be a block composed of a conjugated diene unit (a1) and another monomer unit (a2). . The mass ratio [(a1) / (a2)] of the conjugated diene unit (a1) and the other monomer unit (a2) is preferably (100 to 50) / (0 to 50), more preferably ( 100-70) / (0-30), more preferably (100-90) / (0-10). By setting it as such a range, the molded object excellent in viscoelasticity can be obtained.
In the polymer block (II), the content of vinyl bonds (1,2-vinyl bond and 3,4-vinyl bond) is preferably 25 to 95%, more preferably 25 to 90%, Preferably it is 30 to 85%.

Therefore, when the polymer block (I) is “A ¹ ” and the polymer block (II) is “B ¹ ”, the polymer (P) is (A ¹ -B ¹ ) _m1 , (A ¹ -B ¹⁾ _m2 -A ^1, it is possible to use those represented by _{^{(B 1 -A 1) m3 -B}} 1 or the like. In each general formula, m1 to m3 represent an integer of 1 or more.
Moreover, when the said polymer (P) is a copolymer which has a block more than a triblock, when it is set as a hydride, the molded object which is further excellent in shape retainability and a mechanical property can be obtained. Therefore, in the above general formula, m1 is preferably an integer of 2 or more.

  The polymer (P) may have at least one of the butadiene polymer block (I) and the polymer block (II) in the molecule, and in addition to these, other blocks such as Further, it may be a polymer having a block composed of a monomer unit other than the conjugated diene unit.

  The content ratio [(I) / (II)] of the butadiene polymer block (I) and the polymer block (II) constituting the polymer (P) is preferably (5-60) / (95- 40), more preferably (7-55) / (93-45), still more preferably (7-50) / (93-50). By setting the content ratio of each block in the above range, when it is a hydride, it is possible to obtain a molded product that is particularly excellent in shape retention and mechanical properties.

  As the diene polymer comprising the conjugated diene and the aromatic vinyl compound (hereinafter referred to as “diene polymer (Q)”), the mass ratio of the conjugated diene unit (b1) and the aromatic vinyl compound (b2) [ (B1) / (b2)] is (99-50) / (1-50), and a diene polymer having at least one polymer block in the molecule having a vinyl bond content of 65-95%. When such a diene polymer is used, a molded article having excellent viscoelasticity can be obtained.

  Further, when the diene polymer (Q) is a copolymer having at least two polymer blocks made of an aromatic vinyl compound, when it is a hydride, it is excellent in shape retention and mechanical properties. You can get a body.

In the diene polymer (Q), the content ratio of the polymer block (I) made of an aromatic vinyl compound and the polymer block (II) made of a conjugated diene and an aromatic vinyl compound [(I) / ( II)] is preferably (1-40) / (99-60), more preferably (3-30) / (97-70), and still more preferably (5-20) / (95-80). . By setting the content ratio of each block in the above range, when it is a hydride, it is possible to obtain a molded product that is particularly excellent in shape retention and mechanical properties. Therefore, as the diene polymer (Q), when the polymer block (I) is “A1” and the polymer block (II) is “B1”, B ¹ , (A ¹ -B ¹ ) _m1 , _{^{(a 1 -B 1) m2 -A}} 1, it is possible to use those represented by _{^{(B 1 -A 1) m3 -B}} 1 or the like. In each general formula, m1 to m3 represent an integer of 1 or more.

The above polymer (P) and the diene polymer even at _{^{(Q), (A 1 -B}} 1) n X, (B 1 -A 1) n X, (A 1 -B 1 -A 1) _n X, (B ¹ -A ¹ -B ¹ ) _n X and the like may be such that the polymer molecular chain is extended or branched via a coupling agent residue X. In each general formula, n represents an integer of 2 or more. In each of the above general formulas, when n is 3 or more, when a hydride is used, it is possible to obtain a molded article excellent in shape retention and hot melt viscosity / adhesiveness. As the coupling agent, 1,2-dibromoethane, methyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene-1,2,4 -Triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4-chloromethylbenzene, Bis (trichlorosilyl) ethane and the like can be mentioned.

  Hydrogenation (hydrogenation) of the polymer (P) and the diene polymer (Q) is performed on the olefinically unsaturated bond in the block. By increasing the hydrogenation rate to preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more, light resistance, shape retention, and mechanical properties when the resulting hydride is used as a molded product are obtained. Properties can be improved. The hydrogenation of the polymer (P) and the diene polymer (Q) is disclosed in JP-A-2-133406, JP-A-3-128957, JP-A-5-170844, and the like. It can be performed by a method or the like.

  The isobutylene / isoprene copolymer is generally used as “butyl rubber”. However, isobutylene and isoprene, and other monomers, for example, compounds having a polar group (hereinafter referred to as “polar group-containing compound”). It may also be a copolymer. Further, it may be a partially crosslinked copolymer of this polar group-containing compound.

  As the polar group-containing compound, a compound having at least one selected from a hydroxyl group, an epoxy group, an amino group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a nitrile group, and the like can be used. Moreover, the said partially crosslinked copolymer is normally obtained by copolymerizing the compound which has a polyfunctional unsaturated bond with these polar group containing compounds. Examples of this compound include polyvalent allyl compounds, polyvalent (meth) acrylate compounds, divinyl compounds, bismaleimide compounds, dioxime compounds, and the like.

  The butyl rubber may be a chlorinated isobutylene / isoprene copolymer, a brominated isobutylene / isoprene copolymer or the like in which an isobutylene / isoprene copolymer or the like is halogenated.

Examples of the olefin polymer include polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / α-olefin / non-conjugated diene copolymer, and the like. However, the α-olefin in the ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer is an α-olefin excluding ethylene. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 3-ethyl-1. -Pentene, 1-octene, 1-decene, 1-undecene and the like can be mentioned, and α-olefins having 3 to 12 carbon atoms are preferable, and propylene and 1-butene are particularly preferable. In addition, the alpha-olefin illustrated above can be used individually by 1 type or in combination of 2 or more types.
Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-pentene copolymer, an ethylene / 3-methyl-1-butene copolymer, Ethylene / 1-hexene copolymer, ethylene-3-methyl-1-pentene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-3-ethyl-1-pentene copolymer, ethylene Examples thereof include 1-octene copolymer, ethylene / 1-decene copolymer, and ethylene / 1-undecene copolymer. Of these, ethylene / propylene copolymers and ethylene / 1-butene copolymers are preferred. The ethylene / α-olefin copolymers exemplified above can be used singly or in combination of two or more.

In addition, as the non-conjugated diene in the case of an ethylene / α-olefin / non-conjugated diene copolymer, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1 , 9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nonadiene, dicyclopentadiene, 5-ethylidene-2-norbornene , 5-vinyl-2-norbornene, 2,5-norbornadiene and the like. These can be used alone or in combination of two or more.
Examples of the ethylene / α-olefin / non-conjugated diene copolymer include ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / dicyclohexane. Examples thereof include a pentadiene copolymer and an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer. These can be used alone or in combination of two or more.

  The ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer contain a monomer unit composed of another monomer (a) in each polymer. It may be a polymer. The other monomer (a) is preferably an unsaturated compound having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, or a nitrile group. Such unsaturated compounds can be used singly or in combination of two or more. Moreover, the usage-amount of the said unsaturated compound becomes like this. Preferably it is 0.01-10 mass% with respect to all the monomers, More preferably, it is 0.1-5 mass%.

（上記一般式（１）において、Ｒ^１は、水素原子又は炭素数１〜１０の炭化水素基であり、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立して、水素原子、炭素数１〜１０の炭化水素基又は−ＣＯＯＨであり、Ｙ^１、Ｙ^２及びＹ^３のうち少なくとも１つは−ＣＯＯＨであり、また、Ｙ^１、Ｙ^２及びＹ^３のうち２つ以上が−ＣＯＯＨである場合は、それらは互いに連結して形成された酸無水物（−ＣＯ−（Ｏ）−ＣＯ−）であってもよい。ｐは０〜２の整数であり、ｑは０〜５の整数である。） As an unsaturated compound having a carboxyl group, maleic anhydride, (meth) acrylic acid, a cyclic compound represented by the following general formula (1), or the like can be used.

In (the above general formula (1), ^{R 1} is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon ^atoms, Y 1, ^{Y 2} and ^{Y 3} are each independently a hydrogen atom, 1 to carbon atoms 10 hydrocarbon groups or —COOH, at least one of Y ¹ , Y ² and Y ³ is —COOH, and two or more of Y ¹ , Y ² and Y ³ are —COOH. In the case, they may be acid anhydrides (—CO— (O) —CO—) formed by linking each other, p is an integer of 0-2, and q is an integer of 0-5. is there.)

Examples of the cyclic compound represented by the general formula (1) include 5,6-dimethyl-5,6-dicarboxy-bicyclo [2.2.1] -2-heptene, 5,6-diethyl-5, 6-dicarboxy-bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-5,6-bis (carboxymethyl) -bicyclo [2.2.1] -2-heptene, 5,6 -Diethyl-5,6-bis (carboxymethyl) -bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5-ethyl -5-carboxy-bicyclo [2.2.1] -2-heptene, 5-carboxy-5-carboxymethyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxymethyl-bicyclo [2.2.1] -2-heptene, 5- Chill-5-carboxymethyl - bicyclo [2.2.1] -2-heptene, 8,9-dimethyl-8,9-dicarboxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8,9-diethyl-8,9-dicarboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. These can be used alone or in combination of two or more.

The amount of the cyclic compound represented by the general formula (1) used is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on all monomers. It is.
The ethylene / α-olefin copolymer or ethylene / α-olefin / non-conjugated diene copolymer obtained by copolymerizing the cyclic compound represented by the general formula (1) is preferably a random copolymer. . Moreover, the weight average molecular weight Mw of polystyrene conversion by GPC of the random copolymer obtained by copolymerization is preferably 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, More preferably, it is 5,000-700,000.

  As the olefin polymer related to the present invention, the above-exemplified ethylene / α-olefin copolymer and ethylene / α-olefin / non-conjugated diene copolymer may be used singly or in combination of two or more. Can do.

Examples of the acrylic polymer include a polymer obtained from a monomer containing an alkyl acrylate ester.
Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and n-octyl acrylate. 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, cyanomethyl acrylate, 1-cyanoethyl acrylate, 2-cyanoethyl acrylate, 1-cyanopropyl acrylate, 2-cyanopropyl acrylate, 3-cyano Propyl acrylate, 4-cyanobutyl acrylate, 6-cyanohexyl acrylate, 2-ethyl-6-cyano Hexyl acrylate, 8-cyano-octyl acrylate. These can be used alone or in combination of two or more.

The acrylic polymer may be a resin or a rubber as long as it is a copolymer of an acrylic acid alkyl ester and another monomer. For example, when the acrylic polymer is acrylic rubber, an acrylic acid alkoxyalkyl ester, an ethylenically unsaturated compound, a crosslinkable compound, or the like can be used as another monomer.
Examples of the alkoxyalkyl ester of acrylic acid include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxy Examples include propyl acrylate, 2- (n-propoxy) propyl acrylate, and 2- (n-butoxy) propyl acrylate.

  Examples of the ethylenically unsaturated compounds include compounds having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, and itaconic acid; 1,1-dihydroperfluoroethyl (meth) acrylate 1,1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, 1,1,7- Fluorine-containing acrylic acid ester such as trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth) acrylate, 1,1-dihydroperfluorodecyl (meth) acrylate; 1-hydroxypropyl (meth) acrylate, 2 -Hydro Compounds having a hydroxyl group such as cypropyl (meth) acrylate and hydroxyethyl (meth) acrylate; Monomers having a tertiary amino group such as diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate; methyl methacrylate; Methacrylic acid esters such as octyl methacrylate; Alkyl vinyl ketones such as methyl vinyl ketone; Vinyl and allyl ethers such as vinyl ethyl ether and allyl methyl ether; Vinyl aromatic compounds such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, propionic acid Examples include vinyl and alkyl fumarate.

  Examples of the crosslinkable compound include a diene compound, a (meth) acrylic acid ester having a dihydrodicyclopentadienyl group, an ethylenically unsaturated compound having an epoxy group, an active halogen-containing ethylenically unsaturated compound, and a carboxyl group. Examples thereof include an ethylenically unsaturated compound and an ethylenically unsaturated compound having an active hydrogen group.

Examples of the urethane polymer include those obtained by reacting an organic diisocyanate, a polymer diol, and a chain extender.
Examples of the organic diisocyanate include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, and 3,3′-dichloro-4,4′-diphenylmethane diisocyanate. Aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate. These organic diisocyanates can be used alone or in combination of two or more.

Examples of the polymer diol include polyester diol, polyether diol, polycarbonate diol, polyester polycarbonate diol, and polyester polyether diol.
Among these, as polyester diol, aliphatic polyester diol obtained by reaction of aliphatic diol and aliphatic dicarboxylic acid or their ester-forming derivatives, aliphatic diol and aromatic dicarboxylic acid or their ester-forming derivatives Aromatic polyester diol obtained by the above reaction. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or block copolymers thereof. Further, examples of the polycarbonate diol include polycarbonate diol obtained by reaction of an aliphatic diol and a carbonate compound, polycarbonate diol obtained by reaction of an aromatic diol such as bisphenol A and a carbonate compound, and the like. These polymer diols can be used singly or in combination of two or more.

  Conventionally known chain extenders can be used as the chain extender. The chain extender is, for example, a low molecular weight compound having a molecular weight of 300 or less having two or more active hydrogen atoms capable of reacting with an isocyanate group, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1, Diols such as 6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate, xylylene glycol; hydrazine, ethylenediamine, propylenediamine, Xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, diamines such as adipic acid dihydrazine, isophthalic acid dihydrazine, aminoethyl alcohol, aminopropyl alcohol, etc. Amino alcohols and the like. These can be used alone or in combination of two or more.

  Examples of the polyamide polymer include a copolymer composed of a hard segment made of polyamide and a soft segment made of polyester, polyether, polyester / polyether or the like.

  The polyamide segment has carbon numbers such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Segments derived from 6 or more aminocarboxylic acids; segments derived from lactams such as caprolactam and laurylactam; ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1 , 5-pentanediamine, 3-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, , 9-nonanediamine, 1,10-decanediamine, 1,11-undeca Diamine components such as diamine, 1,12-dodecanediamine, cyclohexanediamine, and glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene- Examples thereof include segments derived from dicarboxylic acid components such as 2,6-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid and diphenoxyethanedicarboxylic acid.

  Examples of the polyester segment include a segment derived from a hydroxycarboxylic acid such as ω-oxycaproic acid; a segment derived from a lactone such as ε-caprolactone; glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Dicarboxylic acid components such as acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, ethylene glycol, diethylene glycol , Triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, Examples thereof include segments derived from diol components such as 1,10-decanediol, cyclohexanedimethanol and cyclohexanediol.

  Examples of the polyether segment include segments such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyhexamethylene glycol.

  Furthermore, as the polyester polyether segment, a segment derived from the dicarboxylic acid component of the above-described polyester segment and a diol component such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, etc. Is mentioned.

  Examples of the polyester polymer include polyesters such as polybutylene terephthalate as hard segments and polyesters such as polytetramethylene glycol ether (PTMG) and PTMEG (condensate of PTMG and terephthalic acid) as soft segments. Polyether type polymer; polyester / polyester type polymer having a polyester as a hard segment and an aliphatic polyester such as polycaprolactone as a soft segment.

  Examples of the fluorine-based polymer include polymers obtained from monomers containing vinylidene fluoride. Examples of other monomers include perfluorovinyl ether, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, ethylene, propylene, and a crosslinkable compound.

Among the polymers exemplified above, diene polymers and olefin polymers are preferred as the polymer contained in the flexible polymer composition. These can form a molded article having transparency by adopting the specific structure as described above. For example, even when it is in close contact with transparent glass, plastic, etc., the transparency is lowered. Is not invited.
The polymer contained in the flexible polymer composition according to the present invention includes, in addition to the polymers exemplified above, an ethylene / vinyl acetate copolymer, a styrene polymer, a polycarbonate, a polyacetal, an epoxy polymer, and the like. These polymers can be used in any combination.

  The flexible polymer composition according to the present invention may be composed only of the above-exemplified polymers, or may contain additives and the like as long as the transparency of the molded product is not impaired. . Additives include softeners, plasticizers, lubricants, cross-linking agents, cross-linking aids, antioxidants, anti-aging agents, heat stabilizers, flame retardants, antibacterial / antifungal agents, weathering agents, UV absorbers, adhesives Examples include an imparting agent, a nucleating agent, a pigment, a dye, an organic filler, an inorganic filler, a silane coupling agent, and a titanium coupling agent.

  The transparent sealing material for organic EL elements of the present invention has not only transparency but also flexibility. In the present invention, when the polymer contained in the flexible polymer composition alone is used as a transparent sealing material for organic EL elements, and at least a part of the polymer contained in the flexible polymer composition May be cross-linked to form a transparent sealing material for organic EL elements. In the latter case, the heat resistance is further improved by having a crosslinked structure.

A crosslinking agent is used when at least a part of the polymer contained in the flexible polymer composition is crosslinked to form the transparent sealing material for an organic EL device of the present invention. For example, organic peroxides, sulfur, sulfur-containing compounds and the like can be mentioned.
Examples of the organic peroxide include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2, 5-dimethylhexane-2,5-dihydroperoxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide, Dicumyl peroxide, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) octane, 1,1-di-t-butylperoxycyclohexane, 2,5 -Dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5- Methyl-2,5-di- (t-butylperoxy) hexyne, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, bazoyl peroxide, m-toluylper Oxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-butyl Examples include peroxy-isopropyl carbonate and t-butyl peroxyallyl carbonate. These can be used alone or in combination of two or more.

  In the case where a copolymer obtained by using the cyclic compound represented by the general formula (1) is formed with a chemical cross-linked structure or a structure having a constraint point similar thereto, a metal ion, a metal compound Etc. can be used. This metal ion also means an ion of an element exemplified below and an ion of a metal compound containing this element. Examples of the metal include lithium, sodium, potassium, aluminum, magnesium, calcium, barium, cesium, strontium, rubidium, titanium, zinc, copper, iron, tin, lead, zirconium, etc. Can be mentioned. The ions containing these elements can also form a crosslinked structure between the copolymers by ionic bonding or electrostatic bonding to the functional group in the random copolymer obtained above. In addition, as a substance for making the ion of the above metal compound, each metal oxide, hydroxide, salt, complex (metal carboxylate, metal acetylacetonate, etc.), an organic compound containing a metal element (having a carbon number) Alkoxides selected from 1 to 8 and containing a metal element).

  The amount of the substance used for forming the ion is 1 equivalent of a unit formed from the cyclic compound constituting the copolymer obtained by using the cyclic compound represented by the general formula (1). , Preferably 0.01 to 50 equivalents, more preferably 0.1 to 10 equivalents, and particularly preferably 0.2 to 5 equivalents. If the amount of the substance used for forming the ions is too small, the resulting molded product has a low crosslink density or a constrained point density and tends to be inferior in mechanical strength and heat resistance. On the other hand, when the amount used is too large, the resulting molded article has a high crosslinking density or a constrained point density, and the hardness may be too high and become brittle.

Furthermore, in order to improve the miscibility of the substance for forming the above ions and the heat resistance of the resulting molded body with respect to the copolymer obtained by using the cyclic compound represented by the general formula (1), In addition to the substance for making the ions, a metal salt of an organic acid such as a carboxylic acid may be added as an activator. As the metal salt of the carboxylic acid, it is preferable to use a metal salt of a monovalent carboxylic acid having 3 to 23 carbon atoms.
Further, the metal element in the metal salt used as the activator may be selected from the metal elements constituting the substance for forming the ion, but the same kind of element as the metal element constituting the substance for forming the ion It is preferable to use a metal salt containing.

In the present invention, it is preferable that the flexible polymer composition contains a liquid substance in order to obtain a molded article with improved flexibility. As this liquid substance, in order to suppress the occurrence of dark spots, the kinematic viscosity at 40 ° C. is preferably 800 mm ² / s (1 cm ² / s = 1 St) or less, more preferably 600 mm ² / s or less, more preferably If it is 0.1-500 mm < ² > / s, the said additive component etc. can be used as it is. That is, as the liquid material, a softener, a plasticizer, a lubricant, a liquid polymer, or the like can be suitably used as long as the kinematic viscosity satisfies the above conditions.

  Examples of the softener include natural or synthetic petroleum softeners such as paraffinic oils, mineral oil softeners such as ethylene / α-olefin oligomers and gilsonite, and fatty acids such as oleic acid and ricinoleic acid. Plasticizers include various fatty acids such as phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, sebacic acid derivatives, fumaric acid derivatives, citric acid derivatives, azelaic acid derivatives, phosphoric acid derivatives, and maleic acid derivatives. Derivatives and the like. Examples of the lubricant include paraffin-based lubricant, hydrocarbon-based lubricant, and metal soap. Examples of the liquid polymer include liquid rubber such as liquid polybutadiene and liquid styrene / butadiene rubber, polyisobutylene, and silicone oil. The liquid substances exemplified above can be used singly or in combination of two or more.

  The amount of the liquid substance used is preferably 50 to 5000 parts by mass, more preferably 50 to 4000 parts by mass, and still more preferably when the total amount of the polymer contained in the flexible polymer composition is 100 parts by mass. Is 50 to 3000 parts by mass, particularly preferably 70 to 2000 parts by mass. When the amount of the liquid substance is less than 50 parts by mass, a molded article having a desired elastic modulus may not be obtained. On the other hand, when the blending amount of the liquid material exceeds 5000 parts by mass, the liquid material may ooze out from the molded body, and it may be difficult to maintain transparency.

  Using the above flexible polymer composition, injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, laminate molding, calendar molding, cast molding, coater molding, roll molding, T-die coater, T-die extrusion molding, injection A molded body having a desired shape can be obtained by a known method such as molding. The resulting molded article is excellent in transparency, and when the thickness is 0.5 mm, the haze is preferably less than 5%, more preferably 4.5% or less, and even more preferably 4% or less. Further, the total light transmittance of the obtained molded body is preferably 90% or more, more preferably 91% or more, and further preferably 92% or more. The said total light transmittance can be obtained in a wide temperature range, for example, can be obtained at -100-110 degreeC, Preferably it is -50-100 degreeC. In addition, the measuring method of a haze and a total light transmittance is mentioned later.

Moreover, the molded object obtained has the outstanding intensity | strength and a softness | flexibility. The shear storage modulus (G ′) obtained by dynamic viscoelasticity measurement under conditions of 30 ° C. and 1 Hz of the obtained molded body is preferably 1 × 10 ¹⁰ dyn / cm ² or less, more preferably 1 × 10 ^8. dyn / cm ² or less, more preferably 1 × ¹⁰ 6 dyn / cm ² or less, and usually, 1 dyn / cm ² or more. A method for measuring the shear storage modulus will be described later.
Moreover, the molded object obtained is excellent also in heat resistance. The obtained molded body preferably has flexibility, transparency, and shape retention at −80 to 110 ° C., more preferably at −50 to 100 ° C.

Since the transparent sealing material for organic EL elements of the present invention has the properties as described above, it is suitable for sealing at least the entire light emitting element and further filling the space surrounding the light emitting element.
The shape of the transparent sealing material for organic EL elements of the present invention is not limited, and can be adapted to the shape of the space. Moreover, it can also be set as the thin body which has a thin part, and can be set as a plate-shaped body, a concave-shaped body, etc. In this case, the thickness of the thinnest part is preferably 2000 μm or less, more preferably 0.1 to 2000 μm, still more preferably 0.1 to 1000 μm, particularly preferably 0.1 to 500 μm, still more preferably 0.1 to 0.1 μm. It can be set to 100 μm.

  The transparent sealing material for organic EL elements of this invention can be arrange | positioned in the predetermined position of EL display panel 1 shown in FIG. 1, for example. That is, in the embodiment shown in FIG. 1, the transparent sealing material 2 for an organic EL element includes a light emitting surface (upper part in FIG. 1) and a sealing member of the light emitting element 3 (the constituent members 31 to 34 in FIG. 1). It is explanatory drawing arrange | positioned in close contact with both so that the space part between 4 may be filled. Since the transparent sealing material for organic EL elements of the present invention is excellent in flexibility as described above, the light-emitting element can be closely adhered so as to sufficiently seal, thereby improving the visibility of images. To do.

Moreover, the transparent sealing material for organic EL elements of this invention can also be used with the form shown in FIG. That is, the light emitting surface (upper part in FIG. 2) of the light emitting element (the constituent members 31 to 34 in FIG. 1) and the sealing member 4 (the one in the shape in FIG. 2) may be referred to as “sealing cans”. ) May be arranged so as to fill the space portion between them.
The method of using the transparent sealing material for organic EL elements of the present invention is not limited to the embodiment as shown in FIGS. 1 and 2, but the above-described properties can be maintained for a long time regardless of the arrangement method. Can be maintained. That is, the transparent sealing material for organic EL elements does not deteriorate with use time, and further, the light emitting elements are less damaged and dark spots are not generated.

The sealing member (number 4 in FIGS. 1 and 2) may be any material that does not significantly impair the visibility of the display content of the display panel. As the material constituting the sealing member, for example, glass, resin, or the like can be used. Examples of the glass include borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, silica glass, low alkali glass, and soda lime glass. In addition, as the resin, polycarbonate resin, polyacetal resin, 1,2-polybutadiene resin, preferably ethylene / vinyl acetate copolymer containing 3% by mass or more of vinyl acetate unit, olefin resin such as polyethylene and polypropylene Fluorine resin such as styrene resin, acrylic resin, vinyl ester resin, saturated polyester resin, polyamide resin, polyvinylidene fluoride, urethane resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. Can be mentioned.
The shape of the sealing member may be a plate shape as shown in FIG. 1 or a lid shape covering the light emitting member and the like as shown in FIG.

Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not restrict | limited at all by these Examples. Further, “%” and “part” in the examples are based on mass unless otherwise specified.
1. Preparation of flexible polymer composition The polymer obtained by the method shown below and a liquid substance were mixed in the proportions shown in Table 1 to prepare flexible polymer compositions (i) to (vii).
1-1. Polymer (1) Hydride of butadiene block polymer (A1)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 3.9 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was carried out at 70 ° C. After completion of the reaction, the temperature of the reaction solution was set to 40 ° C., 100 g of tetrahydrofuran and 3500 g of 1,3-butadiene were added, and further adiabatic polymerization was performed. After 30 minutes, 2.7 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and the reaction solution was stirred and reacted with the polymer terminal lithium alive as a living anion for 20 minutes to obtain lithium hydride. Thereafter, the reaction solution was adjusted to 90 ° C., and 0.8 g of tetrachlorosilane was further added, followed by stirring for about 20 minutes. Next, a hydrogenation catalyst mainly composed of a titanocene compound is added to the reaction solution, a hydrogenation reaction is performed at a hydrogen gas supply pressure of 0.8 MPa for 2 hours, and when the absorption of hydrogen is completed, the reaction solution is kept at normal temperature. The pressure was returned to the reaction vessel. Thereafter, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a hydrogenated block polymer A1. The resulting hydrogenated block polymer A1 has a hydrogenation rate of 99%, a weight average molecular weight of 340,000, the vinyl bond content of the first butadiene polymer block of the polymer before hydrogenation is 15%, The vinyl bond content of the second stage butadiene polymer block was 49%.

(2) Hydride of butadiene block polymer (A2)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 4.1 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was carried out at 70 ° C. After completion of the reaction, the temperature of the reaction solution was set to 35 ° C., and 27 g of tetrahydrofuran and 3500 g of 1,3-butadiene were added for further adiabatic polymerization. After 30 minutes, 2.9 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and while the reaction solution was stirred, the polymer terminal lithium was allowed to react with living living anions for 20 minutes to obtain lithium hydride. Thereafter, the reaction solution was adjusted to 90 ° C., and 0.9 g of tetrachlorosilane was further added, followed by stirring for about 20 minutes. Next, a hydrogenation catalyst mainly composed of a titanocene compound is added to the reaction solution, a hydrogenation reaction is performed at a hydrogen gas supply pressure of 0.8 MPa for 2 hours, and when the absorption of hydrogen is completed, the reaction solution is kept at normal temperature. The pressure was returned to the reaction vessel. Thereafter, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a hydrogenated block polymer A2. The resulting hydrogenated block polymer A2 had a hydrogenation rate of 98%, a weight average molecular weight of 290,000, the vinyl bond content of the first butadiene polymer block of the polymer before hydrogenation was 14%, The vinyl bond content of the second stage butadiene polymer block was 35%.

(3) Butadiene block polymer hydride (A3)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 4.1 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was carried out at 70 ° C. After completion of the reaction, the temperature of the reaction solution was set to 5 ° C., 350 g of tetrahydrofuran and 3500 g of 1,3-butadiene were added, and further adiabatic polymerization was performed. After 30 minutes, 2.9 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and the reaction solution was stirred and reacted with the polymer terminal lithium alive as a living anion for 20 minutes to obtain lithium hydride. Thereafter, the reaction solution was adjusted to 90 ° C., and 0.9 g of tetrachlorosilane was further added, followed by stirring for about 20 minutes. Next, a hydrogenation catalyst mainly composed of a titanocene compound is added to the reaction solution, a hydrogenation reaction is performed at a hydrogen gas supply pressure of 0.8 MPa for 2 hours, and when the absorption of hydrogen is completed, the reaction solution is kept at normal temperature. The pressure was returned to the reaction vessel. Thereafter, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a hydrogenated block polymer A3. The resulting hydrogenated block polymer A3 had a hydrogenation rate of 99%, a weight average molecular weight of 300,000, a vinyl bond content in the first butadiene polymer block of the polymer before hydrogenation of 15%, The vinyl bond content of the second stage butadiene polymer block was 78%.

(4) Diene polymer hydride (A4)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 200 g of styrene and 4.1 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was carried out at 50 ° C. After completion of the reaction, the temperature of the reaction solution was set to 10 ° C., and 750 g of tetrahydrofuran, 200 g of styrene, and 4500 g of 1,3-butadiene were added, and further adiabatic polymerization was performed. After completion of the reaction, 200 g of styrene was further added to conduct adiabatic polymerization.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and the reaction solution was stirred and reacted with the polymer terminal lithium alive as a living anion for 20 minutes to obtain lithium hydride. Thereafter, the reaction solution was set to 90 ° C., a hydrogenation catalyst mainly composed of a titanocene compound was added to the reaction solution, a hydrogenation reaction was performed for 2 hours with a hydrogen gas supply pressure of 0.8 MPa, and when hydrogen absorption was completed, The reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Thereafter, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a hydrogenated block polymer A4. The resulting hydrogenated block polymer A4 had a hydrogenation rate of 99%, a weight average molecular weight of 300,000, and the vinyl bond content of the second stage polymer block of the polymer before hydrogenation was 80%.

(5) Olefin polymer (A5)
75.1 mol% of structural units derived from ethylene, 22.8 mol% of structural units derived from propylene, 1.8 mol% of structural units derived from 5-ethylidene-2-norbornene, and 8-methyl- 8-carboxytetracyclo [4.4.0.1 ^2,5 . 100 parts of a functional group-containing olefin copolymer containing 0.3 mol% of a structural unit derived from 1 ^7,10 ] -3-dodecene and having a weight average molecular weight (Mw) of 16.0 × 10 ⁴ is added to toluene 1000 1 part of zirconium (IV) butoxide (85% 1-butanol solution (manufactured by Wako Pure Chemical Industries, Ltd.)) is used with respect to 1 equivalent of the functional group in the functional group-containing olefin copolymer. ) And stirred at 80 ° C. for 1 hour, and then toluene was removed by drying to obtain a polymer A5.

1-2. Liquid substance B1; a mineral oil-based softener (trade name “PW-32”, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 30.85 mm ² / s.
B2: a mineral oil softener (trade name “PW-90” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 95.54 mm ² / s.
B3: a mineral oil softener (trade name “PW-380” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 381.6 mm ² / s.

  In addition, as the flexible polymer composition (viii) used in the comparative example, thermoplastic polyurethane (manufactured by Kuraray Co., Ltd., trade name “Clamiron U1190”) A6 was used.

2. Preparation and evaluation of transparent encapsulant for organic EL element Example 1
Using the flexible polymer composition (i), a thin plate-like body was obtained by coater molding, and this was used as a transparent sealing material for organic EL devices. This transparent sealing material for organic EL elements was evaluated by the following method. The results are shown in Table 2.
(1) Total light transmittance and haze A melted aluminosilicate thin glass sheet having a thickness of 0.7 mm (product name “Corning 1737” manufactured by Corning) is sandwiched between two thin sheets having a thickness of 0.5 mm, The total light transmittance (%) and haze (%) at 25 ° C. were measured with a total light transmittance haze measuring apparatus (manufactured by BYK-Gardner, trade name “Haze-gard plus 4725”). In addition, the transparency was evaluated as “◯” when the haze was less than 5% and excellent in transparency, and “x” when the transparency was 5% or more and inferior in transparency.
(2) Image Visibility The printed material was brought into close contact with a 500 μm thick transparent sealing material for organic EL elements, and the visibility of the printed material was visually determined. The case where it was good was “◯”, and the case where it was bad was “x”.
(3) Viscoelasticity The shear storage elastic modulus (G ′) and tan δ were measured with a dynamic viscoelasticity measuring device (“MR-500” manufactured by Rheology) under the conditions of a temperature of 30 ° C. and 1 Hz. G ′ was also measured under conditions of 70 ° C. and 1 Hz. When this shear storage elastic modulus exceeded 2 million, it was inferior in flexibility, and when it was 2 million or less, it was evaluated as excellent in flexibility.
(4) Sealing The light emitting device 3 having the anode layer 32 on the substrate 31 made of insulating transparent glass, the light emitting layer 33 on the upper surface thereof, and the cathode layer 34 on the upper surface thereof was manufactured (see FIG. 3). ). Next, the 500 μm-thick organic EL device transparent sealing material 2 produced from the flexible polymer composition (i) was placed on the upper surface of the cathode layer 34 of the light-emitting device 3. Then, insulating transparent glass was installed as the sealing member 4 on the upper surface of the transparent sealing material 2 for organic EL elements, and a model of an EL display panel was produced (see FIG. 1). At this time, when the flexible polymer composition is excellent in flexibility and the space portion generated inside the EL display panel can be brought into close contact without gaps, “◯”, the flexible polymer composition The case where the product was inferior in flexibility and could not be adhered without voids generated inside the EL display panel was designated as “x” as inferior in sealing properties.
(5) Dark Spot Next, the above model was heated at 80 ° C. for 100 hours, and then cooled to room temperature (25 ° C.). Then, the light emitting element was activated, and dark spots (non-light emitting portions) were observed. When the area of the dark spot was less than 5% of the whole, “◯” was given as being excellent in suppressing the occurrence of the dark spot, and when it was 5% or more, “X” was given as being inferior in suppressing the occurrence of the dark spot.

Examples 2-6, 8
Using the flexible polymer compositions (ii) to (vi) and (viii), a transparent sealing material for organic EL devices was obtained in the same manner as in Example 1. Each organic EL element transparent sealing material was evaluated in the same manner as in Example 1. The results are also shown in Table 2.

Examples 7 and 9
Using the flexible polymer compositions (vii) and (ix), they were heated and pressed at 200 ° C. to obtain a transparent sealing material for organic EL elements having a thickness of 500 μm. This transparent sealing material for organic EL elements was evaluated in the same manner as in Example 1. The results are also shown in Table 2.

Comparative Example 1
Evaluation was conducted in the same manner as in Example 7 except that the flexible polymer composition (x) (polymer A6) was heated and pressed at 160 ° C. to obtain a transparent sealing material for organic EL elements having a thickness of 500 μm. did. The results are also shown in Table 2.

3. About Evaluation Results From Table 2, Comparative Example 1 was inferior in transparency, so the image visibility was poor. In addition, the area of the dark spot has increased. On the other hand, each of Examples 1 to 9 was excellent in transparency and flexibility, and was able to fill the space portion generated inside the EL display panel by adhering without any gap. Further, in all of Examples 1 to 9, the image visibility was high, and the occurrence of dark spots could be sufficiently suppressed.

  The transparent sealing material for organic EL elements of the present invention can be suitably used for an organic EL display panel with high visibility. The transparent sealing material for organic EL elements of the present invention can be used for mobile phones, personal digital assistants, desktop computers, notebook computers, televisions, in-vehicle information devices, watches, and the like.

It is explanatory sectional drawing which shows EL display panel. It is explanatory sectional drawing which shows another EL display panel. It is explanatory sectional drawing which shows a light emitting element.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; EL display panel, 2; Transparent sealing material for organic EL elements, 3; Light emitting element, 31; Substrate, 32; Anode layer, 33; Light emitting layer, 34; body.

Claims (14)

  Transparent for an organic EL device used for an electroluminescence display panel comprising: a light emitting device including a substrate, an anode layer, a light emitting layer, and a cathode layer, and a sealing member disposed on the light emitting surface side of the light emitting device. A transparent encapsulant for an organic EL device, which is a sealing material, formed from a flexible polymer composition, and disposed between a light emitting surface of the light emitting device and the sealing member Wood.   The transparent sealing material for organic EL elements according to claim 1, wherein when the thickness of the transparent sealing material for organic EL elements is 0.5 mm, the total light transmittance is 90% or more.   The transparent sealing material for organic EL elements according to claim 1, wherein the flexible polymer composition is an elastomer composition.   The flexible polymer composition includes a diene polymer, an olefin polymer, an acrylic polymer, a urethane polymer, a polyamide polymer, a polyester polymer, a vinyl chloride polymer, a fluorine polymer, and The transparent sealing material for organic EL elements in any one of Claims 1 thru | or 3 containing the at least 1 sort (s) of polymer chosen from a silicone type polymer.   The diene polymer includes styrene / butadiene copolymer and hydride thereof, styrene / isoprene copolymer and hydride thereof, butadiene block copolymer and hydride thereof, styrene / butadiene / styrene block copolymer and The transparent encapsulant for organic EL devices according to claim 4, which is at least one selected from a hydride, a styrene / isoprene / styrene block copolymer and a hydride thereof.   The diene polymer includes a butadiene polymer block (I) having a vinyl bond content of less than 25%, and a mass ratio of the conjugated diene unit (a1) and the other monomer unit (a2) [(a1) / ( a2)] is (100-50) / (0-50), and each of the conjugated diene block weights having at least one polymer block (II) in the molecule having a vinyl bond content of 25-95%. The transparent encapsulant for organic EL devices according to claim 4 or 5, which is a hydride of a conjugated diene block polymer obtained by hydrogenation of the coalescence.   In the diene polymer, the mass ratio [(b1) / (b2)] of the conjugated diene unit (b1) and the aromatic vinyl compound (b2) is (99-50) / (1-50), and the vinyl bond The transparent sealing for organic EL devices according to claim 4, wherein the diene polymer having at least one polymer block in the molecule having a content of 65 to 95% is a hydrogenated diene polymer. Wood.   The transparent sealing material for an organic EL device according to claim 4, wherein the olefin polymer is at least one selected from an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer.   The ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer are selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, and a nitrile group. The transparent sealing material for organic EL elements of Claim 8 which has a functional group.   Furthermore, the transparent sealing material for organic EL elements of Claim 7 or 8 containing a metal ion and / or a metal compound.   The said flexible polymer composition is a transparent sealing material for organic EL elements in any one of Claims 1 thru | or 10 containing a liquid substance. The transparent sealing material for organic EL elements according to claim 11, wherein the liquid substance has a kinematic viscosity at 40 ° C of 800 mm ² / s or less.   The content of the liquid substance is 50 to 5000 parts by mass with respect to a total of 100 parts by mass of the polymer contained in the flexible polymer composition. Stop material.   The transparent sealing material for organic EL elements according to any one of claims 1 to 13, wherein the transparent sealing material for organic EL elements is a thin-walled body having a thinnest portion having a thickness of 0.1 to 1000 µm.

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