CN116003958A - Sealing material composition and sealing material - Google Patents
Sealing material composition and sealing material Download PDFInfo
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- CN116003958A CN116003958A CN202211135991.5A CN202211135991A CN116003958A CN 116003958 A CN116003958 A CN 116003958A CN 202211135991 A CN202211135991 A CN 202211135991A CN 116003958 A CN116003958 A CN 116003958A
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- sealing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The present invention provides a sealing material composition having excellent water vapor barrier properties under high temperature and high humidity conditions. The sealing material composition according to one embodiment of the present invention contains an epoxy resin, a sheet-like inorganic compound, and a photoinitiator, wherein the sheet-like inorganic compound has an average particle diameter of 0.5 [ mu ] m or more and less than 5 [ mu ] m as measured by a dynamic light scattering method, and an average value of 1.3 to 50 in terms of length diameter/thickness, and the sealing material composition is substantially free of a solvent for the main purpose of dissolving the photoinitiator.
Description
Technical Field
The present invention relates to a sealing material composition and a sealing material.
Background
In recent years, devices using an organic thin film, such as a photosensor, an organic memory element, a display element, an organic transistor, an organic thin film solar cell, an organic semiconductor element, and a communication element, have been attracting attention. However, electronic devices, particularly devices using organic thin films, have a problem of reduced lifetime due to intrusion of water or the like. This is because the organic element is deteriorated by moisture or the like, resulting in a reduction in device function. Therefore, a sealing material having water vapor barrier properties is required. Here, the water vapor barrier property refers to a property of suppressing intrusion of moisture from the outside.
As an example of a technique for imparting water vapor barrier properties to a sealing material, a technique described in patent document 1 is given. Patent document 1 discloses a sealing material composition for organic devices, which is obtained by dispersing a sheet-like inorganic compound in a matrix polymer in a stacked state.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-28722
Disclosure of Invention
Problems to be solved by the invention
However, in the conventional technology as described above, there is room for improvement in terms of water vapor barrier properties under high temperature and high humidity. As one aspect of the present invention, an object of the present invention is to realize a sealing material composition excellent in water vapor barrier property under high temperature and high humidity.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present invention has been completed by combining an epoxy resin, a specific-shaped sheet-like inorganic compound, and a photoinitiator, and by using the composition substantially free of a solvent for the purpose of dissolving the photoinitiator, a sealing material composition excellent in water vapor barrier properties at high temperatures and high humidity can be realized. One aspect of the present invention includes the following constitution.
1 > a sealing material composition comprising an epoxy resin, a sheet-like inorganic compound and a photoinitiator, wherein the sheet-like inorganic compound has an average particle diameter of 0.5 [ mu ] m or more and less than 5 [ mu ] m as measured by a dynamic light scattering method and an average value of 1.3 to 50 in terms of length diameter/thickness, and the sealing material composition is substantially free of a solvent for the main purpose of dissolving the photoinitiator.
< 2 > the sealing material composition according to < 1 >, wherein the content of the sheet-like inorganic compound is 20 to 45% by weight.
< 3 > the sealing material composition according to < 1 > or < 2 >, wherein the epoxy resin is an epoxy resin containing a phenol skeleton.
The sealing material composition according to any one of < 1 > to < 3 >, wherein the photoinitiator is a composition containing PF 6 － 、SbF 6 － 、(Rf) n PF 6-n － Or B (C) 6 F 5 ) 4 A sulfonium salt or iodonium salt as a counter anion, said Rf being a perfluoroalkyl group, said n being a real number from 1 to 6.
A sealing material composition according to any one of < 1 > to < 4 > further comprising a silane coupling agent having an epoxy group.
< 6 > a sealing material obtained by curing the sealing material composition according to any one of < 1 > to < 5 >.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one aspect of the present invention, a sealing material composition excellent in water vapor barrier properties at high temperature and high humidity can be provided.
Detailed Description
An embodiment of the present invention will be described below, but the present invention is not limited thereto. Unless otherwise specified in the present specification, "a to B" representing a numerical range means "a or more and B or less".
[ 1, sealing Material composition ]
The sealing material composition according to one embodiment of the present invention contains an epoxy resin, a sheet-like inorganic compound, and a photoinitiator, wherein the sheet-like inorganic compound has an average particle diameter of 0.5 [ mu ] m or more and less than 5 [ mu ] m as measured by a dynamic light scattering method, and an average value of 1.3 to 50 in terms of length diameter/thickness, and the sealing material composition is substantially free of a solvent for the main purpose of dissolving the photoinitiator. Thus, a sealing material composition having excellent water vapor barrier properties at high temperature and high humidity can be provided. In particular, as shown in examples described below, it is surprising that the sealing material composition can obtain water vapor barrier properties at high temperature and high humidity such as 85 ℃ per 85% rh. The water vapor barrier property can be evaluated by the water vapor transmission rate measured by the method described in examples. It can also be said that the water vapor transmission rate indicates the moisture permeability.
When the sealant composition is irradiated with light, the photoinitiator is decomposed to generate an acid. The acid is added to the epoxy groups in the epoxy resin. By subjecting another epoxy group to electrophilic addition reaction with the epoxy group, a cured product obtained by addition polymerization can be obtained. The resulting cured product has a low free volume due to pi-pi stacking of the epoxy resin and is excellent in water vapor barrier properties. Further, by using the sheet-like inorganic compound, the water vapor barrier property can be further improved. In addition, since the sealant composition is substantially free of a solvent for the main purpose of dissolving the photoinitiator, the solvent can be prevented from entering between pi-pi stacking of the epoxy resin to increase the free volume. It is presumed that this can achieve excellent water vapor barrier properties at high temperatures and high humidity. As a result, the free volume of the sealing material obtained by curing the sealing material composition can be suppressed from increasing, and as a result, water vapor permeation can be suppressed even at high temperature and high humidity.
In the present specification, the term "sealing material composition" means a composition for obtaining a sealing material. As described below, the sealing material can be obtained by curing the sealing material composition. The sealant composition may be an uncured composition. The sealing material composition may be referred to as a photocurable resin composition. In the present specification, the term "solvent for dissolving a photoinitiator" means a liquid (including an additive) which is not added for the purpose of improving adhesion, improving compatibility, improving defoaming property, and the like.
In the present specification, "substantially free of solvent" means that the content of the solvent for the main purpose of dissolving the photoinitiator in the sealing material composition is 0.5% by weight or less. The content of the solvent for the purpose of dissolving the photoinitiator in the sealing material composition was 0.5 wt% or less, and was confirmed by gas release detection using GC/MS. The content of the solvent in which the photoinitiator is dissolved as a main object in the sealing material composition is more preferably 0.2% by weight or less.
< 1-1, epoxy resin >
The sealing material composition contains an epoxy resin as a matrix polymer. The epoxy resin can also be said to be a cationically polymerizable compound. The epoxy resin undergoes addition polymerization by an acid generated from a photoinitiator described below, and as a result, a three-dimensional mesh structure is formed. By the pi-pi stacking property of the three-dimensional mesh structure, water vapor permeation can be suppressed. The sealing material composition may contain only the epoxy resin as a matrix polymer, or may contain a matrix polymer other than the epoxy resin, as described below, in addition to the epoxy resin.
Examples of the epoxy resin include: bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, alicyclic type epoxy resin, glycidylamine type epoxy resin, hydrogenated bisphenol A type epoxy resin, etc. In addition, modified epoxy resins may also be used. Examples of the modified epoxy resin include: acrylic modified epoxy resins, polybutadiene modified epoxy resins, graft modified epoxy resins, silylated polyepoxide resins, and the like.
Among them, the epoxy resin is preferably an epoxy resin having a phenol skeleton. Examples of the epoxy resin containing a phenol skeleton include: bisphenol F type epoxy resin, bisphenol a type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, and the like. Epoxy resins may also be used with curing accelerators.
1-2, lamellar inorganic Compound
The sealing material composition contains a sheet-like inorganic compound as a filler. Examples of the sheet-like inorganic compound include: clay, mica, talc, silicate compounds, and the like.
In one embodiment of the present invention, as the sheet-like inorganic compound, an average particle diameter measured by a dynamic light scattering method is 0.5 μm or more and less than 5 μm, and an average value of a long diameter/thickness is 1.3 to 50. The ratio of length to thickness (length/thickness) represents the aspect ratio. By using a sheet-like inorganic compound having a high aspect ratio, the moisture permeation path is lengthened, and water vapor permeation can be suppressed. That is, the sheet-like inorganic compound has a function of detouring moisture when it has invaded into the sealing material.
If the average particle diameter of the sheet-like inorganic compound is 0.5 μm or more as measured by a dynamic light scattering method, the particles are less likely to be secondarily aggregated. If the average particle diameter is less than 5. Mu.m, the particles tend to be stacked. The measurement of the average particle diameter by the dynamic light scattering method can be performed using DLS-6000 manufactured by Otsuka electronics, for example. The average particle diameter is preferably 1 μm or more and less than 5 μm, more preferably 1.5 μm to 4.8 μm, and still more preferably 2 μm to 4.5 μm.
When the average value of the ratio of the long diameter to the thickness (long diameter/thickness) of the sheet-like inorganic compound is 1.3 or more, the inorganic compound is easily dispersed in the sealing material in a state where the directions are aligned. When the average value of the long diameter/thickness is 50 or less, the workability is excellent. The average value of the major diameter/thickness is preferably 1.5 to 25, more preferably 2 to 20.
Next, a sealing material obtained by applying the sealing material composition to a substrate or applying the sealing material composition so as to sandwich two substrates and then curing the composition will be described as an example. In the sealing material, a majority of the sheet-like inorganic compound dispersed in the matrix polymer may be oriented parallel to the substrate. The sheet-like inorganic compound may be dispersed in a stacked state (in a stacked manner). When the proportion of the flaky inorganic compound oriented parallel to the substrate becomes large, the gap between the flaky inorganic compound and the flaky inorganic compound becomes small or small. Further, the stacked state becomes clear. This can exert a function of sufficiently detouring moisture or the like.
Regarding the sheet-like inorganic compound oriented parallel to the substrate, in the X-ray diffraction pattern of the sealing material, a peak attributable to the (00 c) plane (c is a natural number) from the diffraction angle θ is exhibited. Here, the sum of diffraction intensities of all peaks attributable to the (00 c) plane is set to Ip. Further, the sum of diffraction intensities of all peaks attributable to the (abc) plane (a, b) not being 0, that is, all peaks caused by the flaky inorganic compound oriented not parallel to the substrate, was set to Inp. In this case, if the ratio of the two is 0.ltoreq.α.ltoreq.0.1 (non-parallel orientation ratio α=inp/Ip), the function of detouring moisture or the like when it is to be transmitted through the sealing material can be fully exerted. c is a natural number, is a positive (plus) integer, and is free of 0 (zero), usually 1 to 20, preferably 1 to 12. The value of α being 0 means that all the flaky inorganic compounds are oriented parallel to the substrate (inp=0).
The content of the sheet-like inorganic compound in the sealing material composition is preferably 20 to 45% by weight, more preferably 25 to 40% by weight, based on 100% by weight. When the content of the sheet-like inorganic compound is 20% by weight or more, the effect of detouring the moisture can be sufficiently exerted. Further, when the content of the sheet-like inorganic compound is 45% by weight or less, the ratio of the matrix polymer to each other can be sufficiently ensured, and thus the properties to be exhibited by the matrix polymer such as the adhesion to a substrate can be sufficiently exhibited.
< 1-3, photoinitiator >
The sealant composition contains a photoinitiator as a cationic polymerization initiator. In one embodiment of the invention, the photoinitiator is, for example, a powdered solid and is free of solvents for the primary purpose of dissolving the photoinitiator. Although a small amount (about 0 to 10% by weight) of the solvent used in the production process of the photoinitiator sometimes remains in the photoinitiator, the fact that the photoinitiator is solid is not changed even in this case. The shape of the photoinitiator may be not powdery, but may be granular, block, or the like.
Examples of preferred photoinitiators are classified according to cations: sulfonium salt-based initiators, iodonium salt-based initiators, and the like. Examples of preferred photoinitiators are classified according to anions: antimony-based initiators, borate-based initiators, phosphorus-based initiators, and the like. The photoinitiator preferably contains PF 6 － 、SbF 6 － 、(Rf) n PF 6-n － Or B (C) 6 F 5 ) 4 As counter anionsSulfonium salts or iodonium salts. Here, rf is a perfluoroalkyl group, and n is a real number of 1 to 6. Examples of the cations contained in the photoinitiator include: triarylsulfonium, diaryl iodonium, and the like.
The content of the photoinitiator in the sealing material composition is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on 100% by weight. If the content of the photoinitiator is 0.5 wt% or more, the base polymer can be sufficiently crosslinked. When the content of the photoinitiator is 10% by weight or less, the ratio of the matrix polymer to each other can be sufficiently ensured, and thus the properties to be exhibited by the matrix polymer such as the adhesion to a substrate can be sufficiently exhibited. The solvent used for dissolving the photoinitiator (solvent for the purpose of dissolving the photoinitiator) is not particularly limited as long as it is an organic solvent that does not contain a functional group having high reactivity and can dissolve the photoinitiator. Examples of the organic solvent include: ketone solvents, ester solvents, ether solvents, hydrocarbon solvents, and the like. Examples of the ketone solvent include: acetone, methyl ethyl ketone, and the like, and examples of the ester solvent include: propylene carbonate, ethyl acetate, and the like.
< 1-4, other Components >
The sealant composition may contain other components in addition to the epoxy resin, the platy inorganic compound, and the photoinitiator. Examples of the other components include: matrix polymers other than epoxy resins, additives (coupling agents, compatibilizers, defoamers, etc.). The content of the other components in the sealing material composition may be 0 to 15% by weight or 0 to 10% by weight, based on 100% by weight.
Examples of the matrix polymer other than the epoxy resin include: polyurethane resins, polycarbonate resins, polyacrylate resins, modified olefin resins, polyester resins, and the like.
The sealing material composition may contain a coupling agent. This can improve the adhesion to the substrate. Examples of the coupling agent include: gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) gamma-aminopropyl trimethoxysilane, N-phenyl-gamma-aminopropyl trimethoxysilane, vinyl trimethoxysilane, methacryloyl triethoxysilane, mercapto trimethoxysilane, epoxy modified silane, urethane modified silane, amine titanate coupling agent, phosphite titanate coupling agent, pyrophosphoric titanate coupling agent, carboxylic titanate coupling agent, and the like. Among them, epoxy-modified silane, that is, a silane coupling agent having an epoxy group is preferable. Examples of the silane coupling agent having an epoxy group include: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropyl methyldimethoxysilane, 3-epoxypropoxypropyl trimethoxysilane, 3-epoxypropoxypropyl methyldiethoxysilane, 3-epoxypropoxypropyl triethoxysilane, and the like.
Examples of the compatibilizing agent include: aliphatic diene polymer compatibilizing agent, polyolefin compatibilizing agent, alicyclic diene compatibilizing agent, vinylidene compatibilizing agent, compatibilizing agent obtained by mixing vinyl acetate and allyl alcohol, etc.
As the defoaming agent, there may be mentioned: acrylic defoamers, low-viscosity silicone defoamers, alcohol defoamers, fatty acid ester defoamers, polyether defoamers, and the like.
1-5, method for producing sealing Material composition
For example, the sealing material composition can be obtained by blending a sheet-like inorganic compound, a photoinitiator, and other components as needed with a matrix polymer, and mixing them using a bead mill, a homomixer, a ball mill, a three-roll mill, a kneader, or the like. The mixing is preferably performed using a ball mill, a three-roll mill, a kneader, or the like, whereby the sheet-like inorganic compound can be dispersed more simply and uniformly. In the case where the photoinitiator is difficult to mix, the various materials may be mixed by dissolving the photoinitiator in a liquid component among components other than the photoinitiator.
< 1-6, properties of sealing Material composition >
The sealing material composition is preferably a liquid having thixotropic properties at 25 ℃. The viscosity at 25℃at a shear rate of 2 (1/s) is preferably 100 Pa.s or more. The viscosity at a shear rate of 2 (1/s) is preferably 500 Pa.s or less, more preferably 200 Pa.s or less. The thixotropic ratio calculated from the ratio of the viscosity at a shear rate of 2 (1/s) to the viscosity at a shear rate of 10 (1/s) is preferably 1.5 to 6, more preferably 1.5 to 3.
[ 2, sealing Material ]
The sealing material according to one embodiment of the present invention is obtained by curing the sealing material composition. The sealing material may be a cured product obtained from the sealing material composition. Specifically, the sealing material is obtained by subjecting the sealing material composition to a crosslinking reaction. The crosslinking reaction may be a photocuring reaction. The cumulative light amount for photocuring may be, for example, 1J/cm 2 To 20J/cm 2 . In addition, after the photocuring, for example, heat treatment is performed under the condition of 80 ℃ to 100 ℃ x 1 hour, whereby the crosslinking reaction can be completed.
The sealing material is used for sealing electronic devices such as organic devices. Since the sealing material exhibits excellent water vapor barrier properties even under high temperature and high humidity, it can suppress deterioration of the organic device. In the present specification, the organic device means a device having an organic thin film. As the organic device, there may be mentioned: organic electroluminescent devices, photosensors, organic memory elements, display elements, organic transistors, organic thin film solar cells, organic semiconductor elements, communication elements, and the like. As a more specific example of the organic device, there may be mentioned: PM-OLED, AM-OLED, etc. For example, the sealing material may be used as an end face sealing material of an organic device. The sealing material may be sandwiched between two substrates provided in the organic device.
As the sealing material, the water vapor transmission rate at 85℃and 85% RH as measured by the method described in the examples is preferably 60g/m 2 Day or less, more preferably 55g/m 2 Day or less, more preferably 50g/m 2 Day or less.
The sealing material preferably has a glass transition temperature measured by the method described in examples of 125℃or higher, more preferably 130℃or higher, and still more preferably 135℃or higher. From the viewpoint of heat resistance, the glass transition temperature of the sealing material is preferably 125 ℃ or higher.
The present invention is not limited to the above embodiments, and various modifications are possible within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.
[ example ]
Next, an embodiment of the present invention will be described.
[ evaluation method ]
< measurement of Water Vapor Transmission Rate (WVTR) of cured product >
The sealing material composition of examples or comparative examples was applied to a Teflon (registered trademark) sheet using a YD-3 doctor blade manufactured by Ji optical refiner Co., ltd, so that the film thickness was 100. Mu.m. Next, a constant temperature bath provided with a metal halide lamp manufactured by Ushio electric motor company (Mian corporation) was used, and the UV cumulative amount was 6J/cm 2 The mixture was treated at 80℃for 1 hour. Then, the cured film was peeled from the teflon (registered trademark) sheet. The obtained cured film was cut into a predetermined size, and set on a moisture permeable cup manufactured by An Tian refiner manufacturing company to which calcium chloride was added, and a special jig was fixed with a screw. The water vapor transmission rate was calculated from the weight change of this cup before placement and after 24 hours of placement at 85 ℃/85% RH.
< determination of glass transition temperature (Tg) of cured product >
A cured film having a thickness of 100 μm was produced using the sealing material composition of examples or comparative examples in the same manner as described in the above measurement of water vapor transmission rate. The obtained cured film was placed on a tensile force measuring jig of a rheometer manufactured by TA Instruments, and the temperature was raised to 0 to 200 ℃ under the conditions of a frequency of 1Hz, a strain of 0.2 wt% and a temperature raising rate of 10 ℃/min, to conduct viscoelasticity measurement. From the obtained data, the ratio of the storage modulus to the loss modulus, i.e., the maximum point of Tan δ was calculated, and the temperature was taken as the glass transition temperature.
< average particle diameter of sheet-like inorganic Compound and average value of Length/thickness >
The average particle diameter of the flake inorganic compound was measured by a dynamic light scattering method using DLS-6000 manufactured by Otsuka electronics. Further, the average value of the long diameter/thickness of the sheet-like inorganic compound was measured by using an electron microscope JST-IT 100 manufactured by japan electronics corporation. The results are as follows.
"FG-15" manufactured by Japanese talc Co., ltd: the average particle diameter was 1.5. Mu.m, and the average length/thickness was 20.
"P-8" manufactured by Japanese talc Co., ltd: the average particle diameter was 2.8. Mu.m, and the average length/thickness was 30.
"P-4" manufactured by Japanese talc Co., ltd.): the average particle diameter was 4.5. Mu.m, and the average length/thickness was 30.
"P-2" manufactured by Japanese talc Co., ltd.): the average particle diameter was 7.0. Mu.m, and the average length/thickness was 30.
[ example 1 ]
2% by weight of a triarylsulfonium salt type antimony photoinitiator (CPI-110A, powder (no solvent) manufactured by San-Apro Co.) was added to 65% by weight of a bisphenol F type epoxy resin (jER 806 manufactured by Mitsubishi chemical corporation), and the mixture was stirred at 80℃to dissolve the resin. Subsequently, 25% by weight of talc (FG-15 manufactured by Japanese talc Co., ltd.) as a lamellar inorganic compound and 8% by weight of a silane coupling agent (KBM-403 manufactured by Xinyue chemical industry Co., ltd.) as an additive were added to the bisphenol F type epoxy resin in which the photoinitiator was dissolved, and kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
[ example 2 ]
2% by weight of a triarylsulfonium salt type antimony photoinitiator (CPI-110A, powder (no solvent) manufactured by San-Apro Co.) was added to 73% by weight of a bisphenol F type epoxy resin (jER 806 manufactured by Mitsubishi chemical corporation), and the mixture was stirred at 80℃to dissolve the resin. Next, 25% by weight of talc (Japanese talc Co., ltd. "P-8") as a flaky inorganic compound was added to the bisphenol F type epoxy resin in which the photoinitiator was dissolved, and the mixture was kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
[ example 3 ]
2% by weight of a triarylsulfonium salt type antimony photoinitiator (CPI-110A, powder (no solvent) manufactured by San-Apro Co.) was added to 40% by weight of bisphenol F type epoxy resin (jER 806 manufactured by Mitsubishi chemical corporation) and 20% by weight of phenol novolak type epoxy resin (N-740 manufactured by DIC Co.) and stirred at 80℃to dissolve the components. Then, 30% by weight of talc as a lamellar inorganic compound ("P-4" manufactured by Japanese talc Co., ltd.) and 8% by weight of a silane coupling agent as an additive ("KBM-403" manufactured by Xinyue chemical industries Co., ltd.) were added to the photoinitiator-dissolved epoxy resin, and kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
[ example 4 ]
4% by weight of a triarylsulfonium salt type borate photoinitiator (CPI-310B, powder (no solvent) manufactured by San-Apro Co., ltd.) was added to 51% by weight of a bisphenol F type epoxy resin (jER 806 manufactured by Mitsubishi chemical Co., ltd.) and stirred at 80℃to dissolve the resin. Subsequently, 40% by weight of talc as a flaky inorganic compound ("P-8" manufactured by Japanese talc Co., ltd.) and 5% by weight of a silane coupling agent as an additive ("KBM-403" manufactured by Xinyue chemical industries Co., ltd.) were added to the photoinitiator-dissolved epoxy resin, and kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
[ example 5 ]
4% by weight of a triarylsulfonium salt type antimony photoinitiator (CPI-110A, powder (no solvent) manufactured by San-Apro Co.) was added to 59% by weight of a bisphenol F type epoxy resin (jER 806 manufactured by Mitsubishi chemical corporation) and 2% by weight of a silane coupling agent (KBM-403 manufactured by Xin Yue chemical industry Co.) as an additive, and the mixture was stirred at 80℃to dissolve the mixture. Next, 35% by weight of talc (FG-15 manufactured by japan talc corporation) as a flake inorganic compound was added to the photoinitiator-dissolved epoxy resin, and the mixture was kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
Comparative example 1
63% by weight of bisphenol F type epoxy resin (manufactured by Mitsubishi chemical corporation, "jER 806"), 25% by weight of talc (manufactured by Japanese talc corporation, "FG-15"), 8% by weight of silane coupling agent (manufactured by Xinyue chemical industry corporation, "KBM-403") as an additive, and 4% by weight of triarylsulfonium salt type liquid antimony type photoinitiator (manufactured by ADEKA corporation, "SP-170", containing 50% by weight of solvent) were kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration. The liquid antimony-based photoinitiator is obtained by dissolving a solid photoinitiator in a solvent having the same weight as the photoinitiator.
Comparative example 2
63% by weight of bisphenol F type epoxy resin (manufactured by Mitsubishi chemical corporation, "jER 806"), 25% by weight of talc (manufactured by Japanese talc corporation, "FG-15"), 8% by weight of silane coupling agent (manufactured by Xinyue chemical industry corporation, "KBM-403") as an additive, and a liquid photoinitiator obtained by dissolving 2% by weight of triarylsulfonium salt type antimony type photoinitiator (manufactured by San-Apro corporation, "CPI-110A", powder (without solvent)) in 2% by weight of propylene carbonate solvent (manufactured by Tokyo chemical corporation) were kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration. In comparative example 2, the proportion of the propylene carbonate solvent was 50% by weight relative to the total amount of the propylene carbonate solvent and the photoinitiator.
[ comparative example 3 ]
65% by weight of bisphenol F type epoxy resin (manufactured by Mitsubishi chemical corporation, "jER 806"), 25% by weight of talc as a lamellar inorganic compound (manufactured by Japanese talc corporation, "P-2"), 8% by weight of a silane coupling agent as an additive (manufactured by Xinyue chemical industry corporation, "KBM-403"), and 2% by weight of a triarylsulfonium salt type antimony photoinitiator (manufactured by San-Apro corporation, "CPI-110A", powder (without solvent)) were kneaded and dispersed by a three-roll mill. Then, the sealing material composition was prepared by pressure filtration.
[ evaluation results ]
The evaluation results of the examples and comparative examples are shown in table 1.
TABLE 1
First, example 1 having the same composition except for the photoinitiator was compared with comparative examples 1 and 2. As is clear from table 1, in example 1 using the solvent-free photoinitiator, the water vapor permeability was lower than in comparative example 1 using the photoinitiator containing 50 wt% of the solvent, and in comparative example 2 using the photoinitiator in a liquid state formed by dissolving the powdery photoinitiator with the solvent (the content of the solvent in the liquid photoinitiator: 50 wt%), and therefore the water vapor barrier property was improved at high temperature and high humidity. In addition, the glass transition temperature of example 1 was increased as compared with comparative examples 1 and 2. The same tendency was found in the comparison of examples 4 and 5 with comparative examples 1 and 2. It can be considered that: since example 2 was not added with the silane coupling agent and example 3 was added with the phenol novolac type epoxy resin, the glass transition temperature was further increased and the water vapor transmission rate was further decreased as compared with example 1. In addition, regarding comparative example 3, it can be considered that: since the average particle diameter of the inorganic compound used was 5.0 μm or more, the water vapor permeability was increased as compared with example 1.
[ Industrial Applicability ]
One aspect of the present invention is useful for sealing materials requiring water vapor barrier properties at high temperatures and high humidity.
Claims (6)
1. A sealing material composition comprising an epoxy resin, a sheet-like inorganic compound and a photoinitiator,
regarding the sheet-like inorganic compound, an average particle diameter measured by a dynamic light scattering method is 0.5 μm or more and less than 5 μm, an average value of a long diameter/thickness is 1.3 to 50,
the sealant composition is substantially free of solvents that primarily serve the purpose of dissolving the photoinitiator.
2. The sealing material composition according to claim 1, wherein the content of the sheet-like inorganic compound is 20 to 45% by weight.
3. The sealing material composition according to claim 1 or 2, wherein the epoxy resin is an epoxy resin containing a phenol skeleton.
4. The sealing material composition according to claim 1 or 2, wherein the photoinitiator is a composition containing PF 6 － 、SbF 6 － 、(Rf) n PF 6-n － Or B (C) 6 F 5 ) 4 A sulfonium salt or iodonium salt as a counter anion, said Rf being a perfluoroalkyl group, said n being a real number from 1 to 6.
5. The sealing material composition according to claim 1 or 2, further comprising a silane coupling agent having an epoxy group.
6. A sealing material obtained by curing the sealing material composition according to any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021173432A JP2023063118A (en) | 2021-10-22 | 2021-10-22 | Sealant composition and sealant |
| JP2021-173432 | 2021-10-22 |
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| Publication Number | Publication Date |
|---|---|
| CN116003958A true CN116003958A (en) | 2023-04-25 |
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| CN202211135991.5A Pending CN116003958A (en) | 2021-10-22 | 2022-09-19 | Sealing material composition and sealing material |
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| Country | Link |
|---|---|
| JP (1) | JP2023063118A (en) |
| CN (1) | CN116003958A (en) |
| TW (1) | TW202334369A (en) |
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- 2022-09-19 CN CN202211135991.5A patent/CN116003958A/en active Pending
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| JP2023063118A (en) | 2023-05-09 |
| TW202334369A (en) | 2023-09-01 |
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