TW201313805A - Sealing material having barrier properties - Google Patents

Abstract

An objective of this invention is to provide a sealing material composition for organic device capable of sufficiently avoiding intrusion of water, oxygen gas or the like from the outside, and a sealing material having barrier properties for organic device obtained by cross-linking the composition. This invention provides a sealing material composition for organic device containing a plate-like inorganic compound which is stacking-dispersed in a matrix polymer and a sealing material for organic device obtained by cross-linking the sealing member composition.

Description

Packaging material with high barrier properties

The present invention relates to a package material composition for an organic device and a package material having high barrier properties for an organic device obtained by subjecting the composition to a crosslinking reaction.

In recent years, as devices using organic thin films, for example, photosensors, organic storage elements, display elements, organic transistors, organic thin film solar cells, organic semiconductor elements, and communication elements have been attracting attention. For example, an organic thin film solar cell is an organic device in which an organic substance is laminated on an electrode by vapor deposition or the like, and a principle of generating electricity by light irradiation is used. The use of an organic thin film to form a solar cell that is "thin and softer" than conventional tantalum solar cells is expected to be applied to a wider range. In addition, in view of the use of printing technology and the like, the organic thin film solar cell is expected to be a promising solar cell in terms of improvement in production efficiency and reduction in process cost. However, the apparatus using an organic thin film has a problem that the function of the apparatus is deteriorated due to deterioration of moisture, oxygen, or the like, and thus the life is lowered. Therefore, an encapsulating material having high barrier properties is required. Here, the high barrier property means that the intrusion of moisture, oxygen, or the like from the outside is sufficiently suppressed. One of the theoretical explanations for imparting high barrier properties to a sealing material is that a roundabout theory is widely known (Non-Patent Document 1). The roundabout theory is based on the theory that by allowing the filler to be dispersed in the matrix component of the encapsulating material, the amount of penetration per unit time required for the moisture and gas to bypass the gap of the filler (retracting in the filler) becomes smaller (Fig. 1 ).

As a prior art to which the circuitous theory is applied, for example, a photocurable resin composition (Patent Document 1) which is suitable for use as a water-impermeable resin composition and which is excellent in moisture resistance and excellent in moisture resistance, and which is an organic electroluminescence device The encapsulated encapsulant. As the resin composition, a sheet-like inorganic filler having an average particle diameter of more than 5 μm was used. In the case where a large filler is used, as shown in Fig. 2, the filler is randomly dispersed in the matrix, and the effect of suppressing the penetration of moisture and gas is insufficient. In addition, in the paragraph [0009] of Patent Document 1, it is described that the moisture resistance is insufficient when the average particle diameter is less than 5 μm.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1]: JP-A-2006-291072

[Non-patent literature]

[Non-Patent Document 1]: Polymer-based nanocomposites From basic to latest development. Industrial Survey, (2003)

An object of the present invention is to provide a packaging material for an organic device which can sufficiently inhibit entry of moisture, oxygen, or the like from the outside, and a packaging material having high barrier properties for an organic device obtained by crosslinking the composition.

The present invention relates to the following invention.

1. An encapsulating material composition for an organic device, which is laminated in a matrix polymer The flaky inorganic compound is dispersed in a form.

2. An encapsulating material for an organic device obtained by subjecting the encapsulating material composition of the above 1 to a crosslinking reaction.

3. The encapsulating material for an organic device according to the above 2, wherein 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.

4. The encapsulating material for an organic device according to the above 2, wherein the average particle diameter of the flake inorganic compound measured by the Microtrac method is 0.5 μm or more and less than 5 μm, and the ratio of the long diameter to the thickness (long diameter/thickness) The average value is 1.3 to 50.

5. The encapsulating material for an organic device according to the above 4, wherein an average value of the long diameter/thickness is 1.3 to 25.

6. An encapsulating material for an organic device, which is obtained by sandwiching an encapsulating material composition for an organic device in two parallel substrates and performing a crosslinking reaction, and the encapsulating material composition for the organic device is In the matrix polymer, a sheet-like inorganic compound is dispersed and dispersed, and in the X-ray diffraction pattern of the film of the encapsulating material, a diffraction peak due to the flaky inorganic compound in the encapsulating material is confirmed. Among the diffraction peaks, the non-parallel orientation ratio α (Inp/Ip) is in the range of 0 to 0.1; the non-parallel orientation ratio α (Inp/Ip) is in parallel with the substrate by the plate-like inorganic compound The sum of the intensity (Ip) of the diffraction peaks oriented in the direction is the denominator, and the sum (Inp) of the intensity of the diffraction peaks oriented in a direction not parallel to the substrate is a molecule.

7. The encapsulating material for an organic device according to the above 6, wherein the α is Range from 0.0001 to 0.1.

The encapsulating material for an organic device according to any one of the above 6 to 7, wherein Ip is a sum of the intensities of peaks attributable to the (00c) plane, and Inp is an (abc) plane (n or b is neither) The sum of the intensities of the peaks of 0).

The present inventors conducted intensive studies and found that the size and shape of the flake inorganic compound dispersed in the matrix polymer are in a specific range, and the sheet-like inorganic compound above a certain ratio is oriented in parallel with the plane of the substrate. In the case where the state is dispersed, the present invention is completed by exerting a good high barrier property in accordance with the theory of the roundabout.

In the present invention, in order to obtain an encapsulating material which suppresses penetration of gas such as moisture and oxygen, a flake inorganic compound is formulated in a matrix polymer and an additive is formulated as needed. The sheet-like inorganic compound preferably has an average particle diameter of 0.5 μm or more and less than 5 μm as measured by a Microtrac method, and an average value of a ratio of a long diameter to a thickness (long diameter/thickness) of 1.3 to 50 is good. The encapsulating material composition obtained by mixing the raw materials is sandwiched between two parallel substrates to carry out a crosslinking reaction, whereby most of the flake inorganic compounds are obtained in a direction parallel to the plane of the substrate. The encapsulating material is dispersed in an oriented state.

According to the present invention, it is possible to obtain a high barrier property encapsulating material for an organic device which is excellent in the effect of suppressing penetration of moisture and oxygen, and the like, and the life of the device can be extended or the thickness of the package can be reduced.

In the present invention, as the matrix polymer, it is only required to be inorganicized with flakes. The base polymer having good affinity of the compound may be used, and examples thereof include 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 epoxy resin may, for example, be an epoxy resin such as a bisphenol A type, a bisphenol F type, a novolac type, an alicyclic type, a glycidylamine type or a hydrogenated bisphenol A type. Further, examples of the modified epoxy resin include an acrylic modified epoxy resin, a polybutadiene modified epoxy resin, a graft modified epoxy resin, and a halogenated poly epoxy resin. The epoxy resin is preferably used together with a hardening accelerator, a photoradical polymerization initiator, and the like.

Examples of the polyurethane resin include a polyol-based amine ester resin, a polyisocyanate-based amine ester resin, a polyether-based amine ester resin, a polyester-based amine ester resin, and a polycarbonate-based amine ester resin.

The polycarbonate resin may, for example, be a poly-modified bisphenol carbonate resin, a polyphenylene carbonate resin, a polyester carbonate resin, a grafted polycarbonate resin, or a metal atom-chelated polycarbonate resin. Wait.

Examples of the polyacrylate resin include a polyethylene glycol-based polyfunctional acrylate resin, an epoxy-modified acrylate resin, an amine ester-modified acrylate resin, a halogenated acrylate resin, and a modified ether chain acrylate resin. A fatty acrylate resin or the like.

The modified olefin resin may, for example, be an epoxy-modified olefin resin, an acrylate-modified olefin resin, a halogenated olefin resin, a vinyl polymer, a propylene-based polymer, a modified butadiene-based polymer, or a modified styrene. A polymer, a copolymer of each type, etc.

As the polyester resin, an unsaturated polyester resin, an alkyd resin, or the like can be exemplified. Polyethylene terephthalate and modified polyester resin.

Examples of the sheet-like inorganic compound include clay, mica, talc, and citrate compound.

The average particle diameter of the flaky inorganic compound as measured by the Microtrac method is preferably 0.5 μm or more and less than 5 μm, more preferably 1.5 μm to 4.8 μm, particularly preferably 2 μm to 4.5 μm. The Microtrac system uses the DLS-6000 manufactured by Otsuka Electronics. The average of the ratio of the long diameter to the thickness (long diameter/thickness) is preferably from 1.3 to 50, more preferably from 1.5 to 25, particularly preferably from 2 to 20.

When the average particle diameter of the sheet-like inorganic compound is less than 0.5 μm, there is a problem that the particles are secondary aggregated, and when it is 5 μm or more, there is a problem that it is difficult to form a laminate. In addition, when the average value of the long diameter/thickness is less than 1.3, the inorganic compound cannot be said to be in the form of a sheet and cannot be uniformly dispersed in a state in which the direction of the encapsulating material film is uniform; in the average of the long diameter/thickness When the value exceeds 50, there is a problem that the workability is poor.

The encapsulating material of the present invention is characterized in that the dispersing state of the flake inorganic compound dispersed in the matrix polymer, specifically, as shown in Fig. 3, is characterized in that most of the flake inorganic compound is in The two parallel substrates are oriented in parallel directions and are dispersed in a stacked form (stacked).

In the second drawing, the sheet-like inorganic compound which is not parallel to the substrate is also shown. However, when the ratio of the sheet-like inorganic compound which is not parallel to the substrate becomes large, the laminated state becomes unclear, and the sheet-like inorganic compound and The gap of the sheet-like inorganic compound becomes large or large, and the function of sufficiently returning water or oxygen or the like is impaired.

In the sheet-like inorganic compound oriented in the direction parallel to the substrate, in the X-ray diffraction pattern of the encapsulating material, a peak at which the diffraction angle θ is attributed to the (00c) plane (c is a natural number) is exhibited. . Here, the sum of the diffraction intensities of all the peaks that can be attributed to the (00c) plane is Ip, and all the peaks that can be attributed to the (abc) plane (all of which are not 0 or not) are In the case where the sum of the diffraction intensities of all the peaks of the sheet-like inorganic compound not parallel to the substrate is Inp, the ratio of the two (non-parallel orientation ratio α=Inp/Ip) is 0≦α. ≦0.1, it can play a role in the return of moisture and oxygen to penetrate the packaging material.

c is a natural number, an integer of plus, excluding 0 (zero), usually 1 to 20, preferably 1 to 12.

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

The dispersion state of the sheet-like inorganic compound oriented in the direction parallel to the substrate does not need to be laminated so that the center line is perpendicular to the substrate as shown in Fig. 4; as shown in Fig. 5, The sheet-like inorganic compound may be referred to as an inclined center line to the extent that it overlaps (stacked); as shown in Fig. 6, the state shown in Figs. 4 and 5 may be mixed.

Further, Ip and Inp will be described in detail. Fig. 7 is a view showing an X-ray diffraction pattern of a sheet-like inorganic compound powder (a raw material powder not blended in a sealing material), and Fig. 8 is a view showing an X-ray diffraction pattern of a conventional sealing material (Comparative Example 1), Fig. 9 An X-ray diffraction pattern representing the encapsulating material (Example 2) of the present invention. All of the above use talc as the flaky inorganic compound, and it is regarded as the relationship between the diffraction angle 2 θ of the peak and the crystal plane, 2 θ = 9.4 ° corresponds to the (002) plane, 18.9° corresponds to the (004) plane, 28.5° corresponds to the (006) plane, and 36.3° corresponds to the (132) plane.

In Fig. 7, a plurality of diffraction peaks other than the above (002), (004), (006), and (132) planes were also confirmed, indicating that the sheet-like inorganic compound was not oriented in a specific direction. The diffraction peak other than the (00c) plane of Fig. 8 is smaller than that of Fig. 7, and indicates that the sheet-like inorganic compound is oriented in a direction parallel to the substrate. In Fig. 8, a peak corresponding to the (132) plane was observed at a position of 2θ = 36.3°, which is a peak derived from the maximum diffraction intensity of the crystal plane which is not parallel to the substrate. In Fig. 9, the peak at the position corresponding to the (132) plane almost disappears, and the peak intensity corresponding to the (00c) plane is relatively larger than that of Fig. 7 or Fig. 8 . That is, it can be judged that almost all of the flake inorganic compounds in the encapsulating material of the present invention are oriented in a direction parallel to the substrate.

In the present invention, the compounding ratio of the flake inorganic compound is preferably from 20 to 100 parts by weight, particularly preferably from 40 to 80 parts by weight, per 100 parts by weight of the base polymer.

When the amount of the flaky inorganic compound is less than 20 parts by weight, the amount is less than the amount of the entanglement effect; when the amount is more than 100 parts by weight, the ratio of the matrix polymer is relatively small, and the base polymer such as the substrate adhesion is used. The characteristics that should be played will be insufficient.

In the base polymer of the present invention, additives such as an initiator, a coupling agent, a compatibilizer, and an antifoaming agent may be further blended.

The initiator is a peroxide-based initiator, a carboxylic acid-based initiator, a benzophenone-based initiator, a boron-based initiator, a phosphorus-based initiator, and the like. An initiator, a sulfonate initiator, an imidazole initiator, and the like.

As the coupling agent, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, and N-phenyl-γ-aminopropyl can be exemplified. Trimethoxy decane, vinyl trimethoxy decane, triethoxy decane methacrylate, decyl trimethoxy decane, epoxy modified decane, amine ester modified decane, amine based titanate coupling agent, phosphorous acid An ester type titanate coupling agent, a pyrophosphate type titanate coupling agent, a carboxylic acid type titanate coupling agent, or the like.

As the compatibilizing agent, an aliphatic diene polymer-based compatibilizer, a polyolefin-based compatibilizer, an alicyclic diene-based compatibilizer, a vinylidene-based compatibilizer, a mixture of vinyl acetate and propylene can be exemplified. A compatibilizer for alcohols, and the like.

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

The proportion of the additives is preferably from 0.1 to 20 parts by weight based on 100 parts by weight of the base polymer. It is particularly preferably 0.2 to 15 parts by weight based on 100 parts by weight of the base polymer.

In the present invention, the flake inorganic compound is blended in the matrix polymer and the additive is formulated as needed, and is carried out using a bead mill, a homo mixer, a ball mill, a three-roll mill, a kneader or the like. mixing. It is preferred to use a ball mill, a three-roll mill, a kneader or the like for mixing, whereby the sheet-like inorganic compound can be more easily and uniformly dispersed.

After the base polymer, the sheet-like inorganic compound, and the additive are mixed by the above method, a spacer such as a glass bead, a glass rod, or a resin bead may be further mixed in order to keep the interval between the portions to be sealed constant. In the case of mixing the spacers, in order not to deform or destroy the spacers, It is preferred to use a mixing method that does not apply a strong shear force.

The encapsulating material of the present invention is obtained by subjecting the above-mentioned encapsulating material composition to a crosslinking reaction. As the crosslinking reaction, a thermosetting reaction and/or a photocuring reaction and the like can be exemplified. The conditions of the heat hardening can be exemplified by 70 ° C × 2 hours + 130 ° C × 4 hours or 80 ° C × 2 hours or 80 ° C × 24 hours. The conditions of photohardening can be exemplified by the conditions of 1 to 20 J/cm ² .

(Example)

Hereinafter, the present invention will be described in further detail by way of examples, but not limited to these examples.

The organic device used in the experiment of the present invention was produced by the following procedure.

As shown in Fig. 10, an ITO (Indium Tin Oxide) thin film of a transparent electrode material was applied to a substrate of an organic thin film solar cell, and etching was performed to complete the electrode arrangement. On the electrode, poly(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonate (PSS) of a conductive material were applied by a spin coating apparatus, followed by heat treatment at 120 ° C for 20 minutes. On the above, a nanostructure layer obtained by mixing phthalocyanine zinc (ZnPc), phthalocyanine zinc (ZnPc), and fullerene (C60) as a P-type semiconductor material by vacuum evaporation is sequentially applied, and Fullerene (C60) of n-type semiconductor material.

Finally, LiF and Al were used as the cathodes, and coating was carried out by vacuum evaporation in this order. The vapor deposition site is controlled by a shadow mask.

In a glove box filled with nitrogen, the cover coated with the encapsulating material and the substrate are bonded together for pressing, and finally the encapsulation step is completed by ultraviolet irradiation and heat treatment. Also, this example shows the use of glass beads to isolate The object serves as a spacer for device packaging.

Example 1

100 parts by weight of a bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) as a matrix polymer, 50 parts by weight of a sheet-like inorganic compound (mica, average particle diameter: 4.5 μm, long diameter/thickness: 25), and 5 parts by weight The additive (iodine-based photocationic polymerization initiator) and 10 parts by weight of the additive (long-chain alkyl decane coupling agent) are mixed, kneaded and dispersed by a three-roller, and subjected to pressure filtration to encapsulate 2 parts by weight of the device. The mixture is mixed and dispersed to obtain the encapsulating material composition of the present invention.

The composition was applied to the package to be packaged by the dispenser, and the lid portion was bonded thereto, and then irradiated with ultraviolet rays at 10 J/cm ² using an ultraviolet lamp, and then heat-treated at 80 ° C for 1 hour. The package of the device.

Example 2

100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation) and 60 parts by weight of a sheet-like inorganic compound (talc, average particle diameter 3 μm, long diameter/thickness: 20) by a kneader 10 parts by weight of an additive (Sb-based photocationic polymerization initiator) and 6 parts by weight of an additive (epoxy-modified decane coupling agent) are kneaded and dispersed, and subjected to pressure filtration to coat 2 parts by weight of the device. The separator is mixed and dispersed to obtain a package material composition of the present invention. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Example 3

100 parts by weight of acrylic acid as a matrix polymer was changed by a kneading machine Epoxy resin (PHTHALKYD W795, manufactured by Hitachi Chemical Co., Ltd.), 55 parts by weight of a sheet-like inorganic compound (silica, average particle diameter 2 μm, long diameter/thickness 5), and 5 parts by weight of an additive (imidazole hardening start) 10 parts by weight of an additive (epoxy modified decane coupling agent) was kneaded and dispersed, and subjected to pressure filtration, and 2 parts by weight of a device packaging separator was mixed and dispersed to obtain a package material composition of the present invention.

This composition was applied to a device to be packaged by a screen printing apparatus, and after bonding the lid portion, it was thermally cured under the conditions of 70 ° C × 2 hours + 130 ° C × 4 hours to encapsulate the device.

Example 4

100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation) and 60 parts by weight of a flake inorganic compound (talc, average particle diameter: 2.5 μm, long diameter/thickness: 15) by a ball mill 5 parts by weight of an oxime-based photocationic polymerization initiator and 8 parts by weight of an epoxy-modified decane coupling agent are kneaded and dispersed, and subjected to pressure filtration, and 2 parts by weight of the device-packaging separator are mixed and dispersed to obtain The inventive encapsulating material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Example 5

100 parts by weight of an acrylate-type amine ester resin (V-4006, manufactured by DIC) as a matrix polymer, and 65 parts by weight of a sheet-like inorganic compound (talc, average particle diameter: 3 μm, long diameter/thickness: 2) by a kneader 5 parts by weight of an alkylphenone-based photoradical polymerization initiator and 13 parts by weight of an epoxy-modified decane coupling agent are kneaded and dispersed, and subjected to pressure filtration to mix 2 parts by weight of the device packaging separator. Dispersion gives the encapsulating material composition of the present invention. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Comparative example 1

100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation) and 40 parts by weight of a sheet-like inorganic compound (talc, average particle diameter: 10 μm, long diameter/thickness: 100) by a kneader 5 parts by weight of an additive (Sb-based photocationic polymerization initiator) and 15 parts by weight of an additive (epoxy-modified decane coupling agent) were kneaded and dispersed, and subjected to pressure filtration to coat 2 parts by weight of the device. The separator is mixed and dispersed to obtain a package material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Comparative example 2

100 parts by weight of a bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) and 55 parts by weight of a sheet-like inorganic compound (mica, average particle diameter 50 μm, long diameter/thickness 20) as a matrix polymer by a homomixer 5 parts by weight of an additive (Sb-based photocationic polymerization initiator), 20 parts by weight of an additive (epoxy-modified decane coupling agent), kneaded and dispersed, and subjected to pressure filtration to encapsulate 2 parts by weight of the device The mixture is mixed and dispersed to obtain a package material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Comparative example 3

100 parts by weight of a bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) and 50 parts by weight of a sheet-like inorganic compound (talc, an average particle diameter of 22.5 μm, long diameter/thickness by a three-roll machine) 80), 3 parts by weight of additive (triphenylphosphonium borate), 10 parts by weight of additive (epoxy modified oxime) The alkane coupling agent was kneaded, dispersed, and subjected to pressure filtration, and 2 parts by weight of the device packaging separator was mixed and dispersed to obtain a package material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Comparative example 4

100 parts by weight of an acrylate-type amine ester resin (V-4006, manufactured by DIC) as a matrix polymer, 60 parts by weight of a sheet-like inorganic compound (talc, average particle diameter: 30 μm, long diameter/thickness: 20), by a ball mill, 5 parts by weight of an additive (alkyl phenone photopolymerization initiator) and 12 parts by weight of an additive (epoxy modified decane coupling agent) were kneaded and dispersed, and subjected to pressure filtration to package 2 parts by weight of the device. The separator is mixed and dispersed to obtain a package material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 1.

Comparative Example 5

100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation) and 50 parts by weight of a sheet-like inorganic compound (yttria, average particle diameter: 15 μm, long diameter/thickness: 50) by a ball mill 10 parts by weight of an additive (imidazole-based curing initiator) and 10 parts by weight of an additive (epoxy-modified decane coupling agent) are kneaded and dispersed, and subjected to pressure filtration to mix 2 parts by weight of the device packaging separator. Disperse to obtain a package material composition. The packaging of the organic device was carried out under the same conditions as in the above Example 3.

Evaluation method 1

The wide-angle X-ray diffraction measurement of the hardened material of the encapsulating material was carried out by a Smart Lab apparatus manufactured by Rigaku. The calculation system uses the Rigaku "Comprehensive Powder X-ray Analysis Software PDXL" and will be at 2 θ = 3 to The sum of the intensities of the diffraction peaks appearing in the direction parallel to the substrate appearing in the range of 90° is set to Ip, and the diffraction peaks appearing in the same range and oriented in a direction not parallel to the substrate The sum of the intensities is set to Inp.

Evaluation method 2 Life test

The durability test of the encapsulated organic thin film solar cell was carried out under the environmental conditions of 60 ° C and 90% RH.

The organic thin film solar cell device was irradiated with ultraviolet light while performing the durability test, and the fluorescent light-emitting state of the solar cell device was taken. The unlit area is referred to as the dark spot, and the number of dark spots (or the distance entered from the edge of the device) is used as the basis for device life evaluation. The number of dark spots (or the distance from the edge of the device) of the examples and comparative examples was actually measured, and the deterioration rate of the device was evaluated.

The time when the number of dark spots reached 10% of the total number of components was defined as the life of the organic thin film solar cell, and the number of hours taken so far was taken as a result of the durability test.

Evaluation method 3

The measurement of outgas was carried out at 110 ° C using GC/MS (GC/MS of Clarus 500 manufactured by PerkinElmer Japan Co., Ltd. and headspace of TurboMatrix 40). The obtained data was changed to a toluene equivalent value.

Evaluation method 4

The moisture permeability measurement was carried out using a cup method moisture measuring device. The measurement method is based on JIS Z 0208, and the measurement condition is 40. °C, 90% RH.

Evaluation method 5

In the evaluation of the adhesive strength, the encapsulating material composition was first applied between the substrate and the capping material, and the device was packaged by the same method as in the above-described Example 1.

The packaged device substrate and the cover material were held by a jig, and a coaxial tensile test was performed using AG-500NI (manufactured by Shimadzu Corporation), and the tensile strength obtained in the test was defined as the adhesive strength.

The orientation states, characteristics, and results obtained by X-ray diffraction of each of Examples and Comparative Examples are shown in Table 1.

(industrial availability)

According to the present invention, it is possible to provide an encapsulating material which is easy to suppress penetration of gas such as moisture and oxygen, and which is high in barrier properties and is suitable for packaging of an organic device. The packaging material can be applied not only to organic devices such as organic thin film solar cells and display elements, but also to semiconductor devices having high barrier properties. It can be expected to be active in a wider range of fields.

1 is a model diagram of a roundabout theory of moisture and gas in a widely recognized encapsulating material; and FIG. 2 is a model diagram in which an inorganic filler is randomly dispersed in a resin matrix, and water and gas are hardly detoured; 3 is a model diagram in which the inorganic filler of the present invention is arranged in a dense laminated state; and FIG. 4 is a model diagram in which the center line of the inorganic filler of the present invention is vertically arranged in a dense laminated state; FIG. 5 is a model diagram of the present invention. A model diagram in which the center line of the inorganic filler is arranged slightly obliquely in a densely stacked state; and FIG. 6 is a model diagram in which the center line of the inorganic filler of the present invention is vertically and obliquely arranged and arranged in a dense laminated state; 7 shows an example of a wide-angle X-ray diffraction pattern of a sheet-like inorganic compound powder; FIG. 8 shows an example of a wide-angle X-ray diffraction pattern of the package material of Comparative Example 1, and FIG. 9 shows a wide angle of the package material of Example 2. An example of an X-ray diffraction pattern; and FIG. 10 is a schematic view of an apparatus structure of an organic thin film solar cell.

Claims (12)

A package material composition for an organic device which is obtained by laminating a sheet-like inorganic compound in a matrix form in a matrix polymer. An encapsulating material for an organic device obtained by subjecting a sealing material composition of the first application of the patent application to a crosslinking reaction. The encapsulating material for an organic device according to the second aspect of the invention, wherein the base polymer is an epoxy resin, a modified epoxy resin, a polyurethane resin, a polycarbonate resin, a polyacrylate resin, a modified olefin resin, polyester resin. The encapsulating material for an organic device according to the second aspect of the invention, wherein the average particle diameter of the flake inorganic compound measured by the Microtrac method is 0.5 μm or more and less than 5 μm, and the ratio of the long diameter to the thickness (long diameter) The average value of / thickness) is 1.3 to 50. The encapsulating material for an organic device according to claim 4, wherein an average value of the long diameter/thickness is 1.3 to 25. An encapsulating material for an organic device, which is obtained by sandwiching an encapsulating material composition for an organic device in two parallel substrates and performing a crosslinking reaction, and the encapsulating material composition for the organic device is In the matrix polymer, a sheet-like inorganic compound is dispersed in a layered manner; wherein, in the X-ray diffraction pattern of the film of the encapsulating material, a diffraction peak due to the sheet-like inorganic compound in the encapsulating material is confirmed, Among the diffraction peaks, the non-parallel orientation ratio α (Inp/Ip) is in the range of 0 to 0.1, and the aforementioned non-parallel orientation ratio α (Inp/Ip) is oriented in a direction parallel to the substrate by the sheet-like inorganic compound. The sum of the intensities of the diffraction peaks (Ip) The sum of the intensities (Inp) of the diffraction peaks oriented in the direction parallel to the substrate is a numerator. The encapsulating material for an organic device according to claim 6, wherein the α is in the range of 0.0001 to 0.1. The encapsulating material for an organic device according to any one of claims 6 to 7, wherein Ip is a sum of the intensities of peaks attributable to the (00c) plane, and Inp is an (abc) plane (a or b is not the sum of the intensities of the peaks of 0). An encapsulating material for an organic device obtained by crosslinking a sealing material composition of the first application of the patent application by thermal curing or photohardening. An encapsulating material composition for an organic device, which is obtained by laminating and dispersing a sheet-like inorganic compound in a matrix polymer, and the average particle diameter of the flake inorganic compound measured by a Microtrac method is 1 μm or more and less than The average ratio of the long diameter to the thickness (long diameter/thickness) of 5 μm is 1.3 to 50. An encapsulating material for an organic device, which is a packaging material obtained by crosslinking a sealing material composition, and is obtained by sandwiching the encapsulating material composition on two substrates facing each other and performing a crosslinking reaction. In the material, the encapsulating material composition is obtained by laminating and dispersing a sheet-like inorganic compound in a matrix polymer, and the average particle diameter of the flake inorganic compound measured by a Microtrac method is 0.5 μm or more and less than 5 μm. The ratio of the long diameter to the thickness (long diameter/thickness) is from 1.3 to 50; wherein, in the X-ray diffraction pattern of the film of the encapsulating material, It is recognized that the diffraction peak of the sheet-like inorganic compound in the encapsulating material has a non-parallel orientation ratio α (Inp/Ip) in the range of 0 to 0.1 among the diffraction peaks; the non-parallel orientation ratio α (Inp/Ip) The sum of the intensity (Ip) of the diffraction peaks in which the sheet-like inorganic compound is oriented in the direction parallel to the substrate is the denominator, and the sum of the intensities of the diffraction peaks oriented in a direction not parallel to the substrate (Inp ) for the numerator. The encapsulating material for an organic device according to claim 11, wherein Ip is a sum of the intensities of peaks attributable to the (00c) plane, and Inp is an (abc) plane (neither a or b is 0) The sum of the peak intensities.