JP5906550B2 - Encapsulant with high barrier properties - Google Patents

Description

  The present invention relates to a sealing material composition for organic devices and a sealing material having high barrier properties for organic devices obtained by crosslinking reaction of the 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 that utilizes the principle that an organic material is laminated on an electrode in a thin film shape by vapor deposition or the like and generates power by light irradiation. By using an organic thin film, it becomes a “thin and flexible” solar cell than a conventional silicon solar cell, and is expected to be applied in a wide range. Organic thin-film solar cells are also expected as promising solar cells in the future because they can be expected to improve production efficiency and reduce process costs by using printing technology and the like. However, a device using an organic thin film has a problem of deterioration of life due to deterioration due to deterioration of device function due to moisture or oxygen gas. Therefore, a sealing material having high barrier properties is required. Here, the high barrier property means a characteristic that sufficiently suppresses intrusion of moisture, oxygen gas, and the like from the outside. As one of the methods for imparting high barrier properties to the sealing material, a detour theory (Non-Patent Document 1) is widely known. The bypass theory means that by dispersing filler in the matrix component of the sealing material, moisture and gas permeate through the filler gap (bypassing the filler) and permeate less per unit time. The theory is (Fig. 1).
As a conventional technique applying the bypass theory, for example, a photocurable resin composition that is difficult to permeate moisture, has excellent moisture resistance, and can be suitably used as a sealant for sealing an organic electroluminescence element has been proposed. (Patent Document 1). In this resin composition, a plate-like inorganic filler having an average particle diameter exceeding 5 μm is used. When a relatively large filler is used, the filler is randomly dispersed in the matrix as shown in FIG. 2, and the action of suppressing the permeation of moisture and gas is insufficient. Regarding the filler size, [0009] of Patent Document 1 describes that the moisture resistance is insufficient when the average particle diameter is less than 5 μm.

JP 2006-291072 A

From polymer-based nanocomposites to the latest developments. Industrial Research Committee, (2003)

  An object of the present invention is to provide a sealing material composition for an organic device that can sufficiently suppress entry of moisture, oxygen gas, and the like from the outside, and a high barrier property for an organic device obtained by crosslinking reaction of the composition. It is in providing a sealing material.

The present invention relates to the following inventions.
1. A sealing material composition for organic devices, wherein a plate-like inorganic compound is dispersed and contained in a matrix polymer in a stacking shape.
2. The sealing material for organic devices obtained by bridge-reacting the sealing material composition of said 1.
3. 3. The sealing material for organic devices according to 2 above, 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). In the above 2, the average particle diameter of the plate-like inorganic compound measured by the microtrack method is 0.5 μm or more and less than 5 μm, and the average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3-50. The sealing material for organic devices of description.
5. 5. The organic device sealing material according to 4 above, wherein the average value of the major axis / thickness is 1.3 to 25.
6). A sealing material obtained by sandwiching a sealing material composition for an organic device, in which a plate-like inorganic compound is dispersed and contained in a matrix polymer in a stacking manner, between two substrates facing each other in parallel, and undergoing a crosslinking reaction. In the X-ray diffraction pattern of the encapsulant film, a diffraction peak due to the plate-like inorganic compound in the encapsulant is observed, and the plate-like inorganic compound is oriented in the direction parallel to the substrate among the diffraction peaks. The non-parallel orientation ratio α obtained by using the sum of the intensities of diffraction peaks (Ip) as the denominator and the sum of the intensities of diffraction peaks (Inp) as aligned in the direction not parallel to the substrate. The sealing material for organic devices whose (Inp / Ip) is in the range of 0 to 0.1.
7). 7. The organic device sealing material according to 6 above, wherein α is in the range of 0.0001 to 0.1.
8). Any one of 6 to 7 above, wherein Ip is the sum of the intensities of peaks that can be attributed to the (00c) plane, and Inp is the sum of the intensities of the (abc) plane (either a or b is not 0) Encapsulant for organic devices.

  As a result of intensive studies, the inventors have determined that the size and shape of the plate-like inorganic compound dispersed in the matrix polymer are in a specific range, and that the plate-like inorganic compound is parallel to the substrate plane at a certain ratio or more. It has been found that when dispersed in an oriented state, it exhibits good high barrier properties in accordance with the bypass theory, and the present invention has been completed.

  In this invention, in order to obtain the sealing material which suppresses permeation | transmission of a water | moisture content, oxygen gas, etc., a plate-shaped inorganic compound and an additive as needed are mix | blended with a matrix polymer. The plate-like inorganic compound preferably has an average particle size of 0.5 μm or more and less than 5 μm as measured by the microtrack method, and the average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3 to 3. 50 is preferred. Most of the plate-like inorganic compounds were oriented in a direction parallel to the substrate plane by sandwiching the encapsulant composition obtained by mixing these blended raw materials between two parallel substrates facing each other and causing a crosslinking reaction. A sealing material dispersed in a state is obtained.

  According to the present invention, a high-barrier sealing material for organic devices excellent in the effect of suppressing permeation of moisture, oxygen gas, and the like can be obtained, and the life of the device and the reduction of the sealing width can be achieved. .

  In the present invention, the matrix polymer is not particularly limited as long as it has a good affinity with the plate-like inorganic compound, and includes epoxy resin, modified epoxy resin, polyurethane resin, polycarbonate resin, polyacrylate resin, modified olefin resin, polyester resin, and the like. It can be illustrated.

  Examples of the epoxy resin include bisphenol A type, bisphenol F type, novolac type, alicyclic type, glycidylamine type, and hydrogenated bisphenol A type. Examples of the modified epoxy resin include acrylic modified epoxy resin, polybutadiene modified epoxy resin, graft modified epoxy resin, silylated polyepoxy resin, and the like. The epoxy resin is preferably used together with a curing accelerator, a radical photopolymerization initiator and the like.

Examples of the polyurethane resin include polyol urethane resins, polyisocyanate urethane resins, polyether urethane resins, polyester urethane resins, and polycarbonate urethane resins.
Examples of the polycarbonate resin include poly-modified bisphenol carbonate resin, polydiphenyl carbonate resin, polyester carbonate resin, grafted polycarbonate resin, and polycarbonate resin chelated with metal atoms.

  Examples of polyacrylate resins include polyethylene glycol polyfunctional acrylate resins, epoxy-modified acrylate resins, urethane-modified acrylate resins, silylated acrylate resins, modified ether chain acrylate resins, and modified aliphatic acrylate resins.

  Examples of 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 various systems. Etc. can be illustrated.

  Examples of the polyester resin include unsaturated polyester resins, alkyd resins, polyethylene terephthalate, and modified polyester resins.

  Examples of the plate-like inorganic compound include clay, mica, talc, and silicate compound.

  The average particle diameter of the plate-like inorganic compound measured by the microtrack method is preferably from 0.5 μm to less than 5 μm, more preferably from 1.5 μm to 4.8 μm, particularly preferably from 2 μm to 4.5 μm. The micro track method used DLS-6000 manufactured by Otsuka Electronics. The average value of the ratio of the major axis to the thickness (major axis / thickness) is preferably 1.3 to 50, more preferably 1.5 to 25, and particularly preferably 2 to 20.

  When the average particle size of the plate-like inorganic compound is less than 0.5 μm, there is a problem that the particles are agglomerated, and when it is 5 μm or more, there is a problem that it is difficult to form a stacking shape. In addition, when the average value of the major axis / thickness is less than 1.3, the inorganic compound cannot be said to be plate-like and cannot be dispersed in a state in which the directions are aligned in the sealing material film. There is a problem that the processability is inferior.

The sealing material of the present invention is characterized by the dispersion state of the plate-like inorganic compound dispersed in the matrix polymer. Specifically, as shown in FIG. 3, most of the plate-like inorganic compounds face each other in parallel. It is characterized by being oriented in a direction parallel to the two substrates and being dispersed in a stacking shape (to be stacked).
Although FIG. 2 also shows a plate-like inorganic compound that is not parallel to the substrate, when the proportion of such a plate-like inorganic compound that is not parallel to the substrate is increased, the stacking state becomes unclear and the plate-like The gap between the inorganic compound and the plate-like inorganic compound is large or increased, and the function of sufficiently circumventing moisture and oxygen gas is impaired.

The plate-like inorganic compound oriented in the direction parallel to the substrate exhibits a peak that can be attributed to the (00c) plane (c is a natural number) from the diffraction angle θ in the X-ray diffraction pattern of the encapsulant. Here, the sum of diffraction intensities of all peaks that can be attributed to the (00c) plane is Ip, and all peaks that can be attributed to the (abc) plane (either a or b is not 0), that is, parallel to the substrate. When the sum of diffraction intensities of all peaks due to the plate-like inorganic compound is Inp, the ratio between the two (if the non-parallel orientation ratio α = Inp / Ip is 0 ≦ α ≦ 0.1, moisture or A function of detouring when oxygen gas or the like attempts to permeate through the sealing material can be exhibited.
c is a natural number, is a positive (plus) integer, does not include 0 (zero), and is usually 1 to 20, preferably 1 to 12.
When the value of α is 0, it means that all the plate-like inorganic compounds are oriented in a direction parallel to the substrate (Inp = 0).

  The dispersion state of the plate-like inorganic compound oriented in the direction parallel to the substrate does not need to be stacked so that the center line is perpendicular to the substrate as shown in FIG. The center line may be inclined to the extent that it can be said that the inorganic compounds overlap (stacked), and the states shown in FIGS. 4 and 5 may be mixed as shown in FIG.

  Ip and Inp will be described in more detail. FIG. 7 shows the X-ray diffraction pattern of the plate-like inorganic compound powder (raw material powder not blended in the sealing material), and FIG. 8 shows the X-ray diffraction pattern of the conventional sealing material (Comparative Example 1). 9 shows an X-ray diffraction pattern of the sealing material of the present invention (Example 2). In any case, talc is used as the plate-like inorganic compound, and the relationship between the diffraction angle 2θ at which the peak is recognized and the crystal plane is 2θ = 9.4 ° for the (002) plane, 18.9 ° for the (004) plane, 28.5 ° corresponds to the (006) plane and 36.3 ° corresponds to the (132) plane.

  In FIG. 7, many diffraction peaks other than the (002), (004), (006), and (132) planes are also observed, indicating that the plate-like inorganic compound is not oriented in a specific direction. In FIG. 8, the diffraction peaks other than the (00c) plane are smaller than those in FIG. 7, and it is shown that the plate-like inorganic compound is oriented in the direction parallel to the substrate. In FIG. 8, a peak corresponding to the (132) plane is recognized at a position of 2θ = 36.3 °, and this is a peak indicating the largest diffraction intensity from a crystal plane not parallel to the substrate. Yes. In FIG. 9, the peak at the position corresponding to the (132) plane has almost disappeared, and the peak intensity corresponding to the (00c) plane is measured to be larger than those in FIGS. That is, it can be judged that almost all the plate-like inorganic compounds in the sealing material of the present invention are oriented in a direction parallel to the substrate.

  In the present invention, the blending ratio of the plate-like inorganic compound is preferably 20 to 100 parts by weight, more preferably 40 to 80 parts by weight with respect to 100 parts by weight of the matrix polymer.

  If the compounding amount of the plate-like inorganic compound is less than 20 parts by weight, it is not sufficient to exert a detour effect. If it exceeds 100 parts by weight, the ratio of the matrix polymer is relatively reduced, and the matrix adhesion and the like are reduced. The properties that the polymer should exhibit are insufficient.

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

  As initiators, peroxide initiators, carboxylic acid initiators, benzophenone initiators, boron salt initiators, phosphorus initiators, triazine initiators, sulfonate initiators, imidazole initiators Etc. can be illustrated.

  As coupling agents, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, methacryltriethoxysilane , Mercaptotrimethoxysilane, epoxy-modified silane, urethane-modified silane, amine titanate coupling agent, phosphite titanate coupling agent, pyrophosphate titanate coupling agent, carboxylic acid titanate coupling agent, etc. it can.

  Examples of compatibilizers include aliphatic diene polymer compatibilizers, polyolefin compatibilizers, alicyclic diene compatibilizers, vinylidene compatibilizers, and vinyl acetate and allyl alcohol mixed compatibilizers. can do.

  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, and a polyether antifoaming agent.

  The blending ratio of these additives is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the matrix polymer. Particularly preferred is 0.2 to 15 parts by weight per 100 parts by weight of the matrix polymer.

  In the present invention, a plate-like inorganic compound and, if necessary, an additive are added to the matrix polymer, and this is mixed using a bead mill, homomixer, ball mill, three rolls, kneader or the like. Preferably, the plate-like inorganic compound can be more easily and uniformly dispersed by mixing using a ball mill, three rolls, a kneader or the like.

  After mixing the matrix polymer, the plate-like inorganic compound, and the above-described additives by the above method, further mixing a spacer such as a glass bead shape, a glass rod shape, or a resin bead shape in order to make the interval to be sealed constant. Can do. When mixing the spacers, it is preferable to use a mixing method in which a strong shearing force is not applied so that the spacers are not deformed or broken.

The encapsulant of the present invention is obtained by crosslinking reaction of the above encapsulant composition. Examples of the crosslinking reaction include a thermosetting reaction and / or a photocuring reaction. Examples of the thermosetting conditions include 70 ° C. × 2 hr + 130 ° C. × 4 hr, 80 ° C. × 2 hr, or 80 ° C. × 24 hr. Examples of the photocuring conditions include 1 to 20 J / cm ² .

It is a model figure of the detour theory of the water | moisture content and gas in the sealing material recognized widely. It is a model figure of the state in which an inorganic filler is disperse | distributing at random in a resin matrix and a water | moisture content and gas have not detoured much. It is a model figure in which the inorganic filler of the present invention is arranged in a dense stucking state. FIG. 3 is a model diagram in which the center lines of the inorganic filler of the present invention are arranged vertically in a dense stucking state. It is a model figure in which the center line of the inorganic filler of the present invention is slightly inclined and arranged in a dense stucking state. FIG. 3 is a model diagram in which the vertical and inclined center lines of the inorganic filler of the present invention are mixed and arranged in a dense stacking state. 2 shows an example of a wide-angle X-ray diffraction pattern of a plate-like inorganic compound powder. The wide-angle X-ray-diffraction pattern example of the sealing material of the comparative example 1 is shown. The wide-angle X-ray-diffraction pattern example of the sealing material of Example 2 is shown. It is the schematic of the device structure of an organic thin film solar cell.

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

The organic device used in the experiment of the present invention was manufactured by the following process.
As shown in FIG. 10, a transparent electrode material ITO (Indium Tin Oxide) thin film was previously coated on the substrate of the organic thin film solar cell and further etched to complete the electrode arrangement. On the electrode, the electrically conductive materials poly (3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS) were coated by a spin coater, and further heat-treated at 120 ° C. for 20 minutes. Furthermore, zinc phthalocyanine (ZnPc) as a P-type semiconductor material, a nanostructure layer in which zinc phthalocyanine (ZnPc) and fullerene (C60) are mixed, and fullerene (C60) as an n-type semiconductor material are applied in this order by vacuum deposition. did.
Finally, LiF and Al were applied as a cathode in this order by vacuum deposition. The deposition site was controlled by a shadow mask.
A sealing cap coated with a sealing material in a nitrogen-filled glove box and the substrate were bonded together and pressure-bonded, and finally the sealing process was completed by ultraviolet irradiation and heat treatment. A glass bead spacer was used as a device sealing spacer.

Example 1
As a matrix polymer, 100 parts by weight of bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical), 50 parts by weight of a plate-like inorganic compound (mica, average particle diameter 4.5 μm, long diameter / thickness is 25), additive ( Iodine-based photocationic polymerization initiator) 5 parts by weight and additive (long-chain alkylsilane coupling agent) 10 parts by weight are mixed and dispersed by three rolls, pressure filtration is performed, and a device sealing spacer 2 parts by weight were mixed and dispersed to obtain a sealing material composition of the present invention.
This composition is applied to the portion of the device to be sealed using a dispenser, and the cap portion is bonded together. Then, the composition is irradiated with 10 J / cm ² ultraviolet rays using an ultraviolet lamp, and further at 80 ° C. × 1 hr. The device was sealed by heat treatment.

Example 2
As a matrix polymer, 100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical), 60 parts by weight of a plate-like inorganic compound (talc, average particle diameter 3 μm, long diameter / thickness is 20), additive (antimony ( Sb) system photocationic polymerization initiator) 10 parts by weight, additive (epoxy-modified silane coupling agent) 6 parts by weight, kneaded and dispersed by a kneader, pressure filtration, and 2 parts by weight of device sealing spacer are mixed, Dispersion was performed 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 3
As a matrix polymer, 100 parts by weight of an acrylic-modified epoxy resin (phthalkid W795, manufactured by Hitachi Chemical Co., Ltd.), 55 parts by weight of a plate-like inorganic compound (silica, average particle diameter 2 μm, major axis / thickness is 5), additive (imidazole series) Curing initiator) 5 parts by weight, additive (epoxy-modified silane coupling agent) 10 parts by weight, kneaded and dispersed with a kneader, pressure filtered, mixed and dispersed 2 parts by weight of device sealing spacer, An inventive sealing material composition was obtained.
This composition is applied to a place where the device is to be sealed using a screen printing apparatus, the cap part is bonded, and then thermosetting is performed under conditions of 70 ° C. × 2 hr + 130 ° C. × 4 hr to seal the device. went.

Example 4
As a matrix polymer, 100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical), 60 parts by weight of a plate-like inorganic compound (talc, average particle diameter 2.5 μm, major axis / thickness is 15), antimony light 5 parts by weight of a cationic polymerization initiator, 8 parts by weight of an epoxy-modified silane coupling agent, kneaded and dispersed by a ball mill, subjected to pressure filtration, mixed and dispersed with 2 parts by weight of a spacer for device sealing, and sealing of the present invention A material composition was obtained. The organic device was sealed under the same conditions as in Example 1 above.

Example 5
As a matrix polymer, 100 parts by weight of an acrylate type urethane resin (V-4006, manufactured by DIC), 65 parts by weight of a plate-like inorganic compound (talc, average particle diameter 3 μm, long diameter / thickness is 2), alkylphenone-based photoradical 5 parts by weight of a polymerization initiator, 13 parts by weight of an epoxy-modified silane coupling agent, kneaded and dispersed by a kneader, subjected to pressure filtration, and mixed and dispersed by 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.

Comparative Example 1
As a matrix polymer, 100 parts by weight of a bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical), 40 parts by weight of a plate-like inorganic compound (talc, average particle diameter 10 μm, long diameter / thickness is 100), additive (antimony ( Sb) system photocationic polymerization initiator) 5 parts by weight, additive (epoxy-modified silane coupling agent) 15 parts by weight, kneaded and dispersed by a kneader, pressure filtration, mixed with 2 parts by weight of a device sealing spacer, Dispersed to obtain an encapsulant composition. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 2
As a matrix polymer, 100 parts by weight of a bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical), 55 parts by weight of a plate-like inorganic compound (mica, average particle diameter 50 μm, long diameter / thickness is 20), additive (antimony ( Sb) system photocationic polymerization initiator) 5 parts by weight, additive (epoxy-modified silane coupling agent) 20 parts by weight, kneaded and dispersed with a homomixer, pressure filtration, and 2 parts by weight of device sealing spacer mixed And dispersed to obtain an encapsulant composition. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 3
As a matrix polymer, 100 parts by weight of a bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical), 50 parts by weight of a plate-like inorganic compound (talc, average particle diameter 22.5 μm, major axis / thickness is 80), additive ( Triphenylsulfonium borate salt) 3 parts by weight, additive (epoxy-modified silane coupling agent) 10 parts by weight, kneaded and dispersed with three rolls, pressure filtration, mixing and dispersing 2 parts by weight of device sealing spacer And the sealing material composition was obtained. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 4
As a matrix polymer, 100 parts by weight of an acrylate type urethane resin (V-4006, manufactured by DIC), 60 parts by weight of a plate-like inorganic compound (talc, average particle size 30 μm, major axis / thickness is 20), additive (alkylphenone) System radical photopolymerization initiator) 5 parts by weight, additive (epoxy-modified silane coupling agent) 12 parts by weight, kneaded and dispersed by a ball mill, pressure filtration, and 2 parts by weight of device sealing spacer are mixed and dispersed. Thus, a sealing material composition was obtained. The organic device was sealed under the same conditions as in Example 1 above.

Comparative Example 5
As a matrix polymer, 100 parts by weight of bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical), 50 parts by weight of a plate-like inorganic compound (silica, average particle diameter 15 μm, long diameter / thickness is 50), additive (imidazole type) 10 parts by weight of a curing initiator), 10 parts by weight of an additive (epoxy-modified silane coupling agent), kneaded and dispersed by a ball mill, subjected to pressure filtration, mixed and dispersed with 2 parts by weight of a device sealing spacer, and sealed. A stopping material composition was obtained. The organic device was sealed under the same conditions as in Example 3 above.

Evaluation method 1
The wide-angle X-ray diffraction measurement of the cured encapsulant was performed using a Rigaku Smart lab apparatus. The calculation software is “integrated powder X-ray analysis software PDXL” manufactured by Rigaku Corporation. Ip is 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 °. The sum of the intensities of diffraction peaks oriented in a direction not parallel to the substrate appearing in the range was defined as Inp.
Evaluation method 2
Life test A durability test of the sealed organic thin-film solar cell was performed under environmental conditions of 60 ° C. and 90% RH.
While conducting the durability test, the state of the solar cell device that was shining was photographed by applying fluorescence to the organic thin-film solar cell device. The part that did not shine is called a dark spot, and the number of dark spots (or the distance that has entered from the age of the device) is the basis for the device life evaluation. Actually, the number of dark spots (or the approach distance from the device edge) of the example and the comparative example was measured, and the device deterioration rate was evaluated.
When the number of dark spots reaches 10% of the total number of elements, it is defined as the lifetime of the organic thin film solar cell, and the time taken so far is the result of the durability test.
Evaluation method 3
The outgas was measured at 110 ° C. using GC / MS (Clarus 500 GC / MS manufactured by PerkinElmer Japan Co., Ltd. and TurboMatrix 40 headspace combined). The obtained data was converted to a toluene equivalent value.
Evaluation method 4
The moisture permeability was measured using a cup method moisture measuring device. The measurement method conforms to JIS Z 0208, and the measurement conditions are 40 ° C. and 90% RH.
Evaluation method 5
When evaluating the adhesive strength, first, a sealing material composition was applied between the base material and the sealing cap material, and the device was sealed in the same manner as in Example 1.
The sealed device substrate and the sealing cap material are grasped with a jig, and subjected to a coaxial tensile test (AG-500NI manufactured by Shimadzu Corporation), and the tensile strength obtained in the test is defined as the adhesive strength.

  Table 1 shows the alignment state, characteristics, and results of each example and comparative example by X-ray diffraction.

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 a water | moisture content and oxygen, and can provide the sealing material suitable for organic device sealing. This sealing material can be applied not only to organic devices such as organic thin-film solar cells and display elements, but also to semiconductor devices with higher demands on barrier properties, and can be expected to play an active role in a wide range of fields.

Claims (10)

A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3 to 50 A plate-like inorganic compound that is sandwiched between two substrates facing each other in parallel and contains 50 to 100 parts by weight of a inorganic inorganic compound dispersed in a stacking shape is dispersed in a stacking shape. And the manufacturing method of the sealing material for organic devices contained. The method for producing a sealing material for an organic device according to claim 1, 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. 2. The method for producing a sealing material for organic devices according to claim 1, wherein the average value of the major axis / thickness is 1.3 to 25. 3. A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3 to 50 Jo inorganic compound 50-100 parts by weight a method of manufacturing a sealing member that makes scissors crosslinking reaction in the sealing material composition of two substrates in parallel facing the organic device formed by containing dispersed stacking shape In the X-ray diffraction pattern of the encapsulant film, a diffraction peak due to the plate-like inorganic compound in the encapsulant is observed, and the plate-like inorganic compound is oriented in a direction parallel to the substrate. The non-parallel orientation ratio α () obtained by using the sum of the intensity of diffraction peaks (Ip) as the denominator and the sum of the intensity of diffraction peaks aligned in the direction not parallel to the base material (Inp) as molecules. Inp / Ip) is 0 to 0. The manufacturing method of the sealing material for organic devices in the range of 1. The method for producing a sealing material for organic devices according to claim 4, wherein α is in the range of 0.0001 to 0.1. 6. Ip is the sum of the peak intensities that can be attributed to the (00c) plane, and Inp is the sum of the intensities of the (abc) plane (either a or b is not 0). The manufacturing method of the sealing material for organic devices of 1 item | term. A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3 to 50 For organic devices comprising a plate-like inorganic compound dispersed and contained in a stacking manner by sandwiching a composition containing 50 to 100 parts by weight of a inorganic compound between two substrates facing each other in parallel Manufacturing method of sealing material. A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3 to 50 A method for producing a sealing material in which a composition comprising 50 to 100 parts by weight of a dispersed inorganic compound is dispersed and sandwiched between two substrates facing each other in a cross-linking manner , and the X-ray of the sealing material film In the diffraction pattern, a diffraction peak due to the plate-like inorganic compound in the sealing material is observed, and among the diffraction peaks, the sum of the intensity of the diffraction peaks in which the plate-like inorganic compound is oriented in a direction parallel to the substrate ( Ip) is used as the denominator, and the non-parallel orientation ratio α (Inp / Ip) obtained from the sum of the intensity (Inp) of diffraction peaks oriented in a direction not parallel to the substrate is 0 to 0.00. sealant for an organic device in the first range Manufacturing method .   A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3-50 An organic device sealing material comprising 50 to 100 parts by weight of an inorganic compound dispersed and contained in a stacking shape.   A plate having an average particle diameter measured by the microtrack method in 100 parts by weight of a matrix polymer of 0.5 μm or more and less than 5 μm, and an average value of the ratio of the major axis to the thickness (major axis / thickness) is 1.3-50 In the X-ray diffraction pattern of the sealing material film, a diffraction peak due to the plate-like inorganic compound in the sealing material Among the diffraction peaks, the sum (Ip) of the intensity of the diffraction peaks in which the plate-like inorganic compound is oriented in the direction parallel to the substrate is used as the denominator, and is oriented in the direction not parallel to the substrate. An encapsulant for organic devices having a non-parallel orientation ratio α (Inp / Ip) in the range of 0 to 0.1, obtained by using the sum of diffraction peak intensities (Inp) as a molecule.

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