WO2019245054A1 - ゼオライト含有ポリイミド樹脂複合材、ゼオライト含有ポリイミド樹脂前駆体組成物、フィルム、及び電子デバイス - Google Patents
ゼオライト含有ポリイミド樹脂複合材、ゼオライト含有ポリイミド樹脂前駆体組成物、フィルム、及び電子デバイス Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a zeolite-containing polyimide resin composite, a zeolite-containing polyimide resin precursor composition, a film, and an electronic device.
- Polyimide resins generally have a relatively high glass transition temperature compared to other resins.
- polyimide resin tends to have a large average coefficient of thermal expansion at high temperatures, the required initial characteristics of the electronic device must be satisfied by deformation such as warpage of the polyimide resin film in the high-temperature processing process during electronic device production.
- the polyimide resin film is deformed such as warping due to the heat generated by driving the electronic device, peeling or disconnection of the components installed on the resin further occurs, and the required durability characteristics of the electronic device can be satisfied. Problems that cannot be performed may occur. Therefore, the average thermal expansion coefficient of the polyimide resin is required to be low.
- the polyimide resin used as the substrate is required to have a low retardation value and a low haze ratio.
- the in-plane orientation of the polyimide resin is uniform.However, for good image clarity and high transparency, the in-plane orientation of the polyimide resin is preferred. Since it is preferable that they are not aligned, there is a trade-off relationship between prevention of deformation such as warpage, good image clarity, and high transparency (Patent Documents 1-3).
- Patent Documents 1-3 As a technique for eliminating the above trade-off relationship, it is known to devise a unit constituting the resin or to add a filler.
- Patent Documents 1-3 by incorporating a special component into a unit constituting a resin, the average thermal expansion coefficient is relatively low, the image clarity is relatively high, and / or the transparency is relatively low.
- High polyimide resins are described.
- Patent Documents 3 and 4 disclose a polyimide resin having a relatively low average thermal expansion coefficient, a relatively high image clarity, and / or a relatively high transparency by adding silica fine particles to a polyimide resin. A resin composite is described.
- a film using a polyimide resin as described in Patent Documents 1-3 suppresses deformation such as warpage during a high-temperature treatment process, has good image clarity, and has high transparency. It can be expected to be used for members.
- a special component is incorporated in a unit constituting the resin, it is a problem to be a special polyimide resin which has a new problem that the production cost is high.
- a film of a polyimide resin composite material obtained by adding a filler to a polyimide resin as described in Patent Documents 3 and 4 suppresses deformation such as warpage during a high-temperature treatment process, and has good image clarity and transparency.
- a high film it can be expected to be used as a member of an electronic device or the like.
- a special polyimide resin since there is no need to use a special polyimide resin, it can be expected that the resin is generally used at low cost.
- the silica fine particles added as a filler tend to agglomerate. It was found that the formation was conspicuous and the transparency was sometimes reduced.
- the stability of the polyimide resin-containing composition or the polyimide resin precursor-containing composition is low, and from the composition, It was found that the reproducibility of the image clarity of the produced polyimide resin film was poor and also brittle.
- an object of the present invention is to provide, at low cost, a polyimide resin composite material suitable for a member of an electronic device or the like, which has both high suppression properties against deformation such as warpage, good image clarity, and high transparency. I do.
- the present inventors disperse zeolite having a specific structure in a polyimide resin, so that the polyimide resin composite has a small average thermal expansion coefficient (CTE), a low haze ratio, The inventors have found that the retardation value can be reduced, and have reached the present invention. Further, in the present invention, it has been found that the elastic modulus can be increased by the above configuration, and the present invention has been achieved.
- CTE thermal expansion coefficient
- the gist of the present invention is as follows.
- a zeolite-containing polyimide resin composite material for an electronic material device comprising a zeolite containing at least one of d6r and mtw as a structural building unit (CBU) and a polyimide resin.
- CBU structural building unit
- a polyimide resin containing a zeolite containing at least one of d6r and mtw as a structural building unit (CBU) and a polyimide resin.
- [6] The zeolite-containing polyimide resin composite material according to any one of [1] to [5], wherein the zeolite is contained in an amount of 1% by mass to 80% by mass with respect to the zeolite.
- CBU structural building unit
- a zeolite-containing polyimide resin composite which is a cured product of the composition according to [8].
- a polyimide resin composite material suitable for a member of an electronic device or the like which has high suppression of deformation such as warpage, high image clarity, and high transparency, can be provided at low cost.
- FIG. 1 is a cross-sectional view schematically illustrating a configuration of a field-effect transistor element as one embodiment of the present invention.
- FIG. 1 is a cross-sectional view schematically illustrating a configuration of an electroluminescent device as one embodiment of the present invention.
- FIG. 1 is a cross-sectional view schematically illustrating a configuration of a photoelectric conversion element as one embodiment of the present invention.
- BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which represents typically the structure of the solar cell as one Embodiment of this invention.
- BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which represents typically the structure of the solar cell module as one Embodiment of this invention.
- a first aspect of a zeolite-containing polyimide resin composite material includes a zeolite containing at least one of d6r and mtw as a structural building unit (CBU), and a polyimide resin,
- a zeolite-containing polyimide resin composite for electronic material devices also referred to as “electronic devices”.
- a second aspect of the zeolite-containing polyimide resin composite which is another embodiment of the present invention is a zeolite-containing transparent polyimide resin composite, in which any of d6r and mtw is used as a structural building unit (CBU).
- FIG. 1 is a diagram schematically illustrating a resin composite material according to an embodiment of the present invention. Hereinafter, the resin composite material 1 will be described in detail.
- the resin composite 1 contains a zeolite 2 and a polyimide resin 3.
- zeolite refers to a TO 4 unit (T element is an element other than oxygen constituting the skeleton) which is a basic unit including silicon or aluminum and oxygen. Examples include crystalline porous aluminosilicate, crystalline porous aluminophosphate (ALPO), or crystalline porous silicoaluminophosphate (SAPO).
- the TiO 4 unit is composed of several (several to several tens) connected structural units called Composite Building Units (CBU). For this purpose, it has regular channels (tubular pores) and cavities (cavities).
- the resin composite contains a zeolite containing at least one of d6r and mtw as a structural unit (Composite) Building (Unit) (CBU), and the zeolite is used as a filler.
- the zeolite contains a polyimide resin, and has a structural unit that easily forms a cavity in which a part of the imide bond of the polyimide resin easily enters. Therefore, the zeolite is more compatible with the polyimide resin than the conventionally used filler such as silica particles, so that the zeolite hardly causes aggregation.
- a small amount of zeolite can significantly lower the average thermal expansion coefficient of the resin composite, so that even over time, clouding can be prevented, and high transparency can be achieved. Can be maintained. Further, since the content of zeolite as a filler is small, high flexibility can be maintained, which leads to prevention of embrittlement and deformation and good image clarity.
- Examples of the zeolite having d6r include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT , SAV, SBS, SBT, SFW, SSF, SZR, TSC, and zeolite having a -WEN type structure.
- zeolites having mtw include * BEA, BEC, CSV, GON, ISV, ITG, * -ITN, IWS, MSE, MTW, SFH, SFN, SSF, * -SSO, UOS, and UOV type zeolites. Is mentioned.
- the zeolite further has a three-dimensional channel.
- AEI AEI
- AFT AFX
- CHA CHA
- ERI ERI
- KFI KFI
- SAT SAV
- SFW Zeolite having a TSC structure
- the structure having an oxygen eight-membered ring means that the number of oxygen is the largest among pores formed of oxygen forming the zeolite skeleton and T element (element other than oxygen forming the skeleton). In this case, it means a structure in which the number of oxygen elements is 8.
- the content of the zeolite contained in the resin composite material is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more. It is particularly preferably at least 10% by mass, most preferably at least 15% by mass, while it is usually at most 80% by mass, preferably at most 70% by mass, more preferably at most 50% by mass, still more preferably at most 40% by mass. %, Particularly preferably 30% by mass or less, most preferably 20% by mass or less. As described above, if a small amount of zeolite is added to the resin, the obtained average thermal expansion coefficient can be greatly reduced as compared with the case where silica or the like is used as the filler.
- the resin composite material when the zeolite content is 1% by mass or more and 80% by mass or less, the resin composite material can have good image clarity and high transparency while suppressing embrittlement and deformation. . Particularly, when the content is 10% by mass or more and 30% by mass or less, the properties of the resin composite material are more clearly exhibited with a small content as compared with silica or the like, and therefore, it is particularly preferable.
- the zeolite in the resin composite material may contain one kind alone, or may contain two kinds or more in optional combination and ratio. However, at least one of them is a zeolite in which the structural unit ⁇ Composite ⁇ Building @ Unit (CBU) contains either d6r or mtw as described above.
- CBU Compposite ⁇ Building @ Unit
- zeolite is preferably an aluminosilicate in terms of easy production, but gallium, iron, boron, titanium, zirconium instead of silicon or aluminum as long as the effects of the present invention are not significantly impaired.
- Tin, zinc, phosphorus, etc. and may contain gallium, iron, boron, titanium, zirconium, tin, zinc, phosphorus, etc. together with silicon and aluminum.
- the structure of zeolite can be indicated by a code that defines the structure of zeolite defined by International ⁇ Zeolite ⁇ Association (IZA).
- IZA International ⁇ Zeolite ⁇ Association
- the structure of the zeolite is based on an X-ray diffraction pattern obtained by an X-ray structure analyzer (for example, a tabletop X-ray diffractometer D2PHASER manufactured by BRUKER), based on a zeolite structure database 2018 edition (http: // www. .Iza-structure.org / databases /).
- the average coefficient of thermal expansion of the zeolite is not particularly limited, as long as the resin composite material exhibits favorable performance, but is less than 0 ppm / K, preferably -2 ppm / K or less, more preferably -3 ppm / K.
- the resin composite has a low content of zeolite and can maintain high flexibility, while suppressing embrittlement and deformation. High image clarity and high transparency.
- the average coefficient of thermal expansion of zeolite can be measured by calculating a lattice constant using an X-ray diffractometer D8ADVANCE manufactured by Bruker and X-ray diffraction analysis software JADE.
- the average coefficient of thermal expansion of this zeolite is determined by measuring the coefficient of thermal expansion at 60 ° C. and 220 ° C., and taking the average as the average coefficient of thermal expansion.
- the framework density of the zeolite is not particularly limited as long as the resin composite material exhibits favorable performance, but is preferably 17.0 T / 1000 3 or less, more preferably 16.0 T / 1000 3. 3 or less, more preferably 15.0 T / 1000 3 or less, while preferably 12.0 T / 1000 3 or more, more preferably 13.0 T / 1000 3 or more, and still more preferably 14.0 T / 1000 3 or more. is 1000 ⁇ 3 or more.
- the framework density is within the above range, the zeolite can be easily formed into fine particles so as not to be easily aggregated, and can have good image clarity and high transparency while suppressing embrittlement and deformation.
- the framework density indicates the number of T atoms present per unit volume of zeolite, and is a value determined by the structure of zeolite. In the present specification, numerical values described in the IZA zeolite structure database 2018 edition (http://www.iza-structure.org/databases/) may be used.
- Framework density is greater than 16.0T / 1000 ⁇ 3, examples of 17.0T / 1000 ⁇ 3 or less of the zeolite, CSV, ERI, ITG, LTL , LTN, MOZ, MSE, OFF, SAT, SFH, SFN, SSF, * -SSO, and -WEN type zeolites can be mentioned.
- Framework density is greater than 15.0T / 1000 ⁇ 3, examples of 16.0T / 1000 ⁇ 3 or less of the zeolite, AEI, AFT, AFV, AFX , AVL, * BEA, BEC, CHA, EAB, GME, * Zeolite with ITN, LEV, MWW, and SFW type structures.
- Framework density is greater than 14.0T / 1000 ⁇ 3, examples of 15.0T / 1000 ⁇ 3 or less of the zeolite, mention may be made ISV, IWS, KFI, SAS, and the zeolite SAV structure.
- zeolite present in the range of 14.0T / 1000 ⁇ 3 or less may be mentioned EMT, FAU, JSR, SBS, SBT, and the zeolite TSC structure.
- the silica / alumina molar ratio (SAR) of the zeolite is not particularly limited as long as the resin composite material exhibits preferable performance, but is usually 0.1 or more, preferably 0.5 or more, more preferably It is 4 or more, more preferably 9 or more, particularly preferably 12 or more, usually 2,000 or less, preferably 1,000 or less, more preferably 500 or less, and further preferably 100 or less.
- SAR silica / alumina molar ratio
- the moles of the oxide of the replaced element are used.
- the ratio may be converted as a molar ratio of alumina or silica.
- gallium is used instead of aluminum, the molar ratio of gallium oxide may be converted to the molar ratio of alumina.
- the counter cation of zeolite is not particularly limited as long as the resin composite material exhibits preferable performance, but is usually a structure directing agent, a proton, an alkali metal ion, or an alkaline earth metal ion, and is preferably Is a structure directing agent, proton, an alkali metal ion, more preferably a structure directing agent, proton, Li ion, Na ion, K ion, more preferably a structure directing agent, proton, Li ion, Particularly preferred is a proton.
- zeolite In the case of a structure-directing agent, zeolite is preferable because it has flexibility as compared with alkali metal ions or alkaline earth metal ions, and thus easily exhibits an average coefficient of thermal expansion of less than 0 ppm / K. Further, the smaller the size of the alkali metal ion or alkaline earth metal ion, the more preferable the zeolite is because the zeolite easily shows an average thermal expansion coefficient of less than 0 ppm / K. Among them, protons are preferable because the average thermal expansion coefficient of the resin composite material is easily reduced.
- the zeolite is preferably as-made (structure-directing agent-containing type), proton type or alkali metal type, and more preferably as-made, proton type, Li type, Na type or K type. More preferably, it is an as-made, proton type or Li type, and most preferably a proton type.
- the structure directing agent is a template used in the production of zeolite.
- the crystallinity of zeolite is not particularly limited as long as the resin composite material exhibits favorable performance. The reason is that it is estimated that Composite Building Unit (CBU) is a factor that leads to the average thermal expansion coefficient of the resin composite material, rather than the structure defined by the IZA code.
- CBU Composite Building Unit
- the crystallinity of zeolite is obtained by comparing a certain X-ray diffraction peak obtained with an X-ray diffractometer (for example, a tabletop X-ray diffractometer D2PHASER manufactured by BRUKER) with an X-ray diffraction peak of zeolite as a reference. You can ask for it.
- an X-ray diffractometer for example, a tabletop X-ray diffractometer D2PHASER manufactured by BRUKER
- the crystallinity of the LTA-type zeolite having Scientific ⁇ Reports ⁇ 2016, 6, and Article ⁇ number: 29210 ⁇ can be given.
- the average primary particle size of the zeolite is not particularly limited, as long as the resin composite material exhibits preferable performance, but is usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and most preferably. 40 nm. On the other hand, it is usually at most 2,000 nm, preferably at most 1,000 nm, more preferably at most 500 nm, further preferably at most 300 nm, particularly preferably at most 200 nm, most preferably at most 100 nm.
- the average primary particle diameter of the zeolite is within the above range, the zeolite is easily dispersed uniformly in the resin composite, and furthermore, the transparency of the obtained resin composite is increased, and a good image clarity is obtained. It tends to lead to sex.
- the average primary particle diameter of the zeolite is determined by observing the particles with a scanning electron microscope (SEM), measuring the particle diameter of arbitrarily selected 30 or more primary particles, and averaging the particle diameters of the primary particles.
- the particle diameter means the diameter of the circle having the area equal to the projected area of the particle and having the maximum diameter (equivalent circle diameter).
- the zeolite may be in a state of secondary or higher secondary particles in which primary particles are aggregated, as long as the resin composite material exhibits preferable performance.
- the average particle size in that state is not particularly limited, but is usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, particularly preferably 40 nm, and most preferably 50 nm or more.
- it is usually at most 3,000 nm, preferably at most 2,000 nm, more preferably at most 1,000 nm, further preferably at most 500 nm, particularly preferably at most 300 nm, most preferably at most 100 nm.
- zeolite tends to be uniformly dispersed in the resin composite material, and further, the transparency of the obtained resin composite material tends to be high and good image clarity tends to be obtained.
- the average particle diameter of the secondary or higher order particles of the zeolite as in the case of the primary particles, by observing the particles with a scanning electron microscope (SEM), measuring the particle diameter of arbitrarily selected 30 or more particles, The average particle diameter may be determined.
- the particle diameter means the diameter of the circle having the area equal to the projected area of the particle and having the maximum diameter (equivalent circle diameter).
- a laser diffraction type particle size distribution measuring device or a dynamic light scattering type particle size distribution measuring device may be used according to the particle size.
- the method for producing zeolite is not particularly limited, and zeolite can be produced at low cost by a known hydrothermal synthesis method.
- zeolite can be produced at low cost by a known hydrothermal synthesis method.
- it can be produced with reference to the method described in Japanese Patent No. 4896110.
- a structure-directing agent can be used as a template if necessary. Normally, as long as the structure-directing agent can produce the desired zeolite structure, there is no particular limitation, and there is no structure-directing agent. If it can be manufactured by using the above, a structure directing agent may not be used.
- the synthesis time may be shorter than usual, and the synthesis temperature may be controlled at a lower temperature than usual to perform hydrothermal synthesis, or
- the zeolite obtained by the thermal synthesis may be pulverized and / or pulverized by wet pulverization such as a bead mill or a ball mill.
- Examples of the crushing device used for the crushing and / or crushing include, for example, “OB Mill” manufactured by Freund Turbo, “Nano Getter” manufactured by Ashizawa Finetech, “Nano Getter Mini”, “ Star Mill “,” Lab Star “,” Star Burst “manufactured by Sugino Machine Co., Ltd., and the like.
- the crystallinity of the zeolite after pulverization is reduced, but can be recrystallized in a solution containing alumina, silica, or the like, as described in JP-A-2014-189476. .
- a dispersant may be used at the time of wet pulverization.
- the solvents and dispersants mentioned in the constituent components of the ink described below can be used.
- centrifugation can be performed to remove particles having a large average particle diameter in order to further reduce the average particle diameter of the zeolite in the dispersion in which the crushed and / or pulverized zeolite is dispersed. This is preferable because the zeolite can be more easily dispersed in the resin composite material, and further, the transparency of the obtained resin composite material is increased.
- a commercially available device for example, a centrifuge H-36 manufactured by Kokusan Co., Ltd., and a Hitachi micro high-speed centrifuge CF15RN manufactured by Hitachi Koki
- a commercially available device for example, a centrifuge H-36 manufactured by Kokusan Co., Ltd., and a Hitachi micro high-speed centrifuge CF15RN manufactured by Hitachi Koki
- any of a curable resin and a thermoplastic resin can be used without limitation.
- active energy ray-curable resin, and crosslinkable thermosetting resin, etc. are possible, if the curable resin, the uniform distribution of resin and zeolite in the resin composite material is higher than thermoplastic resin This is preferred.
- a thermosetting resin is preferable because the production cost is low because an exposure machine is not used.
- the active energy ray-curable resin composite is, for example, a resin that is cured by ultraviolet light, visible light, infrared light, electron beam, or the like.
- the polyimide resin may be a polyimide resin having a nucleated hydrogenated (also referred to as “hydrogenated”) aromatic compound or a polyimide resin having a non-nucleated hydrogenated aromatic compound.
- a polyimide resin having a nucleated hydrogenated aromatic compound is particularly preferable when used for an electronic device.
- polyimide resin having a nucleated hydrogenated aromatic compound see “New Edition ⁇ Latest Polyimide ⁇ —Basic and Application—” (edited by Japan Polyimide-Aromatic Polymer Study Group, NTT TS (2010) ), WO 2015/125895, WO 2014/98042, and JP-A-2016-128555.
- the dispersant is used by exhibiting an interaction between the imide bond and the unreacted carbonyl group and amino group contained in the polyimide resin and the Si—OH group on the zeolite surface.
- Part of the imide bond contained in the polyimide resin enters the cavity formed from either d6r or mtw into the structural unit ⁇ Composite ⁇ Building @ Unit (CBU) of the zeolite. And so on. Therefore, the zeolite is easily dispersed uniformly in the polyimide resin composite material, and excellent image clarity and high transparency can be provided while suppressing embrittlement and deformation. As a result, clouding can be prevented for a long period of time, and good image clarity and high transparency can be maintained.
- a polyimide resin having a nucleated hydrogenated aromatic compound has a zeolite structure in which a nucleated hydrogenated aromatic compound inhibits ⁇ - ⁇ stacking derived from ⁇ - ⁇ bonds between aromatic compounds.
- zeolites having d6r or mtw have better compatibility, which, in addition to the above-mentioned reasons, has a role of filling the space for the hindered ⁇ - ⁇ stacking by d6r or mtw. It is considered that the compatibility is further improved by serving as a CBU. As a result, white turbidity can be prevented for a long period of time, and better image clarity and higher transparency can be maintained.
- the molecular weight of the polyimide resin is not particularly limited as long as the resin composite material exhibits preferable performance, and is a value of a mass average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) and is usually 1000 or more. , Preferably 3,000 or more, more preferably 5,000 or more. Further, it is usually not more than 200,000, preferably not more than 180000, and more preferably not more than 150,000. When the content is within the above range, solubility in a solvent, viscosity, and the like tend to be easy to handle with ordinary manufacturing equipment, and thus it is preferable.
- Mw mass average molecular weight
- GPC gel permeation chromatography
- the number average molecular weight (Mn) of the polyimide resin is not particularly limited as long as the resin composite exhibits favorable performance, but is usually 500 or more, preferably 1000 or more, and more preferably 2500 or more. Further, it is usually 100,000 or less, preferably 90,000 or less, more preferably 80,000 or less. When the content is within the above range, solubility in a solvent, viscosity, and the like tend to be easy to handle with ordinary manufacturing equipment, and thus it is preferable.
- the number average molecular weight in terms of polystyrene can be determined by the same method as that for the mass average molecular weight.
- the value (Mw / Mn) obtained by dividing Mw of the polyimide resin by Mn is usually 1.5 or more, preferably 2 or more, more preferably 2.5 or more, while it is usually 5 or less, preferably 4. It is 5 or less, more preferably 4 or less. It is preferable that the content is within the above range, in that the uniformity of the zeolite in the resin composite material is increased and a molded article of the resin composite material having excellent smoothness is obtained.
- the glass transition temperature (Tg) of the polyimide resin is usually 80 ° C or higher, preferably 120 ° C or higher, more preferably 170 ° C or higher, further preferably 220 ° C or higher, and particularly preferably 250 ° C or higher.
- the temperature is usually 700 ° C. or lower, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, further preferably 350 ° C. or lower, and particularly preferably 320 ° C. or lower.
- the resin composite material can have good image clarity and high transparency while suppressing embrittlement and deformation.
- Polyimide resin is a material having an average coefficient of thermal expansion of generally greater than 0 ppm / K.
- the average coefficient of thermal expansion of the polyimide resin is not particularly limited, as long as the resin composite material exhibits preferable performance, but is usually 0 ° C. or higher and the glass transition temperature of the resin or lower, in a measurement range in a temperature range of, usually, , Greater than 0 ppm / K, preferably at least 10 ppm / K, more preferably at least 20 ppm / K, even more preferably at least 30 ppm / K, particularly preferably at least 50 ppm / K, and usually at least 200 ppm.
- the resin composite material can have good image clarity and high transparency while suppressing embrittlement and deformation. Further, since only a small amount of zeolite is required, white turbidity can be reduced over a long period of time.
- the average thermal expansion coefficient of the resin can be measured by thermomechanical analysis according to a method based on JIS K7197 (2012). For example, by using a thermomechanical analyzer TMA / SS6100 manufactured by SII Nanotechnology Co., Ltd., it can be measured by the expansion and contraction of the sheet-shaped resin composite material. Specifically, it can be determined from the slope of the coefficient of thermal expansion at two temperatures, usually 60 ° C. and 220 ° C. When the glass transition temperature is 220 ° C. or lower, an average of the measured values at 60 ° C. and the glass transition temperature can be obtained. Further, the glass transition temperature of the resin can be determined from the inflection point measured by thermomechanical analysis.
- the method for producing the polyimide resin is not particularly limited as long as the resin composite exhibits favorable performance, and may be produced by a known method. For example, it can be produced by the method described in “New Edition ⁇ Latest Polyimide ⁇ —Basic and Application—” (edited by Japan Polyimide & Aromatic Polymer Research Society, NTT (2010)).
- the resin composite material may contain other compounds other than zeolite and polyimide resin as long as the effects of the present invention are not significantly impaired.
- the ink or the kneaded material may contain a dispersant, a surface treatment agent, a surfactant, an imidization accelerator, a solvent, and the like, and these residual components may be used. It may be contained in a resin composite material.
- the third aspect of the zeolite-containing polyimide resin composite material according to another embodiment of the present invention is a zeolite-containing polyimide resin containing a zeolite and a polyimide resin having a nuclear hydrogenated aromatic compound.
- a polyimide resin composite material, wherein the composite material has an average thermal expansion coefficient of less than 50 ppm / K at a temperature of 0 ° C.
- the resin has an average thermal expansion coefficient of less than 50 ppm / K at a glass transition temperature or lower and an elastic modulus at 25 ° C. of 4.5.
- the Pa or more and a haze of not more than 5%, zeolite-containing polyimide resin composite material is obtained.
- the average coefficient of thermal expansion of the zeolite-containing polyimide resin composite at 0 ° C. or higher and the glass transition temperature of the polyimide resin or lower can be less than 50 ppm / K. It is preferably at most 45 ppm / K, more preferably at most 40 ppm / K, further preferably at most 35 ppm / K, particularly preferably at most 30 ppm / K. Further, it is usually at least 0 ppm / K, preferably at least 5 ppm / K, more preferably at least 10 ppm / K, further preferably at least 15 ppm / K, particularly preferably at least 20 ppm / K.
- the average thermal expansion coefficient of the resin composite can be measured in the same manner as the above-described average thermal expansion coefficient of the resin.
- the retardation value of the zeolite-containing polyimide resin composite material can be set to 150 nm or less. It is preferably at most 125 nm, more preferably at most 100 nm, further preferably at most 75 nm, particularly preferably at most 50 nm. In addition, there is no preferable lower limit because it is more preferable to be closer to zero.
- the retardation value can be measured using a retardation film / optical material inspection device. For example, using a RETS-100 manufactured by Otsuka Electronics Co., Ltd., a value of a wavelength of 460 nm can be calculated for a film having a thickness of 10 ⁇ m.
- the haze ratio of the zeolite-containing polyimide resin composite is a value with respect to D65 light, and can be usually 5% or less. It is preferably at most 4%, more preferably at most 3%, further preferably at most 2%, particularly preferably at most 1%. In addition, there is no preferable lower limit because it is more preferable to be closer to zero.
- the haze ratio is measured by a method based on JIS K7136 (2000) and JIS K7361-1 (1997). Specifically, it can be measured with a haze meter (for example, a TM Double Beam Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.).
- the light transmittance at a wavelength of 450 nm of the resin composite material is preferably 70% or more, more preferably 75% or more, further preferably 80% or more, particularly preferably 85% or more, and most preferably. Is 90% or more. There is no preferred upper limit since it is preferable to be closer to 100%. By being within the above range, good image clarity and high transparency can be provided.
- the transmittance can be measured with a spectrophotometer (for example, a spectrophotometer UV-2500PC manufactured by Shimadzu Corporation).
- the visible light transmittance of the resin composite material is preferably 60% or more, more preferably 65% or more, further preferably 70% or more, particularly preferably 75% or more, and most preferably 80% or more. There is no preferred upper limit since it is preferable to be closer to 100%. By being within the above range, good image clarity and high transparency can be provided.
- the visible light transmittance can be calculated from a value measured by a spectrophotometer (for example, a spectrophotometer UV-2500PC manufactured by Shimadzu Corporation) by a method defined in JIS R3106 (1998).
- the resin composite has a yellow index (yellowness) value of preferably -20 or more, more preferably -10 or more, further preferably -5 or more, particularly preferably -3 or more, and most preferably. Is greater than or equal to -1. On the other hand, it is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, particularly preferably 3 or less, and most preferably 1 or less. By being within the above range, good image clarity and high transparency can be provided.
- the yellow index value can be measured by a method based on JIS K7373 (2006). Specifically, it can be calculated for a film having a thickness of 10 ⁇ m using a color computer SM5 manufactured by Suga Test Instruments Co., Ltd.
- the elastic modulus of the resin composite material at 25 ° C. (hereinafter, the storage elastic modulus of the resin composite material may be simply referred to as “elastic modulus” in the present specification) is not particularly limited, but is usually 4.0 GPa or more. , Preferably at least 4.2 GPa, more preferably at least 4.5 GPa, even more preferably at least 4.6 GPa, particularly preferably at least 4.7 GPa, while usually at least 8.0 GPa. 0 GPa or less, preferably 7.5 GPa or less, more preferably 7.0 GPa or less, still more preferably 6.8 GPa or less, particularly preferably 6.5 GPa or less.
- the storage elastic modulus of the resin composite material can be measured, for example, by a dynamic viscoelasticity measurement method described in JIS K-7244, using a dynamic viscoelasticity apparatus DMS6100 manufactured by SII Nanotechnology, Inc., measuring temperature range: -100.
- the temperature can be measured in a double-ended tensile mode under the conditions of ° C to 150 ° C, a frequency of 1 Hz, and a heating rate of 5 ° C / min.
- the haze ratio in D65 light, the light transmittance at a wavelength of 450 nm, or the visible light transmittance can be quantitatively quantified by the above-mentioned qualitative judgment. Can be.
- the flexibility of the resin composite material can be quantitatively quantified by a bending resistance test or the like, a qualitative judgment can be made by counting the number of cracks and streaks caused by bending by hand.
- the method for producing the polyimide resin composite material is not particularly limited, as long as the resin composite material exhibits favorable performance, and can be used in a conventional manner such as molding in a heat-melted state, injection molding, or the like. It is often used in the form of a film to take advantage of gas barrier properties. Therefore, in the following, a polyimide resin precursor, a zeolite, and a solvent are mixed to form a zeolite-containing polyimide resin precursor composition (also referred to as “ink”). This will be described as an example of a method of preparing an ink, applying the ink to a support or the like, and then heating and drying the ink. Therefore, the description of the polyimide resin, dispersant, solvent and the like described below is not limited to ink, and may be included in the composite material.
- a polyimide resin Since a polyimide resin is insoluble and insoluble in many solvents, it is molded using a polyimide precursor, polyamic acid, and then converted into a polyimide resin by dehydration / cyclization (imidization).
- the dehydration / cyclization may be performed by heating or using an imidization accelerator described below, and the heating temperature for conversion to the polyimide resin corresponds to the curing temperature described below.
- the polyimide resin precursor means a polyamic acid obtained by polymerizing tetracarboxylic dianhydride and diamine as raw materials in equimolar amounts.
- a polyamic acid obtained by polymerizing tetracarboxylic dianhydride and diamine as raw materials in equimolar amounts.
- an ink obtained by polymerizing tetracarboxylic dianhydride and diamine in the ink is used as it is.
- An ink according to another embodiment of the present invention is a zeolite-containing polyimide resin precursor composition containing at least the above-described zeolite and a polyimide resin precursor, and a mixture of these materials, or a polyimide resin precursor.
- the composition is prepared by mixing a composition containing a polyimide resin or a polyimide resin precursor raw material (tetracarboxylic dianhydride and diamine) and a solvent.
- the content of zeolite in the ink is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, particularly preferably 7% by mass or more. It is most preferably at least 10% by mass, while usually at most 80% by mass, preferably at most 70% by mass, more preferably at most 60% by mass, further preferably at most 50% by mass, particularly preferably at most 40% by mass, most preferably at most 40% by mass. Preferably it is 20 mass% or less.
- the amount of zeolite when calculating the zeolite content is the total amount of zeolite and substances contained in zeolite.
- one type of zeolite may be used alone, or two or more types may be used in any combination and in any ratio.
- the polyimide resin used for the ink the polyimide resin in the resin composite material according to one embodiment of the present invention described above can be used, and is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more. % By mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, while usually 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. %, Particularly preferably 70% by mass or less. When the content is within the above range, the resin can be manufactured without causing precipitation or the like, and an ink in which the dispersion state is kept long can be manufactured.
- one kind of the polyimide resin may be used alone, or two or more kinds thereof may be used in an optional combination and ratio.
- a polyamic acid which is a polyimide resin precursor
- a polyimide resin precursor may be mixed instead of the above-described polyimide resin.
- the content of the polyimide resin precursor in the ink may be equivalent to the content of the above-described resin that can be converted when converted into a polyimide resin.
- an ink containing a polyamic acid which is a polyimide resin precursor, is formed by forming a polyamic acid in the ink by heating and polymerizing an ink obtained by adding an equimolar amount of tetracarboxylic dianhydride and a diamine. Is used as it is as ink.
- tetracarboxylic dianhydride and diamine may be mixed instead of the above-mentioned polyimide resin.
- the content of the polyimide resin precursor raw materials (tetracarboxylic dianhydride and diamine) in the ink may be equivalent to the content of the above resin that can be converted when finally converted into a polyimide resin.
- tetracarboxylic dianhydride examples are not particularly limited as long as the resin composite material exhibits preferable performance.
- "New edition ⁇ Latest polyimide ⁇ -Basic and applied-" (Nippon polyimide / aromatic series) Tetracarboxylic acid dianhydrides described in, for example, Polymer Society of Japan, NTT (2010)), International Publication No. WO 2015/125895, International Publication WO 2014/98042, and JP-A-2016-128555. Things apply.
- tetracarboxylic dianhydride having a nuclear hydrogenated aromatic compound is preferred.
- diamine examples are not particularly limited as long as the resin composite material exhibits preferable performance.
- “New edition ⁇ Latest polyimide ⁇ —Basic and application—” (edited by the Japan Polyimide and Aromatic Polymer Study Group) , NTTS (2010)), WO 2015/125895, WO 2014/98042, JP-A-2016-128555, and the like.
- the heating temperature for forming a polyamic acid by polymerizing equimolar amounts of tetracarboxylic dianhydride and diamine should be lower than the temperature at which the corresponding polyamic acid is further dehydrated and cyclized to be converted to polyimide. Is preferred.
- the solvent is not particularly limited as long as the resin composite material exhibits preferable performance.
- examples thereof include water; aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, and decane; toluene, xylene, chlorobenzene or Aromatic hydrocarbons such as orthodichlorobenzene; alcohols such as methanol, ethanol, isopropanol, 2-butoxyethanol and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; ethyl acetate Esters such as butyl acetate or methyl lactate; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; propylene glycol monomethyl ether acetate (PGMEA);
- aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene because of high solubility of the polyimide resin precursor; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; propylene glycol Ethers such as monomethyl ether acetate (PGMEA), ethyl ether, tetrahydrofuran or dioxane; amides such as N-methylpyrrolidone, dimethylformamide or dimethylacetamide are preferred.
- aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene because of high solubility of the polyimide resin precursor
- halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene
- amides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide are preferred because the solubility of the polyimide resin precursor having a nucleated hydrogenated aromatic compound is high.
- the solvent may or may not remain in the resin composite, and there is no particular limitation on the solvent content or boiling point.
- the content of the solvent in the ink is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, while it is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90 mass% or less. It is preferable that it is within the above range, since the ink has an appropriate viscosity and a resin composite material having an appropriate thickness after drying can be obtained.
- one type of solvent may be used alone, or two or more types may be used in any combination and in any ratio.
- the ink may contain zeolite, a polyimide resin or a polyimide resin precursor or a polyimide resin precursor raw material, and other compounds other than a solvent, for example, a dispersant, a surface treatment agent, a surfactant, and imidization promotion. And the like.
- a dispersant for example, a surface treatment agent, a surfactant, and imidization promotion.
- these dispersants, surface treatment agents, surfactants, and imidization accelerators the above-described dispersants, surface treatment agents, surfactants, and imidization accelerators in the resin composite material can be used.
- the other compound used in the ink is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more in the ink. Is particularly preferably 0.05% by mass or more, while usually 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. It is as follows. When the content is within the above range, zeolite, a polyimide resin, or a polyimide resin precursor can be kept dispersed in the ink without causing precipitation or the like.
- the dispersant means a compound for uniformly dispersing the zeolite in the ink and in the resin composite material after production.
- polysiloxane compounds such as methylhydrogenpolysiloxane, polymethoxysilane, dimethylpolysiloxane or dimethicone PEG-7 succinate and salts thereof; silane compounds (methyldimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyl Trimethoxysilane, dichlorophenylsilane, chlorotrimethylsilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrichlorosilane, octadecyltrimethoxysilane, octadecyltrichlorosilane, trifluoro
- Examples include amine compounds such as dimethylamine, tributylamine, trimethylamine, cyclohexylamine, ethylenediamine or polyethyleneimine, amine carboxylate compounds, and amine phosphate compounds.
- the amine carboxylate compound means a compound having both functional groups of a carboxyl group and an amino group
- the amine phosphate compound means a compound having both functional groups of a phosphoric acid group and an amino group.
- the amine phosphate compound dispersant is preferable because it has a particularly high affinity for zeolite.
- the dispersant one kind may be used alone, and two kinds or more may be used in optional combination and ratio. Further, a surface treating agent or a surfactant described below may function as a dispersant. The dispersant may be completely decomposed, partially decomposed, or not decomposed after the production of the resin composite material.
- the zeolite may be treated with a surface treatment agent to prevent agglomeration of the zeolite and to uniformly disperse the zeolite in the ink as well as in the manufactured resin composite.
- the surface treatment agent is not particularly limited, and a known one may be used.
- Those used as the above-described dispersant or a binder resin such as polyimine, polyester, polyamide, polyurethane, or polyurea may be used as the surface treatment agent. May be.
- One type of surface treatment agent may be used alone, or two or more types may be used in any combination and in any ratio. After the production of the resin composite material, the surface treatment agent may be completely decomposed, partially decomposed, or not decomposed.
- the ink may contain a surfactant for the purpose of preventing dents or uneven drying from occurring in the resin composite material due to attachment of minute bubbles or foreign substances.
- the surfactant is not particularly limited, and a known surfactant (cationic surfactant, anionic surfactant, nonionic surfactant) can be used. Among them, a silicon-based surfactant, a fluorine-based surfactant, or an acetylene glycol-based surfactant is preferable.
- the surfactant examples include Triton X100 (manufactured by Dow Chemical Company) as a nonionic surfactant, Zonyl FS300 (manufactured by DuPont) as a fluorine-based surfactant, BYK-310 as a silicon-based surfactant, BYK-320, BYK-345 (manufactured by BYK-Chemie), and acetylene glycol-based surfactants such as Surfynol 104, Surfinol 465 (manufactured by Air Products), Olfin EXP4036, or Olfin EXP4200 (manufactured by Nissin Chemical Industry) Is mentioned.
- Triton X100 manufactured by Dow Chemical Company
- Zonyl FS300 manufactured by DuPont
- BYK-310 as a silicon-based surfactant
- BYK-320, BYK-345 manufactured by BYK-Chemie
- One surfactant may be used alone, or two or more surfactants may be used in any combination and in any ratio.
- the surfactant may be completely decomposed, partially decomposed, or not decomposed after the production of the resin composite material.
- the surfactant can improve the wettability of the ink described below.
- the wettability can be evaluated by a contact angle in addition to the actual application to the substrate.
- the contact angle of the ink with respect to the PET substrate is usually 45 ° or less, preferably 30 ° or less, and more preferably 15 ° or less.
- the fact that the contact angle is not detected when it spreads over the entire surface of the base material means that the contact angle is not particularly preferably detected.
- the ink can be applied on any substrate.
- the contact angle can be measured with a contact angle meter. For example, it can be measured with DM-501 manufactured by Kyowa Interface Science Co., Ltd.
- the imidization accelerator only needs to be selected according to the method of producing the polyimide resin in the corresponding polyimide resin composite, since the imidization of polyamic acid, which is a polyimide resin precursor, to polyimide may be promoted.
- polyamic acid which is a polyimide resin precursor
- polyimide resin composite since the imidization of polyamic acid, which is a polyimide resin precursor, to polyimide may be promoted.
- “New Edition ⁇ Latest Polyimide ⁇ -Basics and Application-” (edited by Japan Polyimide and Aromatic Polymer Research Society, NTT (2010)), WO 2015/125895, WO 2014/98042 And the imidization accelerators described in JP-A-2016-128555 and the like.
- the imidization accelerator may be used singly, or two or more kinds may be used in an optional combination and ratio.
- the imidization accelerator may be present alone in the composition or may form a complex with a solvent or the like. Further, a multimer may be formed. Note that the imidization accelerator may be completely decomposed, partially decomposed, or not decomposed after the production of the resin composite material.
- the ink is preferably stable for at least 24 hours, and more preferably for at least one week.
- the more stable the ink the more the ink can be synthesized and stored for a long time, and the lower the manufacturing cost.
- the stability of the ink can be evaluated based on the formation of precipitates and changes in viscosity.
- the generation of the precipitate can be determined visually or by a dynamic light scattering particle diameter measuring device.
- the viscosity can be determined by a rotational viscometer method (described in "Physical Chemistry Experiment Handbook" (edited by Ginya Adachi, Yasutaka Ishii, Gohiro Yoshida, Kagaku Doujin (1993)).
- a resin composite material can be manufactured by kneading a polyimide resin or a polyimide resin precursor and zeolite and then heating without using a solvent.
- the zeolite used for the kneaded material can be used, and one kind may be used alone, or two or more kinds may be used in optional combination and ratio.
- a polyimide resin in the resin composite material can be used, and one kind may be used alone or two or more kinds may be used in optional combination and ratio.
- zeolite used for the kneaded material and other compounds other than the polyimide resin may be included.
- it may contain the above-mentioned dispersant, surface treatment agent, surfactant, imidization accelerator and the like.
- the other compounds one kind may be used alone, and two kinds or more may be used in optional combination and ratio.
- the ratio of zeolite, polyimide resin, and other compounds used in the kneaded material is not particularly limited as long as the resin composite produced by heating from the kneaded material exhibits preferable performance.
- the ink and the kneaded material are not particularly limited, can be prepared by a conventionally known method, and can be produced by mixing the components of the ink and the kneaded material.
- a paint shaker for the purpose of improving uniformity, defoaming, etc., a paint shaker, a bead mill, a planetary mixer, a stirring type disperser, a homogenizer, a self-revolving stirring mixer, a three-roll, kneader, a single-screw or a twin-screw kneader. It is preferable to mix using a general kneading device such as a mixer, a stirrer or the like.
- the order of mixing the constituent components is arbitrary as long as there is no particular problem such as the occurrence of a reaction or a precipitate, and any two or more of the constituent components of the ink and the kneaded material are mixed in advance. Then, the remaining components may be mixed, or all may be mixed at once.
- Molding of polyimide resin composite As a method for molding the resin composite material, a method generally used for molding a resin can be used. At that time, heating required for the production of the resin composite material and heating for molding may be performed simultaneously.
- the polyimide resin composite when it has thermoplasticity, it can be molded by filling the resin composite in a desired shape, for example, into a mold.
- a method for producing such a molded article an injection molding method, an injection compression molding method, an extrusion molding method, a compression molding method, or the like can be used.
- the molded article can be molded at a temperature equal to or higher than the melting temperature of the thermoplastic resin and at a predetermined molding speed and pressure.
- the melting temperature is preferably lower than 400 ° C., more preferably 370 ° C. or lower, particularly preferably 340 ° C. or lower, while preferably 80 ° C. or higher, and 90 ° C. or higher. Is more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. It is preferable that the temperature is lower than 400 ° C. because the temperature can be used even in a manufacturing process using a flexible base material such as a roll-to-roll method. Further, the temperature of 80 ° C. or higher is preferable in that the resin can be uniformly melted, and the temperature of 100 ° C. or higher is preferable in that the influence of water can be reduced. It is preferable because it can be performed.
- the resin constituting the polyimide resin composite material is a cured product of the above-described polyimide resin precursor composition
- a thermosetting resin composite material when a resin precursor is used, molding of the resin composite material, That is, curing can be performed under curing temperature conditions according to each composition.
- the curing temperature is preferably lower than 400 ° C., more preferably 370 ° C. or lower, particularly preferably 340 ° C. or lower, while it is preferably 0 ° C. or higher, and is 80 ° C. or higher. Is more preferably 90 ° C. or higher, particularly preferably 100 ° C. or higher, and most preferably 120 ° C. or higher. It is preferable that the temperature is lower than 400 ° C. because the temperature can be used even in a manufacturing process using a flexible base material such as a roll-to-roll method. Further, the temperature of 80 ° C. or higher is preferable in that the curing proceeds to some extent and the unreacted components are prevented from being eluted from the resin composite material. The temperature of 100 ° C. or higher is preferable in that the effect of moisture can be reduced. , 120 ° C. or more is preferred in that the effect of moisture can be further reduced.
- the resin composite material can be formed by laminating on a desired support (lamination step) and then performing heat treatment (heat treatment step).
- the desired support may be removed after the production.
- the heat treatment method for example, a known drying method such as hot air drying or drying with an infrared heater can be adopted. Among them, hot-air drying with a high drying speed is preferable. If it can be dried by air drying, the heat treatment method may be omitted.
- the temperature of the heat treatment is preferably lower than 400 ° C, more preferably 370 ° C or lower, particularly preferably 340 ° C or lower, while it is preferably 80 ° C or higher, and 90 ° C or higher.
- the temperature is more preferably 100 ° C. or more, and particularly preferably 120 ° C. or more. It is preferable that the temperature is lower than 400 ° C. because the temperature can be used even in a manufacturing process using a flexible base material such as a roll-to-roll method.
- the temperature of 80 ° C. or higher is preferable in that the residual solvent in the sheet can be removed, and the temperature of 100 ° C. or higher is preferable in that the influence of water can be reduced. This is preferable because it can be made smaller.
- the heating time is not particularly limited, but is usually 30 seconds or more, preferably 1 minute or more, more preferably 2 minutes or more, and still more preferably 3 minutes or more, while it is usually 24 hours or less, preferably 12 hours or less, Preferably it is 1 hour or less, more preferably 15 minutes or less.
- the above range is preferable in that it can be adapted to a practical manufacturing process such as a roll-to-roll method.
- the material of the support is not particularly limited, but preferred examples of the material of the substrate include an inorganic material such as quartz, glass, sapphire or titania; and a flexible substrate.
- the flexible substrate is a substrate having a radius of curvature of usually 0.1 mm or more and 10,000 mm or less.
- the radius of curvature is preferably 0.3 mm or more, more preferably 1 mm or more, in order to achieve both flexibility and characteristics as a support. 3,000 mm or less, more preferably 1,000 mm or less.
- the radius of curvature can be determined by using a confocal microscope (for example, a shape measuring laser microscope VK-X200 manufactured by KEYENCE CORPORATION) with a substrate bent to a point where no destruction such as strain or crack appears.
- the flexible base material include, but are not limited to, the above-mentioned resins such as epoxy resins; paper materials such as paper or synthetic paper; and metal foils such as silver, copper, stainless steel, titanium, and aluminum.
- Composite materials such as those coated or laminated on the surface in order to impart properties.
- soda glass soda glass, blue plate glass, non-alkali glass and the like can be mentioned.
- alkali-free glass is preferred among these because ions eluted from glass are small.
- the shape of the support is not limited, and for example, a plate, a film, a sheet, or the like can be used.
- the thickness of the support is not limited, but is usually 5 ⁇ m or more, preferably 20 ⁇ m or more, and is usually 20 mm or less, preferably 10 mm or less. It is preferable that the thickness of the support is 5 ⁇ m or more because the possibility of insufficient strength is reduced. It is preferable that the thickness of the support is 20 mm or less, since the cost is suppressed and the weight does not become heavy.
- the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, while it is usually 10 mm or less, preferably 5 mm or less. It is preferable that the thickness of the glass substrate is 0.01 mm or more, because the mechanical strength is increased and the glass substrate is hardly broken. In addition, it is preferable that the thickness of the glass substrate is 5 mm or less because it does not become heavy.
- the roll-to-roll method is a method in which a flexible base material wound in a roll shape is unwound and processed intermittently or continuously while being taken up by a winding roll. is there. According to the roll-to-roll method, it is possible to batch process long substrates on the order of km, so that the production method is more suitable for mass production than the sheet-to-sheet method.
- the size of the roll that can be used in the roll-to-roll system is not particularly limited as long as it can be handled by a roll-to-roll system manufacturing apparatus, but the outer diameter of the roll core is usually 5 m or less, preferably 3 m or less, more preferably 1 m or less. On the other hand, it is usually at least 1 cm, preferably at least 3 cm, more preferably at least 5 cm, further preferably at least 10 cm, particularly preferably at least 20 cm.
- the diameter is equal to or less than the upper limit, the handleability of the roll is high, and when the diameter is equal to or more than the lower limit, the layer formed in each of the following steps reduces the possibility of being broken by bending stress. It is preferred in that respect.
- the width of the roll is usually at least 5 cm, preferably at least 10 cm, more preferably at least 20 cm, while it is usually at most 5 m, preferably at most 3 m, more preferably at most 2 m. It is preferable that the width is equal to or less than the above upper limit in that the handleability of the roll is high.
- a molded body can be obtained by shaving a solid resin composite material formed by a molding method including heat treatment into a desired shape.
- the first aspect of the above-described resin composite material is used for electronic material device applications. Further, the second and third aspects can be used not only for electronic material devices, but also for applications such as catalyst modules, molecular sieve membrane modules, optical members, moisture absorbing members, foods, building members, and packaging members, Above all, it is preferable to use it as a constituent member of an electronic material device, for example, a base material, a getter material film, a sealing material, etc., because the high properties of the resin composite material can be utilized.
- the material containing the resin composite material can be used as a film.
- the film thickness of the resin composite material when used in the form of a film is not particularly limited, but may be appropriately set according to the intended use, and is usually larger than 0.5 ⁇ m, preferably 1 ⁇ m or more.
- the thickness of the resin composite material can be measured by a normal thickness gauge such as a non-contact thickness gauge or a contact thickness gauge.
- a normal thickness gauge such as a non-contact thickness gauge or a contact thickness gauge.
- the non-contact type include a confocal microscope (for example, a shape measurement laser microscope VK-X200 manufactured by Keyence Corporation) and the like.
- a confocal microscope for example, a shape measurement laser microscope VK-X200 manufactured by Keyence Corporation
- An electronic device has two or more electrodes, and a device that controls a current flowing between the electrodes and a generated voltage by using an electric, optical, magnetic, or chemical substance, or a light or an electric field generated by an applied voltage or current.
- a device for generating a magnetic field include a resistor, a rectifier (diode), a switching element (transistor, thyristor), an amplifying element (transistor), a memory element, a chemical sensor, or the like, or a device in which these elements are combined or integrated.
- a photodiode or a phototransistor that generates a photocurrent an electroluminescent element that emits light by applying an electric field
- an optical element such as a photoelectric conversion element or a solar cell that generates an electromotive force by light
- More specific examples of electronic devices are described in S.A. M. Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981).
- the electronic device include a field effect transistor (FET) element, an electroluminescent element (LED), a photoelectric conversion element, and a solar cell.
- FET field effect transistor
- LED electroluminescent element
- solar cell a solar cell
- a field effect transistor (FET) element has a resin composite material as a constituent element.
- a field effect transistor (FET) element according to one embodiment has a semiconductor layer, an insulator layer, a source electrode, a gate electrode, and a drain electrode on a base material.
- the substrate has the resin composite material according to one embodiment of the present invention. Since the resin composite material has a low average coefficient of thermal expansion, it is preferably used as a base material.
- FIG. 2 is a diagram schematically illustrating an example of the structure of the FET element.
- reference numeral 11 denotes a semiconductor layer
- 12 denotes an insulator layer
- 13 and 14 denote source and drain electrodes
- 15 denotes a gate electrode
- 16 denotes a base material
- 17 denotes an FET element.
- FIGS. 2A to 2D each show an FET device having a different structure, but all show structural examples of the FET device.
- these constituent members constituting the FET element and the method of manufacturing the same and known techniques can be used. For example, techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.
- the term “semiconductor” is defined by the carrier mobility in a solid state.
- the carrier mobility is an index indicating how fast (or many) charges (electrons or holes) can be moved.
- the “semiconductor” in this specification has a carrier mobility at room temperature of usually 1.0 ⁇ 10 ⁇ 6 cm 2 / V ⁇ s or more, preferably 1.0 ⁇ 10 ⁇ 5 cm 2 / V ⁇ s or more. It is preferably at least 5.0 ⁇ 10 ⁇ 5 cm 2 / V ⁇ s, more preferably at least 1.0 ⁇ 10 ⁇ 4 cm 2 / V ⁇ s.
- the carrier mobility can be measured, for example, by measuring the IV characteristics of a field-effect transistor.
- the FET element is usually manufactured on the base material 16.
- the material of the base material 16 is not particularly limited as long as the effects of the present invention are not significantly impaired.
- Preferable examples of the material of the base material 16 include an inorganic material such as quartz, glass, sapphire, and titania; and a flexible base material such as a molded product of the above-described resin composite material.
- the flexible substrate is a substrate having a radius of curvature of usually 0.1 mm or more and 10,000 mm or less.
- the radius of curvature is preferably 0.3 mm or more, more preferably 1 mm or more, in order to achieve both flexibility and characteristics as a support. 3,000 mm or less, more preferably 1,000 mm or less.
- the radius of curvature can be determined by using a confocal microscope (for example, a shape measuring laser microscope VK-X200 manufactured by KEYENCE CORPORATION) with a substrate bent to a point where no destruction such as strain or crack appears.
- the flexible base material are not limited as long as the resin composite material according to one embodiment of the present invention is contained.
- Resins such as epoxy resins; paper materials such as paper or synthetic paper; silver, copper, Composite materials such as those obtained by coating or laminating the surface of a metal foil such as stainless steel, titanium or aluminum to impart insulation, and the above-mentioned resin composite moldings.
- the molded body of the resin composite material is preferably a flexible substrate in terms of production such as a roll-to-roll method, but can be used as the substrate 16 even if it is not a flexible substrate.
- the characteristics of the FET can be improved.
- the film quality of the semiconductor layer 11 to be formed is improved by adjusting the hydrophilicity / hydrophobicity of the substrate 16, and in particular, the characteristics of the interface between the substrate 13 and the semiconductor layer 11 are improved.
- Such a substrate treatment include hydrophobizing treatment using hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane and the like; acid treatment using an acid such as hydrochloric acid, sulfuric acid, and acetic acid; sodium hydroxide, potassium hydroxide, Alkaline treatment using calcium hydroxide and ammonia; ozone treatment; fluorination treatment; plasma treatment using oxygen or argon; formation treatment of Langmuir-Blodgett film; formation treatment of other insulator or semiconductor thin films Is mentioned.
- Electroluminescent device (LED) has a component containing a resin composite material.
- An electroluminescent element is a self-luminous element utilizing the principle that a fluorescent substance emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied.
- FIG. 3 is a cross-sectional view schematically showing one embodiment of the electroluminescent device.
- reference numeral 31 denotes a base material
- 32 denotes an anode
- 33 denotes a hole injection layer
- 34 denotes a hole transport layer
- 35 denotes a light emitting layer
- 36 denotes an electron transport layer
- 37 denotes an electron injection layer
- 38 denotes a cathode
- 39 Indicates an electroluminescent element.
- the electroluminescent element does not need to have all of these components, and the necessary components can be arbitrarily selected.
- the hole injection layer 33, the hole transport layer 34, the electron transport layer 36, and the electron injection layer 37 there is no particular limitation on these constituent members constituting the electroluminescent element and the method of manufacturing the same, and known techniques can be used. For example, techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.
- the base material 31 has a resin composite material.
- the resin composite material is preferably used as a material of the base material 31 because of its properties.
- the substrate 31 serves as a support for the electroluminescent element 39, and its material is not particularly limited as long as the effects of the present invention are not significantly impaired.
- the material of the base material 31 include inorganic materials such as quartz, glass, sapphire, and titania; and flexible base materials such as the above-described resin composite moldings.
- the flexible base material are not limited as long as the resin composite material according to one embodiment of the present invention is contained.
- Resins such as epoxy resins; paper materials such as paper or synthetic paper; silver, copper, A composite material such as a metal foil of stainless steel, titanium, aluminum, or the like, whose surface is coated or laminated to impart insulation, and a molded article of a resin composite material.
- the molded body of the resin composite material is preferably a flexible substrate in terms of production such as a roll-to-roll method, but can be used as the substrate 31 even if it is not a flexible substrate.
- soda glass soda glass, blue plate glass, non-alkali glass and the like can be mentioned.
- alkali-free glass is preferred among these because ions eluted from glass are small.
- the shape of the base material 31 is not limited, and for example, a plate-like, film-like, sheet-like or the like can be used.
- the thickness of the substrate 31 is not limited, but is usually 5 ⁇ m or more, preferably 20 ⁇ m or more, and is usually 20 mm or less, preferably 10 mm or less. It is preferable that the thickness of the base material is 5 ⁇ m or more because the possibility that the strength of the electroluminescent element is insufficient is reduced. It is preferable that the film thickness of the base material is 20 mm or less, because the cost is suppressed and the mass is not increased.
- the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, while it is usually 1 cm or less, preferably 0.5 cm or less. It is preferable that the thickness of the glass substrate 31 be 0.01 mm or more, because the mechanical strength increases and the glass substrate 31 is hardly broken. In addition, it is preferable that the thickness of the glass substrate 31 be 0.5 cm or less because the weight does not increase.
- FIG. 3 shows only one embodiment of the electroluminescent device, and the electroluminescent device is not limited to the illustrated configuration.
- the anodes 32 can be stacked in this order.
- the configuration of the electroluminescent element is not particularly limited, and may be a single element or an element having a structure arranged in an array, in which an anode and a cathode are arranged in an XY matrix. May be used.
- the photoelectric conversion element has a component containing a resin composite material.
- a photoelectric conversion element according to one embodiment has at least a pair of electrodes and an active layer existing between the electrodes. Further, the photoelectric conversion element according to one embodiment may have other components including a base material, an electron extraction layer, and a hole extraction layer.
- FIG. 4 is a cross-sectional view schematically illustrating an embodiment of the photoelectric conversion element.
- the photoelectric conversion element shown in FIG. 4 is a photoelectric conversion element used for a general thin-film solar cell, but the photoelectric conversion element is not limited to that shown in FIG.
- the photoelectric conversion element 57 according to one embodiment includes a base 56, a cathode (electrode) 51, an electron extraction layer (buffer layer) 52, an active layer 53, a hole extraction layer (buffer layer) 54, and an anode (electrode) 55. It has a layer structure formed in this order. Note that it is not always necessary to provide the electron extraction layer 52 and the hole extraction layer 54.
- these constituent members constituting the photoelectric conversion element and the method of manufacturing the same and well-known techniques can be used. For example, techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.
- the base 56 has a resin composite material.
- the resin composite material is preferably used as the material of the base material 56 because of its properties.
- the photoelectric conversion element 57 has a base material 56 that normally serves as a support.
- the material of the substrate 56 is not particularly limited as long as the effects of the present invention are not significantly impaired.
- Preferable examples of the material of the substrate 56 include an inorganic material such as quartz, glass, sapphire, or titania; and a flexible substrate such as a molded article of a resin composite material.
- the flexible base material are not limited as long as the resin composite material according to one embodiment of the present invention is contained.
- Resins such as epoxy resins; paper materials such as paper or synthetic paper; silver, copper, Composite materials such as those obtained by coating or laminating the surface of a metal foil such as stainless steel, titanium or aluminum to impart insulation, and the above-mentioned resin composite moldings.
- the molded body of the resin composite material is preferably a flexible substrate in terms of production such as a roll-to-roll method, but can be used as the substrate 56 even if it is not a flexible substrate.
- soda glass soda glass, blue plate glass, non-alkali glass and the like can be mentioned.
- alkali-free glass is preferred among these because ions eluted from glass are small.
- the shape of the substrate 56 is not limited, and for example, a plate-like, film-like, sheet-like, or the like can be used.
- the thickness of the substrate 56 is not limited, but is usually 5 ⁇ m or more, preferably 20 ⁇ m or more, and is usually 20 mm or less, preferably 10 mm or less. It is preferable that the film thickness of the base material 56 be 5 ⁇ m or more because the possibility that the strength of the photoelectric conversion element is insufficient is reduced. It is preferable that the film thickness of the base material 56 is 20 mm or less, because the cost is suppressed and the mass is not increased.
- the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, while it is usually 1 cm or less, preferably 0.5 cm or less. It is preferable that the thickness of the glass substrate 31 be 0.01 mm or more, because the mechanical strength increases and the glass substrate 31 is hardly broken. Further, it is preferable that the thickness of the glass substrate 56 is 0.5 cm or less, because the weight does not increase.
- FIG. 5 is a cross-sectional view schematically illustrating a configuration of a thin-film solar cell that is a solar cell according to an embodiment of the present invention.
- the thin-film solar cell 111 according to the embodiment includes a weather-resistant protective film 101, an ultraviolet cut film 102, a gas barrier film 103, a getter material film 104, a sealing material 105, An element 106, a sealing material 107, a getter material film 108, a gas barrier film 109, and a back sheet 110 are provided in this order.
- the thin-film solar cell 111 has a photoelectric conversion element as the solar cell element 106. Then, light is irradiated from the side where the weather-resistant protective film 101 is formed (the lower side in FIG. 5), and the solar cell element 106 generates power. Note that the thin-film solar cell 111 does not need to have all of these components, and the necessary components can be arbitrarily selected.
- the weather-resistant protective film, back sheet, ultraviolet ray cut film, gas barrier film, getter material film, and sealing material are used for the above-mentioned electronic devices such as a field effect transistor element (FET) and an electroluminescent element (LED). Can be used.
- FET field effect transistor element
- LED electroluminescent element
- the method of manufacturing the thin-film solar cell 111 of the present embodiment is not limited.
- a method of manufacturing the solar cell of the embodiment of FIG. 6 after manufacturing the laminate illustrated in FIG. There is a method of performing.
- the solar cell element 106 of the present embodiment is excellent in heat resistance, and thus is preferable in that deterioration due to the lamination sealing step is reduced.
- the laminate shown in FIG. 5 can be manufactured by using a known technique.
- the method of the lamination sealing step is not particularly limited as long as the effects of the present invention are not impaired.
- wet lamination, dry lamination, hot melt lamination, extrusion lamination, co-extrusion molding lamination, extrusion coating, and light curing adhesive Laminating, thermal laminating and the like can be mentioned.
- a lamination method using a photo-curing adhesive which has a proven track record in sealing organic electroluminescent elements, and a hot-melt laminate or a thermal laminate, which has a track record in solar cells, are preferable. It is more preferable that a material can be used.
- the heating temperature in the laminating step is usually 130 ° C or higher, preferably 140 ° C or higher, and is usually 180 ° C or lower, preferably 170 ° C or lower.
- the heating time of the laminating step is usually 10 minutes or more, preferably 20 minutes or more, and usually 100 minutes or less, preferably 90 minutes or less.
- the pressure in the lamination sealing step is usually at least 0.001 MPa, preferably at least 0.01 MPa, and is usually at most 0.2 MPa, preferably at most 0.1 MPa. By setting the pressure within this range, the sealing is reliably performed, and the thickness of the sealing materials 105 and 107 is prevented from protruding from the end portions and the film thickness is reduced due to excessive pressure, and dimensional stability can be secured.
- a device in which two or more solar cell elements 106 are connected in series or in parallel can be manufactured in the same manner as described above.
- a solar cell includes a solar cell for building materials, a solar cell for cars, a solar cell for interiors, a solar cell for railways, a solar cell for ships, a solar cell for airplanes, a solar cell for spacecraft, and a solar cell for home appliances. It can be used as a battery, a solar cell for a mobile phone, or a solar cell for a toy.
- the solar cell particularly the thin-film solar cell 111 described above, may be used as it is, or may be used as a component of a solar cell module.
- a solar cell particularly a solar cell module 113 including the above-described thin film solar cell 111 on a base 112, and install and use the solar cell module 113 at a place of use. it can.
- the base material 112 As the base material 112, a known technique can be used. For example, as a material of the base material 112, a material described in WO 2013/180230 or JP-A-2015-134703 can be used. Further, a polyimide resin composite material may be used for the base material 112. For example, when a building material plate is used as the base material 112, a solar cell panel for an outer wall of a building can be manufactured as the solar cell module 113 by providing the thin film solar cell 111 on the surface of the plate.
- zeolite-platinum target distance was set to 30 mm, and the zeolite sample surface was vapor-deposited by sputtering for 60 seconds so that the platinum thickness on the zeolite sample surface became about 9 nm, and then observed by SEM.
- the working distance in the SEM was 10 to 11 mm, the acceleration voltage was 10 kV, and the spot size was 30 mm.
- the average primary particle diameter was determined by observing the particles with a scanning electron microscope JSM-6010LV manufactured by JEOL, measuring the particle diameters of arbitrarily selected 30 primary particles, and averaging the particle diameters of the primary particles.
- the particle diameter was defined as the diameter of a circle (equivalent circle diameter) having an area equal to the projected area of the particle.
- the average coefficient of thermal expansion of the zeolite at 60 to 220 ° C. was measured by calculating the lattice constant using an X-ray diffractometer D8ADVANCE manufactured by Bruker and X-ray diffraction analysis software JADE.
- ⁇ Evaluation of film> (Average coefficient of thermal expansion of film)
- the sample shape was 4 mm in width and the distance between the chucks was 20 mm, and the temperature was raised at a rate of 10 ° C./min.
- the retardation value (Rth) of the film was calculated as a value at a wavelength of 460 nm for a film having a film thickness of 10 ⁇ m using a phase difference film / optical material inspection apparatus RETS-100 manufactured by Otsuka Electronics Co., Ltd.
- the haze ratio of the film was measured using a TM Double Beam Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd. The haze ratio used this time is a value for D65 light.
- the storage elastic modulus at each temperature of the resin composite film was measured by a dynamic viscoelasticity measurement method described in JIS K-7244 using a dynamic viscoelasticity apparatus DMS6100 manufactured by SII Nanotechnology Inc. (Measurement temperature range: ⁇ 100 ° C. to 150 ° C., frequency: 1 Hz, heating rate: 5 ° C./min).
- the elastic modulus shown in Table 1 is an elastic modulus at a measurement temperature of 25 ° C.
- Synthesis example 1 Synthesis method of zeolite C1
- sodium hydroxide manufactured by Kishida Chemical Company N, N, N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) manufactured by Seikem as a structure directing agent (SDA), aluminum hydroxide manufactured by Aldrich Co., Ltd.
- Cataloid SI-30 manufactured by Nikki Shokubai Kasei Co., Ltd. was sequentially added.
- the composition of the resulting mixture was 1.0SiO 2 /0.033Al 2 O 3 /0.1NaOH/0.06KOH/0.07TMAdaOH/20H 2 O.
- CHA-type zeolite with respect to SiO 2 was added to the mixture, and the mixture was mixed well. Then, the obtained mixture was placed in a pressure vessel, and rotated at 15 rpm in a 160 ° C. oven. While performing the hydrothermal synthesis for 48 hours. After suction filtration, washing, and drying, a CHA-type zeolite (as-made), zeolite C1, was obtained.
- the average primary particle diameter was 1,000 nm. Further, as a result of measuring the average thermal expansion coefficient of zeolite C1 at 60 to 220 ° C., the average thermal expansion coefficient of zeolite C1 was ⁇ 10 ppm / K.
- the average primary particle diameter was 200 nm.
- the average coefficient of thermal expansion of zeolite C2 at 60 to 220 ° C. was measured.
- the average coefficient of thermal expansion of zeolite C2 was ⁇ 10 ppm / K.
- the composition of the resulting mixture was 1.0SiO 2 /0.025Al 2 O 3 /0.3NaOH/0.3KOH/0.06TMAOH/10H 2 O. After mixing well, the obtained mixture was put into a pressure-resistant container, and hydrothermal synthesis was performed for 5 days while rotating at 15 rpm in an oven at 130 ° C. After suction filtration, washing, and drying, Linde type T zeolite (as-made), which is an intergrowth of OFF type and ERI type, was obtained. This powder was calcined at 600 ° C. for 6 hours in an air stream to obtain zeolite T1.
- the average primary particle diameter was 300 nm. Further, as a result of measuring the average thermal expansion coefficient of zeolite T1 at 60 to 220 ° C., the average thermal expansion coefficient of zeolite T1 was ⁇ 12 ppm / K.
- APC type aluminophosphate was obtained.
- the obtained APC-type aluminophosphate was calcined at 600 ° C. for 6 hours under flowing air to obtain aluminophosphate A1.
- Synthesis Example 5 Synthesis method of silicalite 1
- Water and tetrapropylammonium hydroxide (TPAOH) manufactured by Seikem Co., Ltd. and Snowtex-40 colloidal silica manufactured by Nissan Chemical Co., Ltd. were sequentially added to the container as a structure-directing agent (SDA).
- the composition of the resulting mixture was 1.0SiO 2 /0.4TPAOH/11.8H 2 O.
- the obtained mixture was put into a pressure-resistant container, and hydrothermal synthesis was performed for 20 hours while rotating at 15 rpm in an oven at 100 ° C.
- silicalite-1 type zeolite having MFI type crystals was obtained.
- the obtained silicalite-1 type zeolite was calcined at 600 ° C. for 6 hours under flowing air to obtain silicalite 1.
- the obtained mixture was placed in a pressure-resistant container, subjected to hydrothermal synthesis at 110 ° C. for 96 hours, filtered, and washed with water to obtain an RHO-type zeolite.
- the obtained RHO type was calcined at 600 ° C. for 6 hours under flowing air to obtain zeolite R1.
- the polyimide precursor has a nuclear hydrogenated (hydrogenated) aromatic compound.
- Example 1 Production of resin composite film using polyimide precursor-containing composition M1> (Comparative Example 1-1: Method for producing polyimide resin film 1)
- the polyimide precursor-containing composition M1 was diluted with N-methylpyrrolidone and adjusted so that the polyimide precursor was 20% by mass.
- the obtained ink was applied onto an alkali glass (manufactured by Corning) using an applicator manufactured by Tester Sangyo Co., Ltd., and dried and fired at 330 ° C. for 30 minutes to obtain a polyimide resin film 1.
- the film thickness was 10 ⁇ m.
- the glass transition temperature (Tg) of the polyimide resin film 1 determined from the inflection point when the average thermal expansion coefficient of the film was measured was 320 ° C.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 1-1 Method for producing polyimide resin composite material film 1
- Zeolite C1 was added to N-methylpyrrolidone, and beads milling was performed with a Labstar mini manufactured by Ashizawa Finetech Co., Ltd. to obtain a zeolite dispersion D1 having a zeolite C1 content of 4% by mass.
- zeolite dispersion liquid D1 was centrifuged at 5000 rpm for 30 minutes using a Hitachi micro machine high-speed microcentrifuge CF15RN, and the supernatant was removed to obtain a centrifuged zeolite dispersion liquid.
- the amount of zeolite in the zeolite dispersion after centrifugation was 2.5% by mass.
- D 50 values measured by a dynamic light scattering particle size distribution analyzer (Microtrac Bell Co. Nanotrac WaveII-EX150) was 35 nm.
- Example 1-2 Method for producing polyimide resin composite film 2
- a polyimide resin composite material film 2 was obtained in the same manner as in Example 1, except that 4.8 g of the zeolite dispersion D1 and 4 g of the polyimide precursor-containing composition M1 were mixed.
- the thickness of the film was 6 ⁇ m, and the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 2-1 Method for producing polyimide resin composite material film 3
- a polyimide resin composite film 3 was obtained in the same manner as in Example 1-1, except that zeolite C2 was used instead of zeolite C1.
- the thickness of the film was 21 ⁇ m, and the zeolite content in the obtained film was 28.6% by mass based on the film mass.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 2-2 Method for producing polyimide resin composite material film 4
- a polyimide resin composite film 4 was obtained in the same manner as in Example 1-2, except that zeolite C2 was used instead of zeolite C1.
- the thickness of the film was 21 ⁇ m, and the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 3-1 Method for producing polyimide resin composite material film 5
- 0.24 g of zeolite T1, 0.6 g of a polyimide precursor, and 2.4 g of NMP were mixed and stirred to form an ink.
- the obtained ink was applied with an applicator manufactured by Tester Sangyo Co., Ltd., and dried and fired at 330 ° C. for 30 minutes to obtain a polyimide resin composite film 1.
- the thickness of the film was 44 ⁇ m, and the content of zeolite in the obtained film was 28.6% by mass based on the mass of the film.
- Table 1 shows the average thermal expansion coefficient and the haze ratio of the obtained film.
- Example 3-2 Method for producing polyimide resin composite film 6
- 0.06 g of zeolite T1, 0.6 g of a polyimide precursor, and 2.4 g of NMP were mixed and stirred with a stirrer to obtain an ink.
- the obtained ink was applied using an applicator manufactured by Tester Sangyo Co., Ltd., and dried and fired at 330 ° C. for 30 minutes to obtain a polyimide resin composite film 6.
- the thickness of the film was 21 ⁇ m, and the content of zeolite in the obtained film was 9.1% by mass based on the mass of the film.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, and the haze ratio of the obtained film.
- Example 4-1 Method for producing polyimide resin composite film 7
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average thermal expansion coefficient and the haze ratio of the obtained film.
- Example 5-1 Method for producing polyimide resin composite film 8
- Example 1-2 Method for Producing Polyimide Resin Composite Film 9
- a polyimide resin composite film 9 was produced in the same manner as in Example 1-1 except that silica SC2500-SQ (average primary particle diameter: 200 nm) manufactured by Admatechs was used instead of zeolite T1.
- the thickness of the film was 18 ⁇ m, and the content of zeolite in the obtained film was 9.1% by mass based on the mass of the film.
- Table 1 shows the average coefficient of thermal expansion, the haze ratio, and the elastic modulus of the obtained film.
- Example 1-3 Method for producing polyimide resin composite film 10.
- a polyimide resin composite film 10 was produced in the same manner as in Example 1-1, except that zeolite C1 was replaced with zirconium tungstate fine ZWO-01 manufactured by Furuuchi Co., Ltd., which was a negative expansion material.
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 1-4 Method for producing polyimide resin composite film 11
- a polyimide resin composite film 11 was produced in the same manner as in Example 3-1 except that zeolite A1 was used instead of zeolite T1.
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average thermal expansion coefficient of the obtained film.
- Example 1-5 Method for Producing Polyimide Resin Composite Film 12
- a polyimide resin composite film 12 was produced in the same manner as in Example 3-1 except that silicalite 1 was used instead of zeolite T1.
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average coefficient of thermal expansion, the retardation value, the haze ratio, and the elastic modulus of the obtained film.
- Example 1-6 Method for producing polyimide resin composite film 13
- a polyimide resin composite film 13 was produced in the same manner as in Example 3-1 except that Zeolite Z4A-005 (average primary particle diameter: 50 nm, LTA type zeolite) manufactured by Nakamura Choko Co., Ltd. was used instead of zeolite T1. .
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average thermal expansion coefficient of the obtained film.
- Example 1-7 Method for producing polyimide resin composite film 14
- a polyimide resin composite film 14 was produced in the same manner as in Example 3-1 except that zeolite R1 was used instead of zeolite T1.
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average thermal expansion coefficient of the obtained film.
- Resin composition production example 2 production method of non-hydrogenated polyimide precursor-containing composition M2
- 635 g (2.16 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 445 g of 4,4′-diaminodiphenyl ether were placed.
- (2.22 mol) and 3240 g of N, N-dimethylacetamide were added, and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain a polyimide precursor-containing composition M2 containing 25% by mass of a polyimide precursor.
- the polyimide precursor does not have a nuclear hydrogenated (hydrogenated) aromatic compound.
- Comparative Example 1-8 Method for producing polyimide resin film 2
- a polyimide resin film 2 was produced in the same manner as in Comparative Example 1-1, except that M2 was used instead of the polyimide precursor-containing composition M1.
- Table 1 shows the average thermal expansion coefficient of the obtained film.
- Example 6-1 Method for producing polyimide resin composite film 15
- a polyimide resin composite material film 15 was obtained in the same manner as in Example 1-1, except that zeolite C1 and the polyimide precursor-containing material M2 were used.
- the content of zeolite in the obtained film was 9.1% by mass based on the film mass.
- Table 1 shows the average thermal expansion coefficient of the obtained film.
- the zeolite-containing polyimide resin composite according to the embodiment of the present invention the average thermal expansion coefficient of the resin composite is less than 50 ppm, the retardation value of the resin composite is 150 nm or less, and polyimide It can be seen that the haze ratio of the resin composite material is as low as 5% or less, which is as low as the polyimide resin.
- the zeolite-containing polyimide resin composite according to the embodiment of the present invention has an average thermal expansion. The decrease in coefficient is large.
- Silica having a positive coefficient of thermal expansion and polyimide resin composite containing zirconium tungstate having a negative coefficient of thermal expansion have the same average coefficient of thermal expansion, and the average coefficient of thermal expansion of the filler itself is the average of the resin composite. It does not determine the coefficient of thermal expansion.
- the average coefficient of thermal expansion of the polyimide resin composite containing a specific zeolite is greatly reduced.
- the average coefficient of thermal expansion of the zeolite containing d6r (CHA, ERI) and / or the zeolite containing mtw (BEA) is larger than that of the zeolite-containing polyimide resin composite containing no zeolite. It is presumed that the average thermal expansion coefficient became smaller due to the inclusion of CBU.
- the decrease rate of the average coefficient of thermal expansion when 9.1 mass% of zeolite is contained is 14.0% when using hydrogenated polyimide, compared to 12.0% when using non-hydrogenated polyimide.
- the effect of hydrogenated polyimide was more remarkable. Although the cause is not clear, it is considered that the hydrogenation weakens the ⁇ - ⁇ stack between the resins and enhances the interaction with the zeolite.
- the zeolite-containing polyimide resin composite material according to one embodiment of the present invention high suppression of deformation such as warpage, good image clarity, and all have high transparency, members of electronic devices and the like It can be seen that a zeolite-containing polyimide resin composite material suitable for the above can be provided at low cost.
- the polyimide resin composite material according to one embodiment of the present invention has a high suppression property against deformation such as warpage, a high image clarity, and a high transparency, and is a zeolite-containing polyimide resin composite material suitable for members of electronic devices and the like. Can be provided at low cost.
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Abstract
Description
[1] 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂と、を含有し、電子材料デバイス用である、ゼオライト含有ポリイミド樹脂複合材。
[2] ゼオライトと、ポリイミド樹脂と、を含有するゼオライト含有ポリイミド複合材であって、
0℃以上前記ポリイミド樹脂のガラス転移温度以下における平均熱膨張係数が50ppm/K未満であり、
リタデーション値が150nm以下であり、かつ、
ヘイズ率が5%以下である、ゼオライト含有ポリイミド樹脂複合材。
[3] 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂と、を含有し、透明である、ゼオライト含有ポリイミド樹脂複合材。
[4] 前記ゼオライトが、AEI、AFT、AFX、CHA、ERI、KFI、SAT、SAV、SFW、及びTSC構造のいずれかを有する、[1]~[3]のいずれかに記載のゼオライト含有ポリイミド樹脂複合材。
[5] 25℃における弾性率が4.5GPa以上である、[1]~[4]のいずれかに記載のゼオライト含有ポリイミド樹脂複合材。
[6] ゼオライト含有ポリイミド樹脂複合材前記ゼオライトが、に対し1質量%以上80質量%以下含まれる、[1]~[5]のいずれかに記載のゼオライト含有ポリイミド樹脂複合材。
[7] 前記ポリイミド樹脂が、核水素化された芳香族化合物を有するポリイミド樹脂である、[1]~[6]のいずれかに記載のゼオライト含有ポリイミド樹脂複合材。
[8] 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂前駆体と、を含有する、ゼオライト含有ポリイミド樹脂前駆体組成物。
[9] [8]に記載の組成物の硬化物である、ゼオライト含有ポリイミド樹脂複合材。
[10] [1]~[7]、又は[9]のいずれかに記載のゼオライト含有ポリイミド樹脂複合材を含有するフィルム。
[11] [1]~[7]、又は[9]のいずれかに記載のオライト含有ポリイミド樹脂複合材を含有する電子デバイス。
[12] ゼオライトと、ポリイミド樹脂と、を含有するゼオライト含有ポリイミド複合材であって、
0℃以上前記ポリイミド樹脂のガラス転移温度以下における平均熱膨張係数が50ppm/K未満であり、
25℃における弾性率が4.5GPa以上であり、かつ、
ヘイズ率が5%以下である、ゼオライト含有ポリイミド樹脂複合材。
また、本発明の別の実施形態であるゼオライト含有ポリイミド樹脂複合材の第2の態様は、ゼオライト含有透明ポリイミド樹脂複合材であり、構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂と、を含有し、透明である、ゼオライト含有透明ポリイミド樹脂複合材である。本発明における「透明」とは、ヘイズ率が5%以下のポリイミド樹脂複合材である。
本願明細書では、ゼオライト含有ポリイミド樹脂複合材を、単に「複合材」、「樹脂複合材」、及び「ポリイミド樹脂複合材」とも称する。
図1は、本発明の一実施形態に係る樹脂複合材を模式的に表す図である。以下に、樹脂複合材1について、詳細に説明する。
図1に示すように、樹脂複合材1は、ゼオライト2と、ポリイミド樹脂3と、を含有する。
<1.1 ゼオライト>
樹脂複合材に含有されるゼオライトについて説明する。なお、ゼオライトとは、ケイ素又はアルミニウムと、酸素と、を含んで構成される、TO4ユニット(T元素とは、骨格を構成する酸素以外の元素)を基本単位としたものであり、具体的には、結晶性多孔質なアルミノケイ酸塩、結晶性多孔質なアルミノリン酸塩(ALPO)、又は結晶性多孔質なシリコアルミノリン酸塩(SAPO)が挙げられる。さらに、このTiO4ユニットが、いくつか(数個~数十個)つながった、Composite Building Unit(CBU)と呼ばれる構造単位から成り立っている。そのために、規則的なチャンネル(管状細孔)とキャビティ(空洞)を有している。
樹脂複合材中に含有されるゼオライトの含有率は、特段の制限はないが、通常、1質量%以上、好ましくは3質量%以上、より好ましくは5質量%以上、さらに好ましくは7質量%以上、特に好ましくは10質量%以上であり、最も好ましくは15質量%以上であり、一方、通常、80質量%以下、好ましくは70質量%以下、より好ましくは50質量%以下、さらに好ましくは40質量%以下、特に好ましくは30質量%以下、最も好ましくは20質量%以下である。上述の通り、樹脂に少量のゼオライトを添加すれば、フィラーとしてシリカ等を用いた場合と比較して、得られる平均熱膨張係数を大きく低下させることができる。
ゼオライトの平均熱膨張係数は、樹脂複合材が好ましい性能を示す限りにおいて、特段の制限はないが、0ppm/K未満であり、好ましくは-2ppm/K以下であり、より好ましくは-3ppm/K以下であり、さらに好ましくは-5ppm/K以下であり、特に好ましくは-7ppm/K以下であり、最も好ましくは-10ppm/K以下であり、一方、通常、-1000ppm/K以上であり、好ましくは-900ppm/K以上であり、より好ましくは-800ppm/K以上であり、さらに好ましくは-700ppm/K以上であり、特に好ましくは-500ppm/K以上であり、最も好ましくは-300ppm/K以上である。ゼオライトの平均熱膨張係数が、上記範囲であれば、樹脂複合材は、ゼオライトの含有量が少なく、高いフレキブル性も維持することができた上で、脆化や変形等を抑制しながら、良好な画像明瞭性、及び高い透明性を兼ね備えることができる。
このゼオライトの平均熱膨張係数は、60℃と220℃の熱膨張係数を測定し、その平均をもって平均熱膨張係数とする。
以下に、樹脂複合材に用いられるポリイミド樹脂について述べる。
また、ポリイミド樹脂は、核水素化(「水添」とも称する)された芳香族化合物を有するポリイミド樹脂であっても、核水素化されていない芳香族化合物を有するポリイミド樹脂であってもよいが、ゼオライトとの相溶性が良い、言い換えればゼオライトとの接着性が向上する点から、特に電子デバイスに用いる場合には、核水素化された芳香族化合物を有するポリイミド樹脂であることが好ましい。
樹脂複合材は、ゼオライト、及びポリイミド樹脂以外に、本発明の効果を著しく損なわない限り、その他の化合物を含んでもよい。例えば、後述するように、樹脂複合材を製造する際に、インクや混練物に、分散剤、表面処理剤、界面活性剤、イミド化促進剤、溶媒等を含んでもよく、これらの残留成分が樹脂複合材中に含まれていてもよい。
上述の構成により、従来にない特性を有するゼオライト含有ポリイミド複合材が得られる。具体的には、本発明の別の実施形態であるゼオライト含有ポリイミド樹脂複合材の第3の態様であり、ゼオライトと、核水素化された芳香族化合物を有するポリイミド樹脂と、を含有するゼオライト含有ポリイミド樹脂複合材であって、0℃以上前記ポリイミド樹脂のガラス転移温度以下における該複合材の平均熱膨張係数が50ppm/K未満であり、該複合材のリタデーション値が150nm以下であり、該複合材のヘイズ率が5%以下である、ゼオライト含有ポリイミド複合材、又は、第4の態様であり、ゼオライトと、ポリイミド樹脂と、を含有するゼオライト含有ポリイミド複合材であって、0℃以上前記ポリイミド樹脂のガラス転移温度以下における平均熱膨張係数が50ppm/K未満であり、25℃における弾性率が4.5GPa以上であり、かつ、ヘイズ率が5%以下である、ゼオライト含有ポリイミド樹脂複合材が得られる。
樹脂複合材の貯蔵弾性率は、例えば、JIS K-7244法に記載の動的粘弾性測定法により、エスアイアイ・ナノテクノロジー社製動的粘弾性装置DMS6100を用いて、測定温度範囲:-100℃から150℃、周波数:1Hz、昇温速度:5℃/分の条件下、両持ち引張モードで測定することができる。
ポリイミド樹脂複合材の製造方法は、樹脂複合材が好ましい性能を示す限りにおいて、特段の制限はなく、加熱溶融状態で成形、射出成型する等の常法が使用できるが、ポリイミドの優れた強度やガスバリア性などを活用するためフィルム状にして使用されることも多い。そこで以下において、フィルム状の複合材を作製するのに特に適し、簡易な方法としてポリイミド樹脂前駆体と、ゼオライトと、溶媒と、を混合してゼオライト含有ポリイミド樹脂前駆体組成物(「インク」とも称する)を作製し、インクを支持体等に塗布した後に加熱乾燥する方法を例として説明する。よって以下に記載されたポリイミド樹脂、分散剤、溶媒等の説明はインクに限るものではなく、複合材に含まれていてもよい。
本発明の別の実施形態であるインクは、少なくとも、上述のゼオライトと、ポリイミド樹脂前駆体と、を含有したゼオライト含有ポリイミド樹脂前駆体組成物であり、これらの原料を混合、又は、ポリイミド樹脂前駆体に代えて、ポリイミド樹脂又はポリイミド樹脂前駆体原料(テトラカルボン酸2無水物、及びジアミン)と、溶媒と、を含有した組成物を混合して製造する。
樹脂複合材を成形する方法は、樹脂の成形に一般に用いられる方法を用いることができる。その際、樹脂複合材の製造に必要な加熱と、成形のための加熱とを同時に行ってもよい。
上述の樹脂複合材の第1の態様は、電子材料デバイスの用途で用いられる。また、第2及び第3の態様は、電子材料デバイスだけでなく、例えば、触媒モジュール、分子篩膜モジュール、光学部材、吸湿部材、食品、建築部材、及び包装部材等の用途で用いることができ、なかでも、電子材料デバイスの構成部材、例えば、基材、ゲッター材フィルム、封止材等に用いることは、樹脂複合材の高い特性を活かせるので、好ましい。
以下、電子デバイスとしてのポリイミド樹脂複合材を使用する例を説明する。
電子デバイスは、2個以上の電極を有し、その電極間に流れる電流や生じる電圧を、電気、光、磁気又は化学物質等により制御するデバイス、あるいは、印加した電圧や電流により、光や電場、磁場を発生させる装置である。具体的には、抵抗器、整流器(ダイオード)、スイッチング素子(トランジスタ、サイリスタ)、増幅素子(トランジスタ)、メモリー素子、若しくは化学センサー等、又はこれらの素子を組み合わせ若しくは集積化したデバイスが挙げられる。また、光電流を生じるフォトダイオード若しくはフォトトランジスタ、電界を印加することにより発光する電界発光素子、及び光により起電力を生じる光電変換素子若しくは太陽電池等の光素子も挙げることができる。電子デバイスのより具体的な例は、S.M.Sze著、Physics of Semiconductor Devices、2nd Edition(Wiley Interscience 1981)に記載されているものを挙げることができる。
電界効果トランジスタ(FET)素子は、樹脂複合材を構成要素として有している。一実施形態に係る電界効果トランジスタ(FET)素子は、基材上に、半導体層と、絶縁体層と、ソース電極と、ゲート電極と、ドレイン電極とを有する。
FET素子は、通常基材16上に作製する。基材16の材料は、本発明の効果を著しく損なわない限り特に限定されない。基材16の材料の好適な例は、石英、ガラス、サファイア又はチタニア等の無機材料;上述の樹脂複合材の成形体等のフレキシブル基材が挙げられる。
電界発光素子(LED)は、樹脂複合材を含有する構成要素を有している。電界発光素子は、電界を印加することにより、陽極より注入された正孔と陰極より注入された電子との再結合エネルギーによって蛍光性物質が発光する原理を利用した自発光素子である。
基材31は、電界発光素子39の支持体となるものであり、その材料は、本発明の効果を著しく損なわない限り特に限定されない。基材31の材料の好適な例としては、石英、ガラス、サファイア又はチタニア等の無機材料;上述の樹脂複合材の成形体等のフレキシブル基材が挙げられる。
光電変換素子は、樹脂複合材を含有する構成要素を有している。一実施形態に係る光電変換素子は、少なくとも一対の電極と、該電極間に存在する活性層と、を有する。また、一実施形態に係る光電変換素子は、基材、電子取り出し層、及び正孔取り出し層を含むその他の構成要素を有していてもよい。
光電変換素子57は、通常は支持体となる基材56を有する。
光電変換素子57は、太陽電池、なかでも薄膜太陽電池の太陽電池素子として使用されることが好ましい。図5は、本発明の一実施形態に係る太陽電池である薄膜太陽電池の構成を模式的に表す断面図である。図5に表すように、本実施形態に係る薄膜太陽電池111は、耐候性保護フィルム101と、紫外線カットフィルム102と、ガスバリアフィルム103と、ゲッター材フィルム104と、封止材105と、太陽電池素子106と、封止材107と、ゲッター材フィルム108と、ガスバリアフィルム109と、バックシート110と、をこの順に備える。本実施形態に係る薄膜太陽電池111は、太陽電池素子106として、光電変換素子を有している。そして、耐候性保護フィルム101が形成された側(図5中下方)から光が照射されて、太陽電池素子106が発電するようになっている。なお、薄膜太陽電池111は、これらの構成部材を全て有する必要はなく、必要な構成部材を任意に選択することができる。
太陽電池、特には上述した薄膜太陽電池111は、そのまま用いてもよいし、太陽電池モジュールの構成要素として用いられてもよい。例えば、図6に示すように、太陽電池、特には上述した薄膜太陽電池111を基材112上に備える太陽電池モジュール113を作製し、この太陽電池モジュール113を使用場所に設置して用いることができる。
(ゼオライトの平均一次粒径)
JEOL社製オートファインコーターJFC-1600にて、ゼオライト-白金ターゲット間距離30mmとし、60秒間のスパッタリングにより、ゼオライト試料表面の白金厚みが約9nmになるように蒸着させてから、SEMによる観察を行った。SEMにおける作動距離は10~11mmとし、加速電圧10kV、スポットサイズは30mmとした。平均一次粒子径は、JEOL社製走査電子顕微鏡JSM-6010LVによる粒子の観察において、任意に選択した30個の一次粒子について粒子径を測定し、その一次粒子の粒子径を平均して求めた。なお、粒子径は、粒子の投影面積と等しい面積を持つ、円の直径(円相当径)とした。
BRUKER社製X線回折装置D8ADVANCEとX線回折解析ソフトJADEを用いて格子定数を算出することで、ゼオライトの60~220℃における平均熱膨張係数を測定した。
(フィルムの平均熱膨張係数)
温度範囲60℃~220℃の平均熱膨張係数(CTE)を、エスアイアイ・ナノテクノロジー社製熱機械分析装置TMA/SS6100を使用して測定した。なお、サンプル形状は幅4mm、チャック間距離20mmとし、昇温速度10℃/minで昇温させた。
フィルムのリタデーション値(Rth)は、大塚電子社製位相差フィルム・光学材料検査装置RETS-100を用いて、膜厚10μmの膜に対しての、波長460nmの値として算出した。
フィルムのヘイズ率は、スガ試験機社製TMダブルビーム自動ヘイズコンピュータHZ-2を用いて測定した。今回用いたヘイズ率は、D65光に対する値である。
樹脂複合材フィルムの各温度における貯蔵弾性率を、JIS K-7244法に記載の動的粘弾性測定法により、エスアイアイ・ナノテクノロジー社製動的粘弾性装置DMS6100を用いて、両持ち引張モードで測定した(測定温度範囲:-100℃から150℃、周波数:1Hz、昇温速度:5℃/分)。表1に示す弾性率は、測定温度25℃における弾性率である。
(合成例1:ゼオライトC1の合成方法)
容器内に、キシダ化学社製水酸化ナトリウム、構造規定剤(SDA)として、セイケム社製N,N,N-トリメチル-1-アダマンタアンモニウム水酸化物(TMAdaOH)、アルドリッチ社製水酸化アルミニウム、日揮触媒化成社製Cataloid SI-30を順次加えた。得られた混合物の組成は、1.0SiO2/0.033Al2O3/0.1NaOH/0.06KOH/0.07TMAdaOH/20H2Oであった。その後、種結晶として、SiO2に対して2質量%のCHA型ゼオライトを混合物に加えて、よく混合した後、得られた混合物を耐圧容器に入れ、160℃のオーブン中で、15rpmで回転させながら、48時間水熱合成を行った。吸引濾過、洗浄した後に、乾燥することで、CHA型ゼオライト(as-made)である、ゼオライトC1を得た。
容器内に、水、キシダ化学社製水酸化カリウム、触媒化成工業社製FAU型ゼオライトUSY7を順次加えた。得られた混合物の組成は、1.0SiO2/0.143Al2O3/0.582KOH/36.2H2Oであった。よく混合した後、得られた混合物を耐圧容器に入れ、100℃のオーブン中で、静置させておいて、7日間水熱合成を行った。吸引濾過、洗浄した後に、乾燥することで、CHA型ゼオライトである、ゼオライトC2を得た。
Chemical Engineering Journal、 230、380、2013を参考にして、以下の合成を行った。容器内に、水、キシダ化学社製水酸化ナトリウム、キシダ化学社製水酸化カリウム、構造規定剤(SDA)として、セイケム社製テトラメチルアンモニウム水酸化物(TMAOH)、浅田化学工業社製アルミン酸ソーダ(酸化アルミニウム20.13%、酸化ナトリウム18.9%)、アルドリッチ社製 AS-40コロイダルシリカを順次加えた。得られた混合物の組成は、1.0SiO2/0.025Al2O3/0.3NaOH/0.3KOH/0.06TMAOH/10H2Oであった。良く混合した後、得られた混合物を耐圧容器に入れ、130℃のオーブン中で、15rpmで回転させながら、5日間水熱合成を行った。吸引濾過、洗浄した後に、乾燥することで、OFF型とERI型の連晶である、Linde T型ゼオライト(as―made)を得た。この粉末を600℃、6時間、空気流通下で焼成することにより、ゼオライトT1を得た。
容器内で、キシダ化学社製85%リン酸69gと水130gを混合した。これに、擬ベーマイト(75% Al2O3)40.8gを加えて撹拌させた。2時間撹拌後、トリエチルアミン27.3gと水120gの混合物を加えて、さらに1時間撹拌させた。良く混合した後、得られた混合物を耐圧容器に入れ、190℃のオーブンで、15rpmで回転させながら、12時間水熱合成を行った。吸引濾過、洗浄した後に、乾燥することで、APC型アルミノフォスフェートを得た。得られたAPC型アルミノフォスフェートを600℃、6時間、空気流通下で焼成することにより、アルミノフォスフェートA1を得た。
容器内に、水、構造規定剤(SDA)として、セイケム社製テトラプロピルアンモニウム水酸化物(TPAOH)、日産化学社製スノーテックス-40コロイダルシリカを順次加えた。得られた混合物の組成は、1.0SiO2/0.4TPAOH/11.8H2Oであった。良く混合した後、得られた混合物を耐圧容器に入れ、100℃のオーブン中で、15rpmで回転させながら、20時間水熱合成を行った。吸引濾過、洗浄した後に、乾燥することで、MFI型の結晶を持つ、シリカライト―1型ゼオライトを得た。得られたシリカライト-1型ゼオライトを600℃、6時間、空気流通下で焼成することにより、シリカライト1を得た。
容器内で、クラウンエーテル(18-クラウンー6)0.93gを水6.3gに溶解させ、これにキシダ化学社製水酸化ナトリウム0.45g、70%アルミン酸ソーダ1.74g、キシダ化学社製水酸化セシウム1水和物0.71gを加えて、80℃3h加熱撹拌させた。これに日産化学社製スノーテックス-40コロイダルシリカ10.5gを加えて、良く混合した後、室温で1日放置した。得られた混合物を耐圧容器に入れ、110℃96時間静置で水熱合成し、ろ過、水洗して、RHO型ゼオライトを得た。得られたRHO型を600℃、6時間、空気流通下で焼成することによりゼオライトR1を得た。
(樹脂組成物製造例1:ポリイミド前駆体含有組成物M1の製造方法)
窒素ガス導入管、冷却器、攪拌機を備えた4つ口フラスコに、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物 311g(1.06mol)、3,3’,4,4’-ビシクロヘキシルテトラカルボン酸二無水物 324g(1.06mol)2,2’-ビス(トリフルオロメチル)ベンジジン 340g(1.06mol)、4,4’-ビス(ジアミノジフェニル)スルホン 263g(1.06mol)、N-メチルピロリドン 2890gを加え、80℃で8時間加熱撹拌することで、ポリイミド前駆体を30質量%含むポリイミド前駆体含有組成物M1を得た。該ポリイミド前駆体は、核水素化(水添)された芳香族化合物を有する。
(比較例1-1:ポリイミド樹脂フィルム1の製造方法)
ポリイミド前駆体含有組成物M1を、N-メチルピロリドンで希釈し、ポリイミド前駆体が20質量%となるように調整した。得られたインクをアルカリガラス(コーニング社製)上に、テスター産業社製アプリケーターを用いて塗布し、330℃で30分間、乾燥・焼成を行うことで、ポリイミド樹脂フィルム1を得た。東洋精機製作所社製THICKNESS METER B-1により膜厚を測定した結果、フィルムの膜厚は、10μmであった。なお、フィルムの平均熱膨張係数を測定した時の変曲点から求めた、ポリイミド樹脂フィルム1のガラス転移温度(Tg)は、320℃であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、及び弾性率を表1に示す。
N-メチルピロリドンに、ゼオライトC1を加え、アシザワ・ファインテック社製ラボスターミニで、ビーズミルすることによって、ゼオライトC1の含有量が、4質量%であるゼオライト分散液D1を得た。
ゼオライト分散液D1 4.8g と、ポリイミド前駆体含有組成物M1 4g を混合した以外は、実施例1と同様にして、ポリイミド樹脂複合材フィルム2を得た。フィルムの膜厚は6μmであり、得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、及び弾性率を表1に示す。
ゼオライトC1の代わりにゼオライトC2を用いる以外は実施例1-1と同様にして、ポリイミド樹脂複合材フィルム3を得た。フィルムの膜厚は21μmであり、得られたフィルム内のゼオライトの含有量は、フィルム質量に対して28.6質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、及び弾性率を表1に示す。
ゼオライトC1の代わりにゼオライトC2を用いる以外は実施例1-2と同様にして、ポリイミド樹脂複合材フィルム4を得た。フィルムの膜厚は21μmであり、得られたフィルム内のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、および弾性率を表1に示す。
ゼオライトT1を0.24g、ポリイミド前駆体0.6g、NMP2.4g、となるよう混合し、撹拌子で撹拌することでインクを得た。得られたインクを、テスター産業社製アプリケーターによって塗布し、330℃で30分間、乾燥・焼成を行うことでポリイミド樹脂複合材フィルム1を得た。なお、フィルムの膜厚は、44μmであり、得られたフィルム中のゼオライトの含有量は、フィルム質量に対して28.6質量%であった。得られたフィルムの平均熱膨張係数、及びヘイズ率を表1に示す。
ゼオライトT1を0.06g、ポリイミド前駆体0.6g、NMP2.4g、となるよう混合し、撹拌子で撹拌することでインクを得た。得られたインクを、テスター産業社製アプリケーターによって塗布し、330℃で30分間、乾燥・焼成を行うことでポリイミド樹脂複合材フィルム6を得た。なお、フィルムの膜厚は、21μmであり、得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、及びヘイズ率を表1に示す。
ゼオライトT1の代わりに、触媒化成工業社製FAU型ゼオライトHY(5)(シリカ/アルミナモル比=40)を用いた以外は、実施例3-2と同様の方法によりポリイミド樹脂複合材フィルム7を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、及びヘイズ率を表1に示す。
ゼオライトT1の代わりに、東ソー社製プロトン型*BEA型ゼオライト HSZ-940HOA(シリカ/アルミナモル比=40)を用いた以外は、実施例3-2と同様の方法によりポリイミド樹脂複合材フィルム8を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数を表1に示す。
ゼオライトT1の代わりに、アドマテックス社製シリカ SC2500-SQ(平均一次粒子径200nm)を用いた以外は、実施例1-1と同様の方法によりポリイミド樹脂複合材フィルム9を作製した。なお、フィルムの膜厚は、18μmであり、得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、ヘイズ率、及び弾性率を表1に示す。
ゼオライトC1の代わりに、負膨張材であるフルウチ株式会社製タングステン酸ジルコニウム ファインZWO-01を用いた以外は、実施例1-1と同様の方法によりポリイミド樹脂複合材フィルム10を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、及び弾性率を表1に示す。
ゼオライトT1の代わりに、ゼオライトA1を用いた以外は、実施例3-1と同様の方法によりポリイミド樹脂複合材フィルム11を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数を表1に示す。
ゼオライトT1の代わりに、シリカライト1を用いた以外は、実施例3-1と同様の方法によりポリイミド樹脂複合材フィルム12を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数、リタデーション値、ヘイズ率、及び弾性率を表1に示す。
ゼオライトT1の代わりに、中村超硬社製ZeoalZ4A-005(平均一次粒子径50nm、LTA型ゼオライト)を用いた以外は、実施例3-1と同様の方法によりポリイミド樹脂複合材フィルム13を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数を表1に示す。
ゼオライトT1の代わりに、ゼオライトR1を用いた以外は、実施例3-1と同様の方法によりポリイミド樹脂複合材フィルム14を作製した。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数を表1に示す。
窒素ガス導入管、冷却器、攪拌機を備えた4つ口フラスコに、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物 635g(2.16mol)、4,4’-ジアミノジフェニルエーテル 445g(2.22mol)、N,N-ジメチルアセトアミド 3240gを加え、80℃で6時間加熱撹拌することで、ポリイミド前駆体を25質量%含むポリイミド前駆体含有組成物M2を得た。該ポリイミド前駆体は、核水素化(水添)された芳香族化合物を有さない。
ポリイミド前駆体含有組成物M1の代わりに、M2を用いた以外は、比較例1-1と同様の方法によりポリイミド樹脂フィルム2を作製した。得られたフィルムの平均熱膨張係数を表1に示す。
ゼオライトC1とポリイミド前駆体含有物M2を使う以外は実施例1-1と同様にして、ポリイミド樹脂複合材フィルム15を得た。得られたフィルム中のゼオライトの含有量は、フィルム質量に対して9.1質量%であった。得られたフィルムの平均熱膨張係数を表1に示す。
一般的な無機フィラーであるシリカや、負の熱膨張係数を有するフィラーであるタングステン酸ジルコニウムを含有するポリイミド樹脂複合材に比べ、本発明の実施形態に係るゼオライト含有ポリイミド樹脂複合材は平均熱膨張係数の低下量が大きい。正の熱膨張係数を有するシリカと、負の熱膨張係数を有するタングステン酸ジルコニウムをそれぞれ含むポリイミド樹脂複合材の平均熱膨張係数が同じであり、フィラーそのものの平均熱膨張係数が樹脂複合材の平均熱膨張係数を決定づけるものではない。
特定のゼオライトを含有するポリイミド樹脂複合材は平均熱膨張係数が大きく低下している。d6rを含むゼオライト(CHA、ERI)、及び/又はmtwを含むゼオライト(BEA)を含有するポリイミド樹脂複合体の平均熱膨張係数は、これらを含まないゼオライト含有ポリイミド樹脂複合材と比べて大きく、これらのCBUを含んでいるために平均熱膨張係数がより小さくなったと推測される。
ゼオライト9.1質量%含有時による平均熱膨張係数の減少率は、非水添のポリイミドを用いた際の12.0%に比べて、水添ポリイミドを用いた際は14.0%であり、水添ポリイミドの方が、効果がより顕著にみられた。この原因は定かではないが、水添することで樹脂同士のπ-πスタックが弱るとともに、ゼオライトとの間の相互作用が強まった結果だと考えられる。
2 ゼオライト
3 樹脂
11 半導体層
12 絶縁体層
13、14 ソース電極及びドレイン電極
15 ゲート電極
16 基材
17 FET素子
31 基材
32 陽極
33 正孔注入層
34 正孔輸送層
35 発光層
36 電子輸送層
37 電子注入層
38 陰極
39 電界発光素子
51 カソード
52 電子取り出し層
53 活性層
54 正孔取り出し層
55 アノード
56 基材
57 光電変換素子
101 耐候性保護フィルム
102 紫外線カットフィルム
103、109 ガスバリアフィルム
104、108 ゲッター材フィルム
105、107 封止材
106 太陽電池素子
110 バックシート
111 薄膜太陽電池
112 基材
113 太陽電池モジュール
Claims (11)
- 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂と、を含有し、電子材料デバイス用である、ゼオライト含有ポリイミド樹脂複合材。
- ゼオライトと、ポリイミド樹脂と、を含有するゼオライト含有ポリイミド複合材であって、
0℃以上前記ポリイミド樹脂のガラス転移温度以下における平均熱膨張係数が50ppm/K未満であり、
リタデーション値が150nm以下であり、かつ、
ヘイズ率が5%以下である、ゼオライト含有ポリイミド樹脂複合材。 - 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂と、を含有し、透明である、ゼオライト含有ポリイミド樹脂複合材。
- 前記ゼオライトが、AEI、AFT、AFX、CHA、ERI、KFI、SAT、SAV、SFW、及びTSC構造のいずれかを有する、請求項1~3のいずれか一項に記載のゼオライト含有ポリイミド樹脂複合材。
- 25℃における弾性率が4.5GPa以上である請求項1~4のいずれか一項に記載のゼオライト含有ポリイミド樹脂複合材。
- ゼオライト含有ポリイミド樹脂複合材前記ゼオライトが、に対し1質量%以上80質量%以下含まれる請求項1~5のいずれか一項に記載のゼオライト含有ポリイミド樹脂複合材。
- 前記ポリイミド樹脂が、核水素化された芳香族化合物を有するポリイミド樹脂である、請求項1~6のいずれか一項に記載のゼオライト含有ポリイミド樹脂複合材。
- 構造単位 Composite Building Unit(CBU)としてd6r及びmtwのいずれかを少なくとも含むゼオライトと、ポリイミド樹脂前駆体と、を含有する、ゼオライト含有ポリイミド樹脂前駆体組成物。
- 請求項8に記載の組成物の硬化物である、ゼオライト含有ポリイミド樹脂複合材。
- 請求項1~7、又は9のいずれか一項に記載のゼオライト含有ポリイミド樹脂複合材を含有するフィルム。
- 請求項1~7、又は9のいずれか一項に記載のオライト含有ポリイミド樹脂複合材を含有する電子デバイス。
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WO2022092323A1 (ja) * | 2020-11-02 | 2022-05-05 | 三菱ケミカル株式会社 | ゼオライト、ゼオライトの製造方法、組成物、液状組成物、液状封止剤、樹脂複合材、封止材、封止材の製造方法、及びデバイス |
WO2023210791A1 (ja) * | 2022-04-28 | 2023-11-02 | 三菱ケミカル株式会社 | シリカライト、組成物、液状封止剤、樹脂複合材、封止材、封止材の製造方法、及び電子デバイス |
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KR102556342B1 (ko) * | 2023-01-08 | 2023-07-17 | 주식회사 네이피 | 발효식품을 위한 과발효억제 및 항균 기술 |
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