KR20130014375A - Sealant with high barrier property - Google Patents

Abstract

PURPOSE: An encapsulant with high barrier property is provided to sufficiently suppress penetration, thereby being capable of obtaining a sealant with high barrier property. CONSTITUTION: An encapsulant with high barrier property comprises a plate-like inorganic compound in a matrix polymer which is dispersed in a stacking shape. A sealant for an organic device is obtained by crosslinking a sealant composition. The matrix polymer is an epoxy resin, a modified epoxy resin, a polyurethane resin, a polycarbonate resin, a polyacrylate resin, a modified olefin resin, or a polyester resin. The average particle diameter of a plate-like inorganic compound measured by a microtrack method is 0.5-5 microns. The average value of the long diameter to the thickness ratio is 1.3-50. [Reference numerals] (AA,DD) Substrate; (BB) Present invention; (CC) Electrode·organic thin film

Description

Sealant with high barrier property {Sealant with high barrier property}

This invention relates to the sealing material composition for organic devices, and the sealing material which has high barrier property for organic devices obtained by crosslinking-reacting this composition.

In recent years, as a device using an organic thin film, for example, an optical sensor, an organic storage element, a display element, an organic transistor, an organic thin film solar cell, an organic semiconductor element, a communication element, and the like have attracted attention. For example, an organic thin film solar cell is an organic device using the principle that an organic substance is deposited on a thin film in an electrode by a vapor deposition method or the like, and developed by light irradiation. By using an organic thin film, it becomes a "thin and flexible" solar cell compared with the conventional silicon-type solar cell, and application in the wide range is expected. In addition, organic thin film solar cells are expected to be promising solar cells in the future from the fact that the improvement of production efficiency and the reduction of the process cost can be expected by using a printing technique or the like. However, a device using an organic thin film has a problem of deterioration of life due to deterioration due to moisture, oxygen gas, etc., and deterioration of device function. There is a demand for a sealing material having high barrier properties. Here, high barrier property means the characteristic which fully suppresses penetration | invasion of moisture, oxygen gas, etc. from the exterior. As one of the methods of providing high barrier property to a sealing material, the bypass theory (nonpatent literature 1) is widely known. Bypass theory is the theory that permeation amount per unit time becomes small because water and gas permeate through the filler gap (bypassing the filler) by dispersing the filler in the matrix component of the encapsulant (Fig. 1).

As a prior art applying the bypass theory, for example, a photocurable resin composition has been proposed which is difficult to permeate moisture, has excellent moisture resistance, and can be suitably used as an encapsulant for encapsulating an organic electroluminescent element ( Patent document 1). As for this resin composition, the plate-shaped inorganic filler whose average particle diameter exceeds 5 micrometers is used. When a relatively large filler is used, the filler is randomly dispersed in the matrix as shown in Fig. 2, and the effect of suppressing the permeation of moisture or gas is insufficient. In addition, regarding the filler size, in patent document 1, it is described that moisture resistance becomes inadequate when the average particle diameter is less than 5 micrometers.

Japanese Patent Publication No. 2006-291072

 From polymer nanocomposite foundations to the latest developments. Industrial Research Association, (2003)

The subject of this invention is providing the sealing material composition for organic devices which can fully suppress the invasion of moisture, oxygen gas, etc. from the exterior, and the sealing material which has high barrier property for organic devices obtained by crosslinking-reacting this composition. Is in.

The present invention relates to the following inventions.

1. An encapsulant composition for organic devices, wherein a plate-like inorganic compound is dispersed and contained in a stacking shape in a matrix polymer.

2. The sealing material for organic devices obtained by crosslinking-reacting the sealing material composition of 1 above.

3. Encapsulation material for organic devices as described in said 2 whose matrix polymer is an epoxy resin, a modified epoxy resin, a polyurethane resin, a polycarbonate resin, a polyacrylate resin, a modified olefin resin, and a polyester resin.

4. Encapsulation material for organic devices as described in said 2 whose average particle diameter measured by the microtrack method of a plate-shaped inorganic compound is 0.5 micrometer or more and less than 5 micrometers, and the average value of the ratio (long diameter / thickness) of long diameter and thickness is 1.3-50. .

5. The sealing material for organic devices as described in said 4 whose average value of the said long diameter / thickness is 1.3-25.

6. An encapsulant obtained by sandwiching a crosslinking reaction between two substrates facing each other in parallel with an encapsulant composition for an organic device, in which a plate-like inorganic compound is dispersed and contained in a stacking shape in a matrix polymer, and the X-ray of the encapsulant film In the diffraction pattern, a diffraction peak attributable to the plate-like inorganic compound in the encapsulant is confirmed, and the sum (Ip) of the intensity of the diffraction peaks in which the plate-like inorganic compound is oriented in a direction parallel to the substrate is used as the denominator. The sealing material for organic devices in which the non-parallel orientation rate (alpha) (Inp / Ip) obtained by making the sum (Inp) of the intensity | strengths of the diffraction peaks orientated in the direction not parallel to a base material in the range of 0-0.1.

7. Sealing material for organic devices of said 6 whose said (alpha) exists in the range of 0.0001-0.1.

8. The organic as described in 6 or 7, wherein Ip is the sum of the intensities of the peaks that can be attributed to the (00c) plane, and Inp is the sum of the intensities of the (abc) planes (either a or b is not zero). Encapsulant for the device.

As a result of earnest examination, the present inventors have found that the size and shape of the plate-shaped inorganic compound to be dispersed in the matrix polymer is in a specific range, and when the plate-shaped inorganic compound is dispersed in a state in which the plate-shaped inorganic compound is oriented parallel to the substrate plane, the bypass theory is used. The present inventors have found that perfect high-barrier properties can be achieved, and have completed the present invention.

In this invention, in order to obtain the sealing material which suppresses permeation | transmission of moisture, oxygen gas, etc., a plate-shaped inorganic compound and an additive are mix | blended with a matrix polymer as needed. It is preferable that the average particle diameter measured by the microtrack method of this plate-shaped inorganic compound is 0.5 micrometer or more and less than 5 micrometers, and the average value of the ratio (long diameter / thickness) of a long diameter and a thickness is preferable. The sealing material composition obtained by mixing these compounding materials is sandwiched between two substrates facing in parallel and crosslinked to obtain a sealing material dispersed in a state in which most of the plate-like inorganic compounds are oriented in a direction parallel to the substrate plane. .

By this invention, the high barrier sealing material for organic devices excellent in the effect which suppresses permeation | transmission of moisture, oxygen gas, etc. can be obtained, and long life of a device and reduction of the sealing width can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a model diagram of a bypass theory of water and gas in a widely recognized encapsulant.
FIG. 2 is a model diagram of a state in which an inorganic filler is randomly dispersed in a resin matrix so that moisture and gas are not bypassed.
3 is a model view of the inorganic filler of the present invention arranged in a dense stacking state.
4 is a model diagram in which the centerline of the inorganic filler of the present invention is arranged in a vertically dense stacking state.
5 is a model diagram in which the center line of the inorganic filler of the present invention is slightly inclined and arranged in a dense stacking state.
FIG. 6 is a model view in which the center line of the inorganic filler of the present invention is arranged in a dense stacking state by mixing vertical and inclined ones.
7 shows an example of a wide-angle X-ray diffraction pattern of the plate-shaped inorganic compound powder.
8 shows an example of a wide-angle X-ray diffraction pattern of the encapsulant of Comparative Example 1. FIG.
9 shows an example of a wide-angle X-ray diffraction pattern of the encapsulant of Example 2. FIG.
10 is a schematic diagram of a device structure of an organic thin film solar cell.

In the present invention, the matrix polymer may be any compound having good affinity with a plate-like inorganic compound, and includes epoxy resins, modified epoxy resins, polyurethane resins, polycarbonate resins, polyacrylate resins, modified olefin resins, polyester resins, and the like. It can be illustrated.

Examples of the epoxy resins include epoxy resins such as bisphenol A type, bisphenol F type, novolac type, aliphatic cyclic type, glycidylamine type, and hydrogenated bisphenol A type. Moreover, as a modified epoxy resin, an acrylic modified epoxy resin, a polybutadiene type modified epoxy resin, a graft modified epoxy resin, a silylated polyepoxy resin, etc. can be illustrated. It is preferable to use an epoxy resin together with a hardening accelerator, an optical radical polymerization initiator, etc.

Examples of the polyurethane resin include polyol urethane resins, polyisocyanate urethane resins, polyether urethane resins, polyester urethane resins, polycarbonate urethane resins, and the like.

Examples of the polycarbonate resins include polymodified bisphenol carbonate resins, polydiphenyl carbonate resins, polyester carbonate resins, grafted polycarbonate resins, and polycarbonate resins having chelated metal atoms.

As polyacrylate resin, polyethyleneglycol type polyfunctional acrylate resin,

Epoxy modified acrylate resins, urethane modified acrylate resins, silylated acrylate resins, modified ether chain acrylate resins, modified aliphatic acrylate resins, and the like.

Examples of the modified olefin resins include epoxy modified olefin resins, acrylate modified olefin resins, silylated olefin resins, ethylene polymers, propylene polymers, modified butadiene polymers, modified styrene polymers, and copolymers of respective systems. have.

As polyester resin, unsaturated polyester resin, an alkyd resin, polyethylene terephthalate, a modified polyester resin, etc. can be illustrated.

Clay, mica, talc, a silicate compound, etc. can be illustrated as a plate-shaped inorganic compound.

0.5 micrometer or more and less than 5 micrometers are preferable, as for the average particle diameter measured by the microtrack method of a plate-shaped inorganic compound, 1.5 micrometers-4.8 micrometers are preferable, and especially 2 micrometers-4.5 micrometers are preferable. The microtrack method used DLS-6000 made by Otsuka Denshi. 1.3-50 are preferable, as for the average value of the ratio (long diameter / thickness) of a long diameter, 1.5-25 are preferable, and 2-20 are especially preferable.

When the average particle diameter of a plate-shaped inorganic compound is less than 0.5 micrometer, there exists a problem of particle | grains secondary aggregation, and when it is 5 micrometers or more, there exists a problem which becomes difficult to become a stacking shape. In addition, when the average value of the long diameter / thickness is less than 1.3, the inorganic compound may not be called a plate and cannot be dispersed in a state in which the direction of the encapsulant film is neat, and when it exceeds 50, the workability is inferior. there is a problem.

The encapsulant of the present invention is characterized by the dispersed state of the plate-like inorganic compound dispersed in the matrix polymer, and specifically, as shown in FIG. 3, most of the plate-like inorganic compound is parallel to two substrates facing in parallel. Direction, and is dispersed in a stacking shape (to be stacked).

In addition, although the plate-shaped inorganic compound which is not parallel to a base material is shown in FIG. 2, when the ratio of the plate-shaped inorganic compound which is not parallel to this base material becomes large, a stacking state will become unclear and the gap between a plate-shaped inorganic compound and a plate-shaped inorganic compound will become large or large. The function of sufficiently bypassing moisture, oxygen gas, or the like is impaired.

The plate-shaped inorganic compound oriented in the direction parallel to the substrate shows a peak that can be attributed to the (OOc) plane (c is a natural number) from the diffraction angle θ in the X-ray diffraction pattern of the encapsulant. Here, the sum of the diffraction intensities of all peaks attributable to the (00c) plane is set to Ip, and all the peaks attributable to the (abc) plane (either a or b are not zero), that is, the substrate. When the sum of the diffraction intensities of all the peaks due to the non-parallel plate-like inorganic compound is Inp, the ratio (non-parallel orientation ratio α = Inp / Ip is 0 ≦ α ≦ 0.1 means that water, oxygen gas, etc. When trying to penetrate the encapsulant, it can exert a function of bypassing.

c is a natural number and is a positive integer (plus), does not contain 0 (zero), and is usually 1-20, preferably 1-12.

When the value of α is 0, it means that all the plate-like inorganic compounds are oriented in the direction parallel to the substrate (Inp = 0).

The dispersed state of the plate-like inorganic compound oriented in the direction parallel to the base material does not have to be stacked such that the center line is perpendicular to the base material as shown in FIG. 4, and the plate-shaped inorganic compound is overlapped (stacking shape) as shown in FIG. 5. The centerline may be inclined to such an extent that it may be possible, and the state as shown in FIG. 4 and FIG. 5 may be mixed as shown in FIG. 6.

Ip and Inp are demonstrated in more detail. Fig. 7 shows the X-ray diffraction pattern of the plate-shaped inorganic compound powder (raw material powder not blended into the encapsulant), Fig. 8 shows the X-ray diffraction pattern of the conventional encapsulant (Comparative Example 1), and Fig. 9 shows the encapsulation of the present invention. The X-ray diffraction pattern of the ash (Example 2) is shown. In all, talc is used as the plate-like inorganic compound, and the relationship between the diffraction angle 2θ and the crystal plane where the peak is confirmed is 2θ = 9.4 ° (002) plane, 18.9 ° (004) plane, 28.5 ° (006) plane , 36.3 ° corresponds to the (132) plane.

In FIG. 7, many diffraction peaks other than the said (002), (004), (006), and (132) plane were also confirmed, and it shows that the plate-shaped inorganic compound is not orientating to a specific direction. In FIG. 8, diffraction peaks other than the (00c) plane are reduced from FIG. 7, and the plate-shaped inorganic compound is oriented in the direction parallel to a base material. In Fig. 8, the peak corresponding to the (132) plane is confirmed at the position of 2θ = 36.3 °, which is the peak representing the largest diffraction intensity from the crystal plane that is not parallel to the substrate. In FIG. 9, the peak at the position corresponding to the (132) plane is almost extinguished, and the peak intensity corresponding to the (00c) plane is relatively larger than that in FIG. 7 or FIG. 8. That is, it can be judged that almost all the plate-shaped inorganic compounds in the sealing material of this invention are oriented in the direction parallel to a base material.

In this invention, 20-100 weight part is preferable with respect to 100 weight part of matrix polymers, and, as for the compounding ratio of a plate-shaped inorganic compound, 40-80 weight part is more preferable.

When the amount of the plate-shaped inorganic compound is less than 20 parts by weight, the amount of the bypass action is insufficient, and when it exceeds 100 parts by weight, the proportion of the matrix polymer is relatively low, and the properties of the matrix polymer such as substrate adhesion are insufficient. Do.

In the matrix polymer of the present invention, additives such as an initiator, a coupling agent, a compatibilizer, and an antifoaming agent can be added.

Examples of the initiator include peroxide initiators, carboxylic acid initiators, benzophenone initiators, boron salt initiators, phosphorus initiators, triazine initiators, sulfonate initiators, imidazole initiators and the like.

Examples of the coupling agent include γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and methacryl Triethoxysilane, mercaptotrimethoxysilane, epoxy modified silane, urethane modified silane, amine titanate coupling agent, phosphite titanate coupling agent, pyrroline acid titanate coupling agent, carboxylic acid titanate coupling agent Etc. can be illustrated.

Examples of the compatibilizer include aliphatic diene polymer compatibilizers, polyolefin compatibilizers, aliphatic cyclic diene compatibilizers, vinylidene compatibilizers, and compatibilizers in which vinyl acetate and allyl alcohol are mixed.

Examples of the antifoaming agent include an acrylic antifoaming agent, a low viscosity silicone antifoaming agent, an alcohol antifoaming agent, a fatty acid ester antifoaming agent, a polyether antifoaming agent, and the like.

As for the compounding ratio of these additives, 0.1-20 weight part is preferable with respect to 100 weight part of matrix polymers. Especially preferably, it is 0.2-15 weight part with respect to 100 weight part of matrix polymers.

In this invention, a plate-shaped inorganic compound and an additive are mix | blended with a matrix polymer as needed, and this is mixed using a bead mill, a homo mixer, a ball mill, a three roll, a kneader, etc. Preferably, by mixing using a ball mill, a three roll, a kneader, etc., a plate-shaped inorganic compound can be disperse | distributed more simply and uniformly.

After mixing the matrix polymer, the plate-like inorganic compound, and the above-described additives by the above method, spacers such as glass bead phase, glass rod phase, and resin bead phase may be further mixed in order to make the interval to be sealed constant. When mixing the spacers, it is preferable to use a mixing method in which no strong shearing force is applied so that the spacers are not deformed or destroyed.

The sealing material of this invention is obtained by crosslinking-reacting the said sealing material composition. As a crosslinking reaction, a thermosetting reaction and / or photocuring reaction etc. can be illustrated. The conditions of thermosetting can illustrate 70 degreeC * 2hr + 130 degreeC * 4hr, or 80 degreeC * 24hr. The conditions of photocuring can illustrate the conditions of 1-20 J / cm <2>.

Example

In the following Examples, the present invention will be described in more detail, but is not limited to these Examples.

The organic device used for the experiment of this invention was produced with the following process.

As shown in FIG. 10, the electrode arrangement was completed by previously coating a transparent electrode material ITO (Indium Tin Oxide) thin film on the board | substrate of an organic thin film solar cell, and further etching. On the electrodes, the electrically conductive materials poly (3,4-ethylenedioxythiophene) (PEDOT) and polystyrenesulfonic acid (PSS) were coated by a spin coat apparatus, and further heat treated at 120 ° C. for 20 minutes. The nanostructure layer which mixed zinc phthalocyanine (ZnPc), zinc phthalocyanine (ZnPc), and fullerene (C60) as a P-type semiconductor material, and fullerene (C60) as an n-type semiconductor material were apply | coated by vacuum deposition in this order. It was.

Finally, LiF and Al were used as vacuum electrodes in this order by vacuum evaporation. The deposition site was controlled by a shadow mask.

The sealing cap was coated with a sealing cap coated with a sealing material and a substrate in a glove box filled with nitrogen, and finally, the sealing process was completed by ultraviolet irradiation and heat treatment. In addition, a glass bead spacer was used as a spacer for sealing a device.

Example 1

As the matrix polymer, 100 parts by weight of a bisphenol A epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation), 50 parts by weight of a plate-like inorganic compound (mica, an average particle diameter of 4.5 µm, and a long diameter / thickness of 25) and an additive (iodine-based photocationic polymerization) 5 parts by weight of an initiator) and 10 parts by weight of an additive (long chain alkyl silane coupling agent) are mixed, kneaded and dispersed with a three roll, filtered under pressure, 2 parts by weight of a device sealing spacer is mixed and dispersed, and the sealing material of the present invention. A composition was obtained.

After apply | coating this composition to the place to be sealed of the said device using a dispenser, after bonding a cap part, 10 J / cm <2> ultraviolet-ray irradiation using an ultraviolet lamp and 80 degreeC * 1hr further Heat treatment was performed under the conditions of to seal the device.

Example 2

As a matrix polymer, 100 weight part of bisphenol F-type epoxy resins (jER807, Mitsubishi Chemical Corporation), 60 weight part of plate-shaped inorganic compounds (talc, average particle diameter of 3 micrometers, long diameter / thickness is 20), and an additive (antimony (Sb) type | system | group) 10 parts by weight of a photocationic polymerization initiator), 6 parts by weight of an additive (epoxy-modified silane coupling agent), kneading and dispersing by kneader, and pressure filtration to mix and disperse 2 parts by weight of a device sealing spacer, the sealing material of the present invention. A composition was obtained. The organic device was sealed under the same conditions as in Example 1 above.

Example 3

As the matrix polymer, 100 parts by weight of an acrylic modified epoxy resin (phthalicide W795, manufactured by Hitachi Kasei), 55 parts by weight of a plate-like inorganic compound (silica, an average particle diameter of 2 μm, and a long diameter / thickness of 5) and an additive (imidazole-based curing initiator) ) 5 parts by weight, 10 parts by weight of an additive (epoxy-modified silane coupling agent) and kneading and dispersing by kneader, and pressure filtration were carried out to mix and disperse 2 parts by weight of the spacer for device sealing to obtain a sealing material composition of the present invention.

This composition was apply | coated to the place to encapsulate a device using a screen printing apparatus, and after bonding a cap part, it thermosetted on the conditions of 70 degreeC * 2hr + 130 degreeC * 4hr, and sealed the device. .

Example 4

As a matrix polymer, 100 weight part of bisphenol F-type epoxy resins (jER807, Mitsubishi Chemical Corporation), 60 weight part of plate-shaped inorganic compounds (talc, average particle diameter of 2.5 micrometers, long diameter / thickness is 15), antimony photocationic polymerization initiator 5 By weight, 8 parts by weight of the epoxy-modified silane coupling agent and kneaded and dispersed by a ball mill, pressure filtration was carried out, and 2 parts by weight of the device sealing spacer were mixed and dispersed to obtain a sealing material composition of the present invention. The organic device was sealed under the same conditions as in Example 1 above.

Example 5

As a matrix polymer, 100 weight part of acrylate-type urethane resin (V-4006, DIC), 65 weight part of plate-shaped inorganic compounds (talc, 3 micrometers of average particle diameters, long diameter / thickness are 2), alkylphenone type radical photopolymerization initiator 5 weight part, 13 weight part of epoxy-modified silane coupling agents, and kneading-dispersion were carried out by kneader, pressure filtration was performed, 2 weight part of device sealing spacers were mixed and dispersed, and the sealing material composition of this invention was obtained. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 1

As a matrix polymer, 100 weight part of bisphenol F-type epoxy resins (jER807, Mitsubishi Chemical Corporation), 40 weight part of plate-shaped inorganic compounds (talc, average particle diameter of 10 micrometers, long diameter / thickness is 100), additive (antimony (Sb) type | system | group) 5 parts by weight of a photocationic polymerization initiator), 15 parts by weight of an additive (epoxy-modified silane coupling agent), and kneading and dispersing were carried out by kneader, and pressure filtration was carried out to mix and disperse 2 parts by weight of a spacer for device sealing to obtain a sealing material composition. . The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 2

As a matrix polymer, 100 weight part of bisphenol-A epoxy resin (jER828, Mitsubishi Chemical Corporation), 55 weight part of plate-shaped inorganic compounds (Mica, 50 micrometers of average particle diameters, long diameter / thickness are 20), and an additive (antimony (Sb) type | system | group) 5 parts by weight of a photocationic polymerization initiator), 20 parts by weight of an additive (epoxy-modified silane coupling agent), and a kneading and dispersing by a homo mixer, performing pressure filtration to mix and disperse 2 parts by weight of the device sealing spacer, the sealing material composition Got it. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 3

As a matrix polymer, 100 weight part of bisphenol-A epoxy resin (jER828, Mitsubishi Chemical Corporation), 50 weight part of plate-shaped inorganic compounds (talc, average particle diameter of 22.5 micrometers, long diameter / thickness is 80), and an additive (triphenylsulfonium borate Salt), 3 parts by weight, an additive (epoxy modified silane coupling agent), 10 parts by weight and kneading and dispersion by three rolls, and pressure filtration, 2 parts by weight of the device sealing spacer was mixed and dispersed to obtain a sealing material composition. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 4

As a matrix polymer, 100 weight part of acrylate type urethane resin (V-4006, DIC make), 60 weight part of plate-shaped inorganic compounds (talc, an average particle diameter of 30 micrometers, long diameter / thickness is 20), and an additive (alkyl phenone optical radical) 5 parts by weight of a polymerization initiator), 12 parts by weight of an additive (epoxy modified silane coupling agent) and a ball mill were kneaded and dispersed, and pressure filtration was carried out to mix and disperse 2 parts by weight of a device sealing spacer to obtain a sealing material composition. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 5

As a matrix polymer, 100 weight part of bisphenol F-type epoxy resins (jER807, Mitsubishi Chemical Corporation), 50 weight part of plate-shaped inorganic compounds (silica, 15 micrometers of average particle diameters, 50 diameter / thickness), and an additive (imidazole-type hardening initiator) ) 10 parts by weight, 10 parts by weight of an additive (epoxy modified silane coupling agent), and a kneading and dispersion by a ball mill, pressure filtration, 2 parts by weight of the device sealing spacer was mixed and dispersed to obtain a sealing material composition. The organic device was sealed under the same conditions as in Example 3.

Evaluation method 1

The wide-angle X-ray diffraction measurement of the hardened | cured material of the sealing material was performed by the Rigaku Smart lab apparatus. The software for calculation uses Rigaku Corporation "Comprehensive Powder X-ray Analysis Software PDXL", and the sum of the intensities of diffraction peaks oriented in the direction parallel to the substrate appearing in the range of 2θ = 3 to 90 ° is set to Ip. The sum of the intensities of the diffraction peaks oriented in the direction not parallel to the substrate appearing in the range was set to Inp.

Evaluation method 2

Life test

The durability test of the sealed organic thin film solar cell was done on the environmental conditions of 60 degreeC and 90% RH.

While performing the durability test, the fluorescent state was applied to the organic thin film solar cell device, thereby photographing the shiny state of the solar cell device. A part that is not shining is called a dark spot, and the number of dark spots (or the distance entered from the edge of the device) is the basis of the device life evaluation. Actually, the number of dark spots (or the entry distance from the device edge) of the Examples and Comparative Examples was measured to evaluate the device degradation rate.

When the number of dark spots reaches 10% of the total number of devices, it is defined as the lifetime of the organic thin film solar cell, and the number of hours spent therein is the result of the durability test.

Evaluation method 3

The measurement of outgas was performed at 110 degreeC using GC / MS (The head space of TurboMatrix 40 was combined with GC / MS of Clarus 500 by Perkin Elmer Japan.). The obtained data was converted into toluene conversion value.

Evaluation method 4

Moisture permeability measurement was performed using the cup method moisture measuring apparatus. The measuring method conforms to JIS Z 0208, and the measuring conditions are 40 degreeC and 90% RH.

Evaluation method 5

When evaluating the adhesive strength, first, the encapsulant composition was applied between the substrate and the encapsulation cap member, and the device was encapsulated in the same manner as in Example 1.

The encapsulated device base material and the encapsulation cap material are held by a jig, a coaxial tensile test (AG-500NI manufactured by Shimadzu Seisakusho) is carried out, and the tensile strength obtained in the test is taken as the adhesive strength.

Table 1 shows the orientation state, characteristics and results of X-ray diffraction of each Example and Comparative Example.

Industrial availability

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the high barrier property which is easy to suppress permeation | transmission of gas, such as water and oxygen, and can provide the sealing material suitable for the sealing of organic devices. This encapsulant can be applied not only to organic devices such as organic thin film solar cells and display elements, but also to semiconductor devices with high demands on barrier properties, and thus can be expected to be active in a wide range of fields.

Claims (12)

A sealing material composition for organic devices in which a plate-like inorganic compound is dispersed and contained in a stacking shape in a matrix polymer. The sealing material for organic devices obtained by crosslinking-reacting the sealing material composition of Claim 1. The method of claim 2,
The sealing material for organic devices whose matrix polymer is an epoxy resin, a modified epoxy resin, a polyurethane resin, a polycarbonate resin, a polyacrylate resin, a modified olefin resin, and a polyester resin. The method of claim 2,
The sealing material for organic devices whose average particle diameter measured by the microtrack method of a plate-shaped inorganic compound is 0.5 micrometer or more and less than 5 micrometers, and the average value of the ratio (long diameter / thickness) of long diameter and thickness is 1.3-50. 5. The method of claim 4,
The sealing material for organic devices whose average value of the said long diameter / thickness is 1.3-25. An encapsulant obtained by sandwiching a crosslinking reaction between two substrates facing each other in parallel with an encapsulant composition for an organic device in which a plate-like inorganic compound is dispersed and contained in a matrix polymer, wherein the X-ray diffraction pattern of the encapsulant film WHEREIN: The diffraction peak resulting from the plate-shaped inorganic compound in a sealing material is confirmed, The sum (Ip) of the intensity of the diffraction peak which the plate-shaped inorganic compound orientates in the direction parallel to a base material among the diffraction peaks is made into a denominator, The encapsulation material for organic devices in which the non-parallel orientation rate (alpha) (Inp / Ip) obtained by making sum (Inp) of the intensity | strengths of the diffraction peaks orientated in the direction not parallel to (A) is in the range of 0-0.1. The method according to claim 6,
The sealing material for organic devices in which said (alpha) exists in the range of 0.0001-0.1. 8. The method according to claim 6 or 7,
An encapsulant for an organic device, wherein Ip is the sum of the intensities of the peaks that can be attributed to the (00c) plane, and Inp is the sum of the intensities of the (abc) planes (either a or b is not zero). The sealing material for organic devices obtained by crosslinking-reacting the sealing material composition of Claim 1 by thermosetting or photocuring. In the matrix polymer, a plate-shaped inorganic compound having an average particle diameter of 1 to 5 µm, and a mean value of a long diameter and a thickness ratio (long diameter / thickness) of 1.3 to 50, dispersed and contained in a stacking shape, is contained in the matrix polymer. An encapsulant composition for an organic device. In the matrix polymer, a plate-shaped inorganic compound having an average particle diameter of 0.5 to 5 µm, and a mean value of a long diameter and a ratio (long diameter / thickness) of 1.3 to 50, dispersed and contained in a stacking shape, contained in the matrix polymer. An encapsulant obtained by crosslinking the encapsulant composition to be crosslinked, the encapsulant obtained by sandwiching between two substrates facing in parallel and crosslinking, wherein the plate-like inorganic compound in the encapsulant in the X-ray diffraction pattern of the encapsulant film. The diffraction peak resulting from is confirmed, The sum (Ip) of the intensity | strength (Ip) of the diffraction peak which the plate-shaped inorganic compound orientates in the direction parallel to a base material among the diffraction peaks, makes it a denominator, and orients it in the direction not parallel to a base material The nonparallel compounding ratio (alpha) (Inp / Ip) obtained by making sum (Inp) of the intensity | strength of a diffraction peak into a molecule | numerator exists in the range for 0-0.1. The method of claim 11,
An encapsulant for an organic device, wherein Ip is the sum of the intensities of the peaks that can be attributed to the (00c) plane, and Inp is the sum of the intensities of the (abc) planes (either a or b is not zero).

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