TW202446842A - Polyimide resin composites, films and electronic devices containing zeolite - Google Patents

Abstract

The present invention addresses the problem of inexpensively providing a polyimide resin composite material which has all of high unsusceptibility to deformations, e.g., warpage, high image clearness, and high transparency and is suitable for use as members for electronic devices, etc. The polyimide resin composite material is a zeolite-containing polyimide resin composite material comprising a polyimide resin and a zeolite which includes d6r and/or mtw units as composite building units (CBUs), and is for use in electronic material devices.

Description

Polyimide resin composites, films and electronic devices containing zeolite

The present invention relates to a polyimide resin composite material containing zeolite, a polyimide resin precursor composition containing zeolite, a film and an electronic device.

In recent years, the development of electronic devices with excellent flexibility using resin films has been actively progressing. Specifically, for example, OLED (organic electroluminescent element) using polyimide resin film as a substrate is used, and further used in display devices.

Compared to other resins, polyimide resin generally has a higher glass transition temperature. However, because polyimide resin tends to have a larger average thermal expansion coefficient at high temperatures, there are problems such as warping and other deformations of the polyimide resin film during the manufacture of electronic devices due to the high temperature treatment process, which cannot meet the initial characteristics required by the electronic device. In addition, the polyimide resin film warps and other deformations due to the drive heat of the electronic device, causing the parts installed on the resin to peel off and break, and cannot meet the durability characteristics required by the electronic device. Therefore, a lower average thermal expansion coefficient is required for polyimide resin.

Furthermore, in a display device using OLED, since the displayed image is observed through the substrate, image clarity and transparency are important characteristics. Therefore, the polyimide resin used as the substrate is required to have a lower retardation value and haze rate.

On the other hand, in order to prevent deformation such as warping, the in-plane alignment of the polyimide resin is preferably aligned. However, in order to obtain good image clarity and high transparency, the in-plane alignment of the polyimide resin is preferably misaligned. Therefore, there is a sawtooth relationship in preventing deformation such as warping and obtaining good image clarity and high transparency (patent documents 1~3).

As a technique to get rid of the sawing relationship mentioned above, it is known that the unit constituting the resin is drilled or a filler is added. For example, Patent Documents 1 to 3 state that by combining special components in the unit constituting the resin, a polyimide resin having a lower average thermal expansion coefficient, higher image clarity, and/or higher transparency can be obtained. In addition, Patent Documents 3 and 4 state that by adding silica particles to the polyimide resin, a polyimide resin composite having a lower average thermal expansion coefficient, higher image clarity, and/or higher transparency can be obtained. [Prior Technical Documents] [Patent Documents]

[Patent Document 1] International Publication No. 2015/125895 [Patent Document 2] International Publication No. 2014/007112 [Patent Document 3] Japanese Patent Publication No. 2016-204569 [Patent Document 4] International Publication No. 2014/051050

(Invent the problem you want to solve)

Films using polyimide resins as described in Patent Documents 1 to 3 are expected to be used in components of electronic devices, etc., as they can suppress deformation such as warping during high-temperature processing, have good image clarity, and high transparency. However, since special components are combined in the units constituting the resin, there is a problem of high manufacturing costs, which has become a new issue for special polyimide resins.

On the other hand, as described in Patent Documents 3 and 4, a film of a polyimide resin composite material in which a filler is added to a polyimide resin is a film that suppresses deformation such as warping during a high-temperature treatment process, has good image clarity, and has high transparency, and can be expected to be used as a component of electronic devices, etc. In addition, since a special polyimide resin is not required, it can be expected to be used at a low cost as a whole. However, after reviewing the case, the inventors of this case found that in the case of the resin composite material described in Patent Documents 3 and 4, because the silicon dioxide particles added as fillers tend to condense easily, some of them become turbid over time and the transparency decreases. Furthermore, it was found that if a large amount of silica particles were not added, it would be difficult to reduce the average thermal expansion coefficient of the resin composite, and thus the stability of the composition containing the polyimide resin or the composition containing the polyimide resin precursor was low, and the polyimide resin film produced from the composition lacked image clarity and reproducibility and was relatively fragile.

Therefore, the subject of the present invention is to provide, at a low cost, a polyimide resin composite material that has high suppression of deformation such as warping, good image clarity, and high transparency, and can be used for components such as electronic devices. (Technical means to solve the problem)

In view of the above facts, the inventors of this case conducted in-depth research and found that by dispersing zeolite of a specific structure in a polyimide resin, the average coefficient of thermal expansion (CTE) of the polyimide resin composite can be reduced, the haze rate can be reduced, and the retardation value can be reduced, thereby completing the present invention. In addition, the inventors also found that the elastic modulus can be increased by the above structure, thereby completing the present invention.

That is, the gist of the present invention is as follows. [1] A polyimide resin composite material containing zeolite, for use in electronic material devices, comprising: a composite building unit (CBU) of zeolite containing at least one of d6r and mtw; and a polyimide resin. [2] A polyimide resin composite material containing zeolite, comprising zeolite and a polyimide resin; wherein, the average thermal expansion coefficient at a temperature above 0°C and below the glass transition temperature of the polyimide resin is less than 50 ppm/K; the retardation value is less than 150 nm; and the haze rate is less than 5%. [3] A transparent polyimide resin composite containing zeolite, comprising: a composite building unit (CBU) of zeolite containing at least one of d6r and mtw; and a polyimide resin. [4] A polyimide resin composite containing zeolite as described in any one of [1] to [3], wherein the zeolite has any one of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW and TSC structures. [5] A polyimide resin composite containing zeolite as described in any one of [1] to [4], wherein the elastic modulus at 25°C is 4.5 GPa or more. [6] A zeolite-containing polyimide resin composite material as described in any one of [1] to [5], wherein the zeolite is contained in an amount of 1% by mass or more and 80% by mass or less relative to the zeolite-containing polyimide resin composite material. [7] A zeolite-containing polyimide resin composite material as described in any one of [1] to [6], wherein the polyimide resin is a polyimide resin having a nucleus-hydrogenated aromatic compound. [8] A zeolite-containing polyimide resin precursor composition comprising: a composite building unit (CBU) being a zeolite containing at least one of D6R and MTW; and a polyimide resin precursor. [9] A zeolite-containing polyimide resin composite material, which is a cured product of the composition described in [8]. [10] A film, which is a film, which is a zeolite-containing polyimide resin composite material described in any one of [1] to [7] and [9]. [11] An electronic device, which is a zeolite-containing polyimide resin composite material described in any one of [1] to [7] and [9]. [12] A polyimide resin composite material containing zeolite, comprising zeolite and polyimide resin; wherein, the average thermal expansion coefficient at a temperature above 0°C and below the glass transition temperature of the polyimide resin is less than 50 ppm/K; the elastic modulus at 25°C is greater than 4.5 GPa; and the haze rate is less than 5%. (Compared with the efficacy of the prior art)

A polyimide resin composite material that can be used in electronic devices and other components and has high resistance to deformation such as warping, good image clarity, and high transparency can be provided at a low price.

The following is a detailed description of the implementation form of the present invention, but such description is only an example of the implementation form of the present invention, and the present invention is not limited to such content without exceeding its gist.

The first aspect of the polyimide resin composite material containing zeolite in one embodiment of the present invention comprises: the structural unit Composite Building Unit (CBU) is a zeolite containing at least one of D6R and MTW, and a polyimide resin; the polyimide resin composite material containing zeolite belongs to an electronic material device (also referred to as "electronic device"). Furthermore, the second aspect of the polyimide resin composite material containing zeolite in another embodiment of the present invention is a transparent polyimide resin composite material containing zeolite, which comprises: the structural unit Composite Building Unit (CBU) is a zeolite containing at least one of D6R and MTW, and a polyimide resin; it is a transparent transparent polyimide resin composite material containing zeolite. The term "transparent" in the present invention refers to a polyimide resin composite material having a haze rate of 5% or less. In the specification of this case, the polyimide resin composite material containing zeolite is sometimes referred to as a "composite material", "resin composite material", and "polyimide resin composite material". Figure 1 is a schematic diagram of a resin composite material of an embodiment of the present invention. The following is a detailed description of the resin composite material 1.

<1. Resin composite material 1> As shown in FIG1 , the resin composite material 1 contains: zeolite 2 and polyimide resin 3. <1.1 Zeolite> The zeolite contained in the resin composite material is described. In addition, the so-called zeolite is a basic unit composed of a TO ₄ unit (T element is an element other than oxygen constituting the skeleton) containing silicon or aluminum and oxygen, and specific examples include: crystalline porous aluminum silicate, crystalline porous aluminum phosphate (ALPO), or crystalline porous aluminum silicophosphate (SAPO). In addition, a plurality of TO ₄ units (several to dozens) are connected to form a structural unit generally called Composite Building Unit (CBU). Therefore, there are regular channels (tubular pores) and cavities (holes).

The resin composite material contains a structural unit Composite Building Unit (CBU) which is a zeolite containing one or more of D6R and MTW, and the zeolite is used as a filler. The zeolite contains a polyimide resin and has a structural unit that easily forms a cavity that allows a part of the imide bonds of the polyimide resin to easily enter. Therefore, compared with conventional fillers such as silica particles, the zeolite has better compatibility with the polyimide resin and is not easy to agglomerate.

Furthermore, in the above-mentioned resin composite material, since a small amount of zeolite can be used to significantly reduce the average thermal expansion coefficient of the resin composite material, it can prevent whitening over time and maintain high transparency. In addition, since the content of zeolite, which is a filler, is small, it can also maintain high flexibility, and can also prevent embrittlement and deformation, and present good image clarity.

Zeolites with d6r include, for example, 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 -WEN type zeolites.

Furthermore, examples of zeolites having mtw include: ^* BEA, BEC, CSV, GON, ISV, ITG, ^* -ITN, IWS, MSE, MTW, SFH, SFN, SSF, ^* -SSO, UOS, and UOV type zeolites.

Furthermore, in order to have a three-dimensional interaction with a portion of the imide bonds contained in the polyimide resin, a zeolite having a further three-dimensional channel is more preferred, for example: AEI, AFT, AFX, ^* BEA, BEC, CHA, EMT, ERI, FAU, GME, ISV, ITG, ^* -ITN, IWS, JSR, KFI, MOZ, MSE, OFF, SAT, SAV, SBS, SBT, SFW, SZR, TSC, UOS, UOV, and -WEN type zeolites.

Among them, particularly preferred are zeolites having a structure with less than 8-membered oxygen rings from the viewpoint of easy micronization, and specific examples thereof include zeolites having AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structures.

In this specification, the structure having an oxygen 8-membered ring refers to a structure in which the largest number of oxygen elements is 8 in the pores formed by oxygen forming the zeolite framework and T elements (elements other than oxygen forming the framework).

(Content of zeolite in resin composite) The content of zeolite in the resin composite 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, more preferably 7% by mass or more, particularly preferably 10% by mass or more, and most preferably 15% by mass or more. On the other hand, it is usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 30% by mass or less, and most preferably 20% by mass or less. As mentioned above, if a small amount of zeolite is added to the resin, the average thermal expansion coefficient obtained can be greatly reduced compared to the case where silica or the like is used as a filler.

Therefore, if the zeolite content is 1 mass % or more and 80 mass % or less, the resin composite material can suppress embrittlement, deformation, etc., and has good image clarity and high transparency. In particular, if it is 10 mass % or more and 30 mass % or less, the properties of the resin composite material can be more clearly exerted with a small content compared to silicon dioxide, etc., so it is particularly preferred.

The resin composite material may contain one type of zeolite alone or two or more types in any combination and ratio. However, at least one of the zeolites is zeolite D6R or MTW contained in the Composite Building Unit (CBU) as described above.

Specifically, from the perspective of ease of production, zeolite is preferably aluminum silicate. Within the scope of not significantly impairing the effects of the present invention, silicon or aluminum may be replaced by elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, and phosphorus. The zeolite may also contain elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, and phosphorus together with silicon and aluminum.

The structure of zeolite can be expressed by the code for defining the structure of zeolite established by the International Zeolite Association (IZA). In addition, the structure of zeolite can be identified by using the Zeolite Structure Database 2018 Edition (http://www.iza-structure.org/databases/) based on the X-ray diffraction pattern obtained by an X-ray structure analysis device (e.g., the desktop X-ray diffraction device D2PHASER manufactured by BRUKER).

(Average thermal expansion coefficient of zeolite) The average thermal expansion coefficient of zeolite is less than 0ppm/K, preferably -2ppm/K or less, more preferably -3ppm/K or less, even more preferably -5ppm/K or less, particularly preferably -7ppm/K or less, and optimally -10ppm/K or less, provided that the resin composite material exhibits better performance. There are no special restrictions otherwise. On the other hand, it is usually -1000ppm/K or more, preferably -900ppm/K or more, more preferably -800ppm/K or more, even more preferably -700ppm/K or more, particularly preferably -500ppm/K or more, and optimally -300ppm/K or more. If the average thermal expansion coefficient of zeolite is within the above range, the resin composite can maintain high flexibility even with a low zeolite content, and can have good image clarity and high transparency while suppressing embrittlement and deformation.

In addition, the average thermal expansion coefficient of zeolite can be measured by using the X-ray diffraction device D8ADVANCE manufactured by BRUKER and the X-ray diffraction analysis software JADE to calculate the lattice constant. The average thermal expansion coefficient of the zeolite is obtained by measuring the thermal expansion coefficients at 60°C and 220°C, and then taking the average value as the average thermal expansion coefficient.

Furthermore, the framework density of zeolite is not particularly limited, provided that the resin composite material exhibits better performance. Preferably, it is 17.0T/1000Å ³ or less, more preferably 16.0T/1000Å ³ or less, and even more preferably 15.0T/1000Å ³ or less. On the other hand, it is preferably 12.0T/1000Å ³ or more, more preferably 13.0T/1000Å ³ or more, and even more preferably 14.0T/1000Å ³ or more. If the framework density is within the above range, the zeolite is not easily agglomerated and is easily micronized. In addition, it can have both good image clarity and high transparency while suppressing embrittlement and deformation.

In addition, the so-called framework density refers to the number of T atoms present per unit volume of zeolite, and is a value determined by the structure of the zeolite. In this manual, the values recorded in the 2018 edition of the IZA Zeolite Structure Database (http://www.iza-structure.org/databases/) may be used.

Examples of zeolites having a framework density greater than 16.0 T/1000Å ³ and less than 17.0 T/1000Å ³ include zeolites of CSV, ERI, ITG, LTL, LTN, MOZ, MSE, OFF, SAT, SFH, SFN, SSF, ^* -SSO, and -WEN type structures.

Examples of zeolites having a framework density greater than 15.0 T/1000Å ³ and less than 16.0 T/1000Å ³ include zeolites of AEI, AFT, AFV, AFX, AVL, ^* BEA, BEC, CHA, EAB, GME, ^* -ITN, LEV, MWW, and SFW structures.

Examples of zeolites having a framework density greater than 14.0 T/1000Å ³ and less than 15.0 T/1000Å ³ include zeolites of ISV, IWS, KFI, SAS, and SAV structures.

Examples of zeolites having a framework density within the range of 14.0 T/1000Å ³ or less include zeolites of EMT, FAU, JSR, SBS, SBT, and TSC type structures.

Furthermore, the silica/alumina molar ratio (SAR) of the zeolite is not particularly limited, provided that the resin composite material exhibits better performance, and is generally 0.1 or more, preferably 0.5 or more, more preferably 4 or more, more preferably 9 or more, and particularly preferably 12 or more, and is generally 2000 or less, preferably 1000 or less, more preferably 500 or less, and more preferably 100 or less. If the silica/alumina molar ratio (SAR) is within the above range, the relative amount of cations can be appropriately controlled, and the manufacturing cost of the zeolite can also be reduced.

Furthermore, when replacing silicon and aluminum constituting the _TO4 unit with gallium, iron, boron, titanium, zirconium, tin, zinc, phosphorus and other elements, the molar ratio of the oxide of the element used instead can be converted into the molar ratio of aluminum oxide or silicon dioxide. Specifically, when replacing aluminum with gallium, the molar ratio of gallium oxide can be converted into the molar ratio of aluminum oxide.

Furthermore, the relative cations of the zeolite are not particularly limited under the premise that the resin composite shows better performance. Generally, they are structure-directed reagents, protons, alkali metal ions, and alkali-earth metal ions. Preferably, they are structure-directed reagents, protons, and alkali metal ions. More preferably, they are structure-directed reagents, protons, Li ions, Na ions, and K ions. More preferably, they are structure-directed reagents, protons, and Li ions. Protons are particularly preferred. In the case of structure-oriented reagents, zeolite is preferred because it is softer than alkali metal ions and alkali earth metal ions, and thus it is easier for zeolite to show an average thermal expansion coefficient of less than 0 ppm/K. In addition, the smaller the size of alkali metal ions and alkali earth metal ions is, the easier it is for zeolite to show an average thermal expansion coefficient of less than 0 ppm/K, and thus it is preferred. In the case of protons in particular, it is preferred because it is easier to reduce the average thermal expansion coefficient of resin composites.

That is, the zeolite is preferably as-made (including structure-directed reagent type), proton type, alkali metal type, more preferably as-made, proton type, Li type, Na type, K type, still more preferably as-made, proton type, Li type, and the best is proton type.

In addition, the so-called structure-directing reagent is the template used in the production of zeolite.

The crystallinity of zeolite is based on the premise that the resin composite material shows better performance, and there is no special limitation otherwise. The reason is speculated that the Composite Building Unit (CBU) is a factor related to the average thermal expansion coefficient of the resin composite material, compared to the structure determined by the IZA code.

The crystallinity of zeolite can be obtained by using an X-ray diffraction device (e.g., D2PHASER, a desktop X-ray diffraction device manufactured by BRUKER), or by comparing the X-ray diffraction peak with the X-ray diffraction peak of a standard zeolite. A specific calculation example is the crystallinity of LTA zeolite in Scientific Reports 2016, 6, Article number: 29210.

The average primary particle size of zeolite is not particularly limited, provided that the resin composite material exhibits better performance. It is usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, particularly preferably 30 nm or more, and most preferably 40 nm or more. On the other hand, it is usually 2000 nm or less, preferably 1000 nm or less, more preferably 500 nm or less, more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 100 nm or less. If the average primary particle size of zeolite is within the above range, the zeolite in the resin composite material is easily and uniformly dispersed, and thus there is a tendency for the obtained resin composite material to have high transparency and good image clarity.

The average primary particle size of zeolite is obtained by measuring the particle size of 30 or more primary particles selected at random during particle observation using a scanning electron microscope (SEM), and then averaging the particle sizes of the primary particles. In this case, the particle size refers to the diameter of a circle having an area equal to the projected area of the particle and having the maximum diameter (equivalent circular diameter).

Zeolite can be in a state of secondary or higher-order particles agglomerated from primary particles, provided that the resin composite material exhibits better performance. The average particle size of this state is not particularly limited, and is usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, more preferably 30 nm or more, particularly preferably 40 nm or more, and most preferably 50 nm or more. On the other hand, it is usually 3000 nm or less, preferably 2000 nm or less, more preferably 1000 nm or less, more preferably 500 nm or less, particularly preferably 300 nm or less, and most preferably 100 nm or less. If it is within the above range, the zeolite in the resin composite material is easily and uniformly dispersed, and there is a tendency to cause the obtained resin composite material to have high transparency and good image clarity.

In addition, the average particle size of the secondary and higher order particles of zeolite is obtained by measuring the particle size of 30 or more particles selected at random during particle observation using a scanning electron microscope (SEM), and then averaging the particle sizes of the particles. At this time, the particle size refers to the diameter of a circle with an area equal to the projected area of the particle and having the maximum diameter (equivalent circular diameter). Alternatively, the _D50 value measured by a particle size distribution measuring device can be used. The particle size distribution measuring device is matched with the particle size, and a laser diffraction particle size distribution measuring device or a dynamic light scattering particle size distribution measuring device can be used.

The method for producing zeolite is not particularly limited, and it can be produced cheaply by a known hydrothermal synthesis method. For example, when producing CHA type zeolite, it can be produced by referring to the method described in Japanese Patent No. 4896110.

In the method for producing zeolite, a structure-directing reagent may be used as a template as needed. Generally, there is no particular limitation if the structure-directing reagent can produce the target zeolite structure. If the zeolite can be produced without the structure-directing reagent, the structure-directing reagent may not be used.

In addition, when producing zeolite with a smaller average particle size, hydrothermal synthesis can be performed with a shorter synthesis time than usual and a synthesis temperature controlled to be lower than usual, or the zeolite obtained by hydrothermal synthesis can be crushed and/or pulverized using a wet mill such as a bead mill or a ball mill.

The crushing and/or pulverizing device used in the above crushing and/or pulverizing can be exemplified by "OB MILL" manufactured by FREUND-TURBO, "NANO GETTER", "NANO GETTER MINI", "STARMILL", and "LABSTAR" manufactured by Ashizawa Finetech, and "Star Burst" manufactured by Sugino Machine. In addition, the crystallinity of zeolite is generally reduced after pulverization, but it can be recrystallized in a solution containing aluminum oxide, silicon dioxide, etc., as described in the method described in Japanese Patent Publication No. 2014-189476.

From the viewpoint of suppressing the reagglomeration of the crushed and/or pulverized zeolite, it is preferable to perform wet pulverization in a solvent so that the zeolite with a smaller average particle size is dispersed in the solvent. Among them, from the viewpoint of reducing the average particle size, bead milling is more preferable. In addition, in order to suppress the reagglomeration after dispersion, a dispersant may be used during wet pulverization. The above-mentioned solvent and dispersant may be, for example, the solvent and dispersant exemplified in the components of the ink described later.

Furthermore, in the dispersion in which the crushed and/or pulverized zeolite is dispersed, particles with a larger average particle size can be removed by centrifugal separation for the purpose of further reducing the average particle size of the zeolite. This makes it easier for the zeolite to be uniformly dispersed in the resin composite material, and the transparency of the obtained resin composite material is improved, which is preferred. In addition, the centrifuge used in the centrifugal separation can be a commercially available device (for example: the centrifuge H-36 manufactured by KOKUSAN, and the Hitachi micro high-speed centrifuge CF15RN manufactured by Hitachi Industries).

＜1.2. Polyimide resin＞ The following is an explanation of the polyimide resin used in resin composites.

Polyimide resins can be used as curable resins and thermoplastic resins without limitation. Among them, cross-linkable curable resins such as active energy ray curable resins and thermosetting resins are preferred because the resin and zeolite in the resin composite are more evenly distributed than thermoplastic resins. In particular, thermosetting resins are preferred because they do not require an exposure machine and can reduce manufacturing costs. In addition, the so-called active energy ray curable resin composite refers to a resin that is cured using, for example, ultraviolet rays, visible light, infrared rays, electron beams, etc. Furthermore, the polyimide resin may be a polyimide resin having a nucleus-hydrogenated (also called "hydrogenated") aromatic compound, or a polyimide resin having an aromatic compound that has not been nucleus-hydrogenated. From the perspective of good compatibility with zeolite, in other words, improved adhesion with zeolite, it is preferable to use a polyimide resin having a nucleus-hydrogenated aromatic compound, especially when used in electronic devices.

Specific examples of polyimide resins having a nuclear hydrogenated aromatic compound include polyimide resins exemplified in "Newly Revised Latest Polyimide - Fundamentals and Applications -" (Compiled by the Japanese Polyimide and Aromatic Polymer Research Society, NTS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042, and Japanese Patent Publication No. 2016-128555.

The compatibility of polyimide resin and zeolite can be considered as follows. For example: (1) The imide bonds contained in the polyimide resin and the unreacted carbonyl and amine groups interact with the Si-OH groups on the surface of the zeolite, producing a dispersing function similar to that of a dispersant; (2) Some of the imide bonds contained in the polyimide resin enter the cavity formed by either d6r or mtw in the zeolite structural unit Composite Building Unit (CBU). Therefore, zeolite is easily dispersed evenly in the polyimide resin composite material, and can have good image clarity and high transparency while suppressing embrittlement and deformation. As a result, whitening can be prevented for a long time, and good image clarity and high transparency can be maintained.

Among them, in the polyimide resin with a nucleus-hydrogenated aromatic compound, the nucleus-hydrogenated aromatic compound hinders the π-π stacking derived from the π-π bonds between the aromatic compounds, thereby improving the compatibility with the zeolite. In particular, the compatibility with the zeolite with D6R or MTW is improved. In addition to the above reasons, it can also be considered that the CBU of D6R or MTW plays a role in burying the space of the hindered π-π stacking, thereby improving the compatibility. As a result, whitening can be prevented for a long time, and good 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 better performance. The mass average molecular weight (Mw) value of polystyrene conversion measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 3000 or more, and more preferably 5000 or more. In addition, it is usually 200000 or less, preferably 180000 or less, and more preferably 150000 or less. Within the above range, the solubility in solvents, viscosity, etc. tend to be easily handled by ordinary manufacturing equipment, so it is preferred.

Furthermore, the number average molecular weight (Mn) of the polyimide resin is also under the premise that the resin composite material shows better performance, and there is no special restriction otherwise. It is usually 500 or more, preferably 1000 or more, and more preferably 2500 or more. In addition, it is usually below 100000, preferably below 90000, and more preferably below 80000. Within the above range, the solubility in the solvent, viscosity, etc. tend to be easily handled by ordinary manufacturing equipment, so it is preferred. The number average molecular weight converted to polystyrene can be obtained in the same way as the above mass average molecular weight.

Furthermore, the value of Mw divided by Mn (Mw/Mn) of the polyimide resin is usually 1.5 or more, preferably 2 or more, more preferably 2.5 or more, and is usually 5 or less, preferably 4.5 or less, more preferably 4 or less. It is preferable to be within the above range from the viewpoint of improving the uniformity of zeolite in the resin composite and obtaining a resin composite molded product having excellent smoothness.

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, more preferably 220°C or higher, and particularly preferably 250°C or higher. Also, it is usually 700°C or lower, preferably 500°C or lower, more preferably 400°C or lower, more preferably 350°C or lower, and particularly preferably 320°C or lower. By keeping the temperature within the above range, the resin composite can have good image clarity and high transparency while suppressing embrittlement and deformation.

The polyimide resin is generally a material having an average thermal expansion coefficient greater than 0 ppm/K. The average thermal expansion coefficient of the polyimide resin is not particularly limited, provided that the resin composite material exhibits better performance. Within the measurement range in the temperature range above 0°C and below the glass transition temperature of the resin, it is generally greater than 0 ppm/K, preferably 10 ppm/K or more, more preferably 20 ppm/K or more, more preferably 30 ppm/K or more, and particularly preferably 50 ppm/K or more. Furthermore, it is generally less than 200 ppm/K, preferably less than 150 ppm/K, more preferably less than 125 ppm/K, more preferably less than 100 ppm/K, and particularly preferably less than 75 ppm/K. By keeping the above range, the resin composite material can have good image clarity and high transparency while suppressing embrittlement and deformation. In addition, since only a small amount of zeolite is required, the whitening can be reduced for a long time.

In addition, the average thermal expansion coefficient of the resin can be measured by thermomechanical analysis according to the method of JIS K7197 (2012). For example, the thermal mechanical analysis device TMA/SS6100 manufactured by SII NanoTechnology can be used to measure the expansion and contraction of the resin composite material formed into a sheet. Specifically, it can be obtained by taking the slope of the thermal expansion coefficient at two temperatures of 60°C and 220°C. When the glass transition temperature is below 220°C, the average of the measured values at 60°C and the glass transition temperature can be obtained. In addition, the glass transition temperature of the resin can be obtained from the inflection point measured by thermomechanical analysis.

Furthermore, the method for producing polyimide resin is not particularly limited as long as the resin composite material shows better performance. It can be produced according to the known method. For example, it can be produced according to the method described in "Newly Revised Latest Polyimide - Fundamentals and Applications -" (Compiled by the Japanese Polyimide and Aromatic Polymer Research Society, NTS (2010)).

<1.3. Other compounds> In addition to zeolite and polyimide resin, the resin composite may also contain other compounds without significantly damaging the effect of the present invention. For example, as described later, when manufacturing the resin composite, it may also contain ink, or contain a dispersant, a surface treatment agent, a surfactant, an imidization accelerator, a solvent, etc. in the kneaded material, and the residual components of these may also be contained in the resin composite.

<1.4. Characteristics of zeolite-containing polyimide resin composites> The above-mentioned structure can obtain a zeolite-containing polyimide resin composite having unprecedented characteristics. Specifically, the third embodiment of the zeolite-containing polyimide resin composite of another embodiment of the present invention contains: zeolite, and a polyimide resin having a nucleus-hydrogenated aromatic compound; wherein, at a temperature above 0°C and below the glass transition temperature of the polyimide resin, the average thermal expansion coefficient of the composite is less than 50 ppm/K, and the retardation value of the composite is less than 150 nm. , the composite has a haze rate of 5% or less; or, the zeolite-containing polyimide resin composite of the fourth embodiment contains zeolite and polyimide resin; wherein the average thermal expansion coefficient above 0°C and below the glass transition temperature of the polyimide resin is less than 50ppm/K, the elastic modulus at 25°C is above 4.5GPa, and the haze rate is less than 5%.

The average thermal expansion coefficient of the polyimide resin composite material containing zeolite can be set to less than 50ppm/K at a temperature above 0°C and below the glass transition temperature of the polyimide resin. It is preferably below 45ppm/K, more preferably below 40ppm/K, still more preferably below 35ppm/K, and particularly preferably below 30ppm/K. Furthermore, it is usually above 0ppm/K, preferably above 5ppm/K, more preferably above 10ppm/K, still more preferably above 15ppm/K, and particularly preferably above 20ppm/K. In addition, the average thermal expansion coefficient of the resin composite material can be measured in the same manner as the average thermal expansion coefficient of the above-mentioned resin.

Furthermore, the retardation value of the polyimide resin composite containing zeolite can be set to be below 150nm. It is preferably below 125nm, more preferably below 100nm, even more preferably below 75nm, and particularly preferably below 50nm. Again, since the closer to zero the better, there is no better lower limit. In addition, the retardation value can be measured using a phase difference film and optical material inspection device. For example, using RETS-100 manufactured by Otsuka Electronics Co., Ltd., for a film with a film thickness of 10μm, it can be calculated based on the value at a wavelength of 460nm.

Furthermore, the haze rate of the polyimide resin composite containing zeolite is a value for D65 light, which can usually be set below 5%. It is preferably below 4%, more preferably below 3%, even more preferably below 2%, and particularly preferably below 1%. Moreover, since the closer to zero the better, there is no better lower limit. In addition, the haze rate can be measured according to the methods of JIS K7136 (2000) and JIS K7361-1 (1997). Specifically, it can be measured using a haze meter (for example, TM double-beam automatic haze computer HZ-2 manufactured by SUGA Testing Instruments Co., Ltd.).

The transmittance of the resin composite material for light with a wavelength of 450nm is preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, particularly preferably 85% or more, and most preferably 90% or more. Since the closer to 100%, the better, there is no upper limit. By setting it within the above range, good image clarity and high transparency can be achieved. In addition, the transmittance can be measured using a spectrophotometer (e.g., spectrophotometer UV-2500PC manufactured by Shimadzu Corporation).

The visible light transmittance of the resin composite is preferably 60% or more, more preferably 65% or more, even more preferably 70% or more, particularly preferably 75% or more, and most preferably 80% or more. Since the closer to 100%, the better, there is no upper limit. By setting it within the above range, it can have both good image clarity and high transparency. In addition, the visible light transmittance is a value measured by a spectrophotometer (e.g., spectrophotometer UV-2500PC manufactured by Shimadzu Corporation), which can be calculated according to the method defined in JIS R3106 (1998).

The yellowing index (yellowness) value of the resin composite is preferably -20 or more, more preferably -10 or more, more preferably -5 or more, particularly preferably -3 or more, and the best value is -1 or more. On the other hand, it is preferably 20 or less, more preferably 10 or less, more preferably 5 or less, particularly preferably 3 or less, and the best value is 1 or less. By setting it within the above range, good image clarity and high transparency can be achieved. In addition, the yellowing index value can be measured according to the method of JIS K7373 (2006). Specifically, it can be calculated using a color computer SM5 manufactured by SUGA Testing Instrument Co., Ltd. for a film with a film thickness of 10μm.

The elastic modulus of the resin composite at 25°C (hereinafter in the specification of this case, the storage elastic modulus of the resin composite is sometimes referred to as "elastic modulus") is not particularly limited, and is usually 4.0GPa or more, preferably 4.2GPa or more, more preferably 4.5GPa or more, more preferably 4.6GPa or more, and particularly preferably 4.7GPa or more. On the other hand, it is usually 8.0GPa or less, more preferably 7.5GPa or less, more preferably 7.0GPa or less, particularly preferably 6.8GPa or less, and optimally 6.5GPa or less. By setting it within the above range, deformation such as warping can be highly suppressed. The storage elastic modulus of resin composites can be measured, for example, using the dynamic viscoelasticity measurement method described in JIS K-7244, using the dynamic viscoelasticity device DMS6100 manufactured by SII NanoTechnology, under the conditions of a measurement temperature range of -100°C to 150°C, a frequency of 1Hz, and a heating rate of 5°C/min, in a double-sided tensile mode.

The cloudiness of the resin composite material over time can be quantitatively quantified using the haze rate of D65 light, the transmittance of light with a wavelength of 450nm, or the transmittance of visible light, but can only be qualitatively determined by visual inspection.

Furthermore, the flexibility of the resin composite material can be quantitatively quantified by using a bending resistance test, but it can be qualitatively determined by counting the number of cracks and streaks caused by bending by hand.

<1.5. Method for producing polyimide resin composites containing zeolite> The method for producing polyimide resin composites is based on the premise that the resin composites show better performance. There are no special restrictions on the rest. The conventional methods such as molding and injection molding in a heated molten state can be used. In order to make use of the excellent strength and gas barrier properties of polyimide, most of them are formed into a film before use. Therefore, the following is a simple method that is particularly suitable for the production of film-like composites. It is explained by taking the method of mixing a polyimide resin precursor, zeolite, and a solvent to produce a polyimide resin precursor composition containing zeolite (also called "ink"), and then applying the ink to a support body, etc., and then heating and drying it. Therefore, the descriptions of polyimide resins, dispersants, solvents, etc. described below are not limited to inks but also cover composite materials.

Since polyimide resin is insoluble in most solvents, it is converted into polyimide resin by dehydration and cyclization (imidization) after being molded using polyamide acid, which is a polyimide precursor. At this time, dehydration and cyclization are performed by heating, and an imidization accelerator described below may also be used. The heating temperature when converting to polyimide resin is equivalent to the curing temperature described below.

The so-called polyimide resin precursor refers to a polyamide obtained by polymerizing tetracarboxylic dianhydride and diamine in equimolar ratios. In general, polyamide is used directly in inks in which tetracarboxylic dianhydride and diamine are polymerized.

<1.5.1. Composition of ink> Another embodiment of the present invention is an ink that contains at least: the above-mentioned zeolite and a polyimide resin precursor; these raw materials are mixed, or the polyimide resin precursor is replaced by 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, more preferably 5% by mass or more, particularly preferably 7% by mass or more, and most preferably 10% by mass or more. On the other hand, it is usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 20% by mass or less. By setting it within the above range, it is possible to produce an ink in which the zeolite does not precipitate and can maintain a dispersed state for a long time. In addition, the amount of zeolite when calculating the zeolite content is the total amount of zeolite and the substances contained in the zeolite.

In addition, the zeolite may be used alone or in combination of two or more in any combination and ratio in the ink.

The polyimide resin used in the ink can be the polyimide resin in the resin composite material of the first embodiment of the present invention, and is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. On the other hand, it is usually 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less. By setting it within the above range, it is possible to produce an ink in which the resin does not precipitate and can maintain a dispersed state for a long time.

The polyimide resin may be used alone or in combination of two or more in any combination and ratio in the ink.

Furthermore, instead of the polyimide resin, a polyamide which is a polyimide resin precursor may be mixed. In addition, the content of the polyimide resin precursor in the ink may be equivalent to the content of the above resin when it is converted into a polyimide resin.

Generally speaking, ink containing polyamide, which is a precursor of polyimide resin, is prepared by adding equimolar amounts of tetracarboxylic dianhydride and diamine to the ink, polymerizing the ink by heating, and forming polyamide in the ink, which can then be used directly as ink.

Therefore, tetracarboxylic dianhydride and diamine may be mixed instead of the above polyimide resin. In addition, the content of the polyimide resin precursor raw materials (tetracarboxylic dianhydride and diamine) in the ink only needs to be equivalent to the content of the above resin when it can be converted into the final polyimide resin.

In addition, specific examples of tetracarboxylic dianhydride are not particularly limited as long as the resin composite material exhibits better performance, such as tetracarboxylic dianhydride listed in "Newly Revised Latest Polyimide - Foundation and Application -" (Compiled by the Japanese Polyimide and Aromatic Polymer Research Society, NTS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042, and Japanese Patent Publication No. 2016-128555. Among them, tetracarboxylic dianhydride having an aromatic compound that has been nuclear hydrogenated is preferred.

Furthermore, specific examples of diamines are not particularly limited as long as the resin composite material exhibits better performance, such as diamines listed in "Newly Revised Latest Polyimide - Fundamentals and Applications -" (Compiled by the Japanese Polyimide and Aromatic Polymer Research Society, NTS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042, and Japanese Patent Publication No. 2016-128555.

The heating temperature for polymerizing tetracarboxylic dianhydride and diamine in equimolar amounts to form polyamide is preferably a temperature lower than the temperature at which the polyamide undergoes dehydration and cyclization to be converted into polyimide.

The solvent is not particularly limited as long as the resin composite material exhibits better performance. Examples include: water; aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, or decane; aromatic hydrocarbons such as toluene, xylene, chlorobenzene, or o-dichlorobenzene; alcohols such as methanol, ethanol, isopropanol, 2-butoxyethanol, 1-methoxy-2-propanol; acetone, methyl ethyl alcohol, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl ether, methyl Ketones such as ketone, cyclopentanone, or cyclohexanone; esters such as ethyl acetate, butyl acetate, or methyl lactate; halogens such as chloroform, dichloromethane, dichloroethane, trichloroethane, or trichloroethylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), ethyl ether, tetrahydrofuran, or dioxane; amides such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide, etc.

Among them, from the viewpoint of high solubility of the polyimide resin precursor, preferred are aromatic hydrocarbons such as toluene, xylene, chlorobenzene, or o-dichlorobenzene; halogens such as chloroform, dichloromethane, dichloroethane, trichloroethane, or trichloroethylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), ethyl ether, tetrahydrofuran, or dioxane; and amides such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide.

In particular, since polyimide resin precursors having nucleohydrogenated aromatic compounds have high solubility, amides such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide are preferred.

Furthermore, since the solvent may or may not remain in the resin composite, there is no particular restriction on the content and boiling point of the solvent.

The content of the solvent in the ink is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. On the other hand, it is usually 99% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less. When it is within the above range, the ink has a moderate viscosity and a resin composite material with a moderate thickness can be obtained after drying.

The solvent may be used alone or in combination of two or more in any ratio in the ink.

Furthermore, the ink may also contain zeolite, polyimide resin or polyimide resin precursor or polyimide resin precursor raw material, and other compounds other than the solvent, for example, it may also contain: dispersant, surface treatment agent, surfactant, imidization accelerator, etc. Such dispersant, surface treatment agent, surfactant, imidization accelerator may be the dispersant, surface treatment agent, surfactant, imidization accelerator in the above-mentioned resin composite.

The amount of other compounds that can be used in the ink is usually 0.001 mass % or more, preferably 0.003 mass % or more, more preferably 0.005 mass % or more, even more preferably 0.01 mass % or more, and particularly preferably 0.05 mass % or more in the ink, and is usually 10 mass % or less, preferably 7 mass % or less, more preferably 5 mass % or less, even more preferably 3 mass % or less, and particularly preferably 1 mass % or less. By setting it within the above range, even if the zeolite, polyimide resin, or polyimide resin precursor is precipitated in the ink, the dispersion state can be maintained.

The so-called dispersant refers to the compound used to evenly disperse zeolite in the ink and the resin composite after manufacture. For example: polysiloxane compounds and their salts such as methyl hydropolysiloxane, polymethoxysilane, dimethyl polysiloxane, or silane PEG-7 succinate; silane compounds (methyldimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, dichlorophenylsilane, trimethylsilyl chloride, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrichlorosilane, octadecyltrimethoxysilane, octadecyltrichlorosilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyl The present invention can be used to prepare the present invention with a preferred embodiment of the present invention. The present invention can be used to prepare the present invention with a preferred embodiment of the present invention. The present invention can be used to prepare the present invention with a preferred embodiment of the present invention. The present invention can be used to prepare the present invention with a preferred embodiment of the present invention. In addition, the so-called carboxylic acid amine compound refers to a compound having both a carboxyl group and an amine group as functional groups; the so-called phosphate amine compound refers to a compound having both a phosphate group and an amine group as functional groups.

Among them, dispersants of amine phosphate compounds are preferred because of their particularly high affinity for zeolite.

The dispersant may be used alone or in combination of two or more in any combination and ratio. The surface treatment agent and surfactant described below also function as a dispersant. In addition, the dispersant may be completely decomposed, partially decomposed, or not decomposed after the resin composite is manufactured.

In order to prevent zeolite from agglomerating and to disperse the zeolite evenly in the ink and the resin composite after manufacture, the zeolite can also be treated with a surface treatment agent.

The surface treatment agent is not particularly limited, and a known agent may be used, or the above-mentioned dispersant may be used, or a binder resin such as polyimide, polyester, polyamide, polyurethane, polyurea, etc. may be used as the surface treatment agent.

The surface treatment agent may be used alone or in combination of two or more in any combination and ratio. In addition, the surface treatment agent may be completely decomposed, partially decomposed, or not decomposed after the resin composite material is manufactured.

When manufacturing resin composites, the ink may also contain a surfactant for the purpose of preventing the resin composite from being dented or drying unevenly due to tiny bubbles or foreign matter adhering to the resin composite.

The surfactant is not particularly limited, and known surfactants (cationic surfactants, anionic surfactants, nonionic surfactants) can be used. Among them, silicon-based surfactants, fluorine-based surfactants, or acetylene glycol-based surfactants are preferred. Specific examples of the surfactant include TRITON X100 (manufactured by Dow Chemical) as a non-ionic surfactant, ZONYL FS300 (manufactured by DuPont) as a fluorine-based surfactant, BYK-310, BYK-320, BYK-345 (manufactured by BYK Chemical Co., Ltd.) as a silicon-based surfactant, and SURFYNOL 104, SURFYNOL 465 (manufactured by Air Products), OLFINE EXP4036, or OLFINE EXP4200 (manufactured by Nissin Chemical Industries, Ltd.) as an acetylene glycol-based surfactant.

The surfactant may be used alone or in combination of two or more in any combination and ratio. In addition, the surfactant may be completely decomposed, partially decomposed, or not decomposed after the resin composite is manufactured.

Furthermore, the use of surfactants can improve the wettability of the ink described later. In addition to the actual coating on the substrate, the wettability can also be evaluated by the contact angle. The contact angle of the ink is usually below 45°, preferably below 30°, and more preferably below 15° with respect to the PET substrate. In addition, since the contact angle is not detected when it is extended to one side of the substrate, it is particularly preferably not detected. By setting it below 45°, the ink can be coated on all substrates. In addition, the contact angle can be measured using a contact angle meter. For example, it can be measured using the DM-501 manufactured by Kyowa Interface Sciences.

The imidization accelerator can be any one that can accelerate the imidization of polyamic acid, which is a precursor of the polyimide resin, into polyimide, and can be selected in accordance with the method for producing the polyimide resin in the polyimide resin composite. Examples include imidization accelerators described in "Newly Revised Latest Polyimide - Fundamentals and Applications -" (Compiled by the Japanese Polyimide and Aromatic Polymer Research Society, NTS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042, and Japanese Patent Publication No. 2016-128555.

The imidization accelerator may be used alone or in combination of two or more in any combination and ratio. In addition, the imidization accelerator may exist alone in the composition or may form a complex with a solvent or the like. In addition, a polymer may be formed. In addition, the imidization accelerator may be completely decomposed, partially decomposed, or not decomposed after the resin composite is produced.

The ink is preferably stable for more than 24 hours, and more preferably for more than 1 week. The longer the stable state lasts, the more ink can be synthesized and stored for a long time, which can reduce the manufacturing cost.

Ink stability can be evaluated by sediment formation, viscosity change, etc. Sediment formation can be determined visually or by using a dynamic light scattering particle size measuring device. Viscosity can be determined by a rotational viscometer method (described in "Handbook of Physical and Chemical Experiments" (edited by Ginya Adachi, Yasuki Ishii, and Gohiro Yoshida, Chemical Research (1993)).

As mentioned above, the resin composite material is an example of being manufactured using coating ink, but the manufacturing method of the polyimide resin composite material is not limited to this. For example, the resin composite material can also be manufactured by kneading a polyimide resin or a polyimide resin precursor with zeolite without using a solvent and then heating it.

The zeolite used in the kneaded material may be any zeolite in the resin composite material, and may be used alone or in combination of two or more in any ratio.

The resin used in the kneaded material may be a polyimide resin in a resin composite material, and one type may be used alone or two or more types may be used in any combination and ratio.

Furthermore, the mixture may contain other compounds other than the zeolite and polyimide resin used in the kneading product. For example, the above-mentioned dispersant, surface treatment agent, surfactant, imidization accelerator, etc. may be contained. The other compounds may be used alone or in any combination and ratio.

The ratio of zeolite, polyimide resin, and other compounds used in the mixture is not particularly limited as long as the resin composite material produced by heating the mixture exhibits better performance.

Among them, in order to easily adjust the viscosity during the molding process of the resin composite film, it is best to manufacture the polyimide resin composite by applying ink.

The ink and the mixed material are not particularly limited and can be mixed by a known method and can be manufactured by mixing the components of the ink and the mixed material. In addition, at this time, for the purpose of improving uniformity and defoaming, it is best to use a general mixing device and agitator such as a paint vibrator, a bead mill, a planetary mixer, a stirring disperser, a homogenizer, a self-revolving stirring mixer, a three-roller mill, a kneader, a single-shaft or three-shaft mixer, etc. for mixing.

The order of mixing the components can be arbitrary as long as no reaction or sedimentation occurs. It is also possible to first mix any two or three or more components of the ink and mixed material and then mix the remaining components. Alternatively, all components may be mixed at once.

<1.5.2. Molding of polyimide resin composites> The method for molding the resin composite can be the method generally used for molding resins. At this time, the heating required for manufacturing the resin composite and the heating for molding can also be performed at the same time.

For example, when the polyimide resin composite material has thermoplasticity, the resin composite material can be formed into a desired shape by, for example, filling it into a mold. Such a molded body can be manufactured by, for example, injection molding, injection compression molding, extrusion molding, and compression molding.

When the polyimide resin constituting the resin composite is a thermoplastic resin, the molding of the molded body can be carried out at a temperature above the melting temperature of the thermoplastic resin and at a predetermined molding speed and pressure.

The melting temperature is preferably less than 400°C, more preferably less than 370°C, and particularly preferably less than 340°C. On the other hand, it is preferably more than 80°C, more preferably more than 90°C, even more preferably more than 100°C, and particularly preferably more than 120°C. When it is less than 400°C, it is a temperature that can be used in the manufacturing process using a flexible substrate such as the roller-on-roller method, so it is preferred. Moreover, when it is more than 80°C, the resin can be uniformly melted, so it is preferred; when it is more than 100°C, the influence of water can be reduced, so it is preferred; when it is more than 120°C, the influence of water can be further reduced, so it is preferred.

Furthermore, when the resin constituting the polyimide resin composite is a thermosetting resin composite that is a cured product of the above-mentioned polyimide resin precursor composition (when a resin precursor is used), the molding, i.e., the curing, of the resin composite can be carried out under the curing temperature conditions that match the respective components.

The curing temperature is preferably less than 400°C, more preferably less than 370°C, and particularly preferably less than 340°C. On the other hand, it is preferably above 0°C, preferably above 80°C, more preferably above 90°C, particularly preferably above 100°C, and most preferably above 120°C. When it is less than 400°C, it is a temperature that can be used in the manufacturing step using a flexible substrate such as the roller-on-roller method, so it is preferred. Moreover, when it reaches 80°C or more, it is preferred because curing is performed to a certain extent, and the dissolution of unreacted components from the resin composite is suppressed; when it reaches 100°C or more, the influence of moisture can be reduced, so it is preferred; when it reaches 120°C or more, the influence of moisture can be further reduced, so it is preferred.

When the resin composite material is fluid, the resin composite material can be formed by laminating it on the desired support (lamination step) and then performing a heat treatment (heat treatment step). In addition, the desired support can also be removed after manufacturing.

The heat treatment method may be a known drying method such as hot air drying, drying using an infrared heater, etc. Among them, hot air drying with a fast drying speed is preferred. If air drying is sufficient, the heat treatment method may be omitted.

The temperature of the heat treatment is preferably less than 400°C, more preferably less than 370°C, and particularly preferably less than 340°C. On the other hand, it is preferably more than 80°C, more preferably more than 90°C, even more preferably more than 100°C, and particularly preferably more than 120°C. When it is less than 400°C, it is a temperature that can be used in the manufacturing step using a flexible substrate such as the roller-on-roller method, so it is preferred. Moreover, when it is more than 80°C, it is preferred because residual solvents in the sheet can be removed; when it is more than 100°C, it is preferred because the influence of moisture can be reduced; when it is more than 120°C, it is preferred because the influence of moisture can be further reduced.

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 more preferably 3 minutes or more. On the other hand, it is usually 24 hours or less, preferably 12 hours or less, more preferably 1 hour or less, and more preferably 15 minutes or less. If it is within the above range, it can be applied to practical manufacturing steps such as the roller-on-roller method, so it is preferred.

The material of the support is not particularly limited. Preferred examples of the material of the substrate include inorganic materials such as quartz, glass, sapphire or titanium dioxide; and flexible substrates.

The so-called "flexible substrate" refers to a substrate whose radius of curvature is usually greater than 0.1 mm and less than 10,000 mm. In addition, in order to take into account both the bendability and the support characteristics when manufacturing flexible electronic devices, the radius of curvature is preferably greater than 0.3 mm, more preferably greater than 1 mm, and on the other hand, preferably less than 3,000 mm, more preferably less than 1,000 mm. In addition, the radius of curvature can be obtained by using a conjugate focus microscope (e.g., KEYENCE shape measurement laser microscope VK-X200) for a substrate that is bent to no damage such as strain or cracking.

Specific examples of the flexible substrate are not limited, and examples thereof include resins such as epoxy resins; paper materials such as paper or synthetic paper; and composite materials such as metal foils such as silver, copper, stainless steel, titanium, and aluminum that are coated or laminated to impart insulation.

In addition, among these, if a flexible substrate can be used, it can be manufactured using a roller-on-roller method to improve productivity.

When using a resin substrate, attention must be paid to the gas barrier properties. That is, if the gas barrier properties of the substrate are too low, the resin composite material may be degraded by the external air passing through the substrate, so it is best to avoid this. Therefore, when using a resin substrate, it is best to ensure the gas barrier properties by providing a dense silicon oxide film on at least one of the board surfaces.

Examples of the glass include sodium glass, blue plate glass, and alkali-free glass. Among these, alkali-free glass is preferred because of the small amount of ions dissolved in the glass.

The shape of the support is not limited, and for example, a plate, a film, or a sheet can be used.

Furthermore, the film thickness of the support is not limited, but is usually 5 μm or more, preferably 20 μm or more, and is usually 20 mm or less, preferably 10 mm or less. If the film thickness of the support is 5 μm or more, the possibility of insufficient strength can be reduced, which is preferred. If the film thickness of the support is 20 mm or less, the cost can be suppressed and the weight does not increase, which is preferred.

When the support is made of glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and is usually 10 mm or less, preferably 5 mm or less. If the film thickness of the glass substrate is 0.01 mm or more, the mechanical strength can be increased and cracking is not easy to occur, so it is preferred. In addition, if the film thickness of the glass substrate is 5 mm or less, it does not become heavy, so it is preferred.

In addition, the so-called "roller-to-roller method" is a method in which a flexible substrate wound into a roll is unwound, and processing is performed while it is intermittently or continuously transported and taken up by a take-up roller. The roller-to-roller method can process long substrates of the order of kilometers, and is therefore a production method more suitable for mass production than the board-to-board method.

The size of the roller that can be used in the roller-to-roller method is not particularly limited, provided that the roller-to-roller manufacturing device can be used for processing. The outer diameter of the roller core is usually less than 5m, preferably less than 3m, and more preferably less than 1m. On the other hand, it is usually more than 1cm, preferably more than 3cm, more preferably more than 5cm, more preferably more than 10cm, and particularly preferably more than 20cm. If the diameter is below the upper limit, the handling property of the roller is high, so it is better; if it reaches the lower limit, the layer formed according to the following steps is less likely to be damaged by bending stress, so it is better. The width of the roller is usually 5 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and is usually 5 m or less, preferably 3 m or less, more preferably 2 m or less. If the width is below the upper limit, the roller is easy to handle and is therefore preferred. If it is above the lower limit, the resin composite material has a high degree of freedom in its use and is therefore preferred.

In addition, it is not necessary to use a support body, and a molded body can be obtained by cutting a solid resin composite material formed by a molding method including heat treatment into a desired shape.

<2.  Application of resin composites> The first aspect of the above-mentioned resin composite is used for electronic material devices. In addition, the second and third aspects can be used not only for electronic material devices, but also for applications such as catalyst modules, molecular screening modules, optical components, moisture absorption components, food, building components, and packaging components. Among them, components used for electronic material devices, such as substrates, getter material films, and sealing materials, are preferred because they can utilize the high properties of resin composites.

Furthermore, the material containing the resin composite is used as a film. By forming the film, not only the gas barrier property of the polyimide resin can be utilized, but also the aforementioned high transparency, flexibility, image clarity, etc. are also advantageous. When used in the form of a film, the film thickness of the resin composite is not particularly limited and can be appropriately set in accordance with the target use. It is usually greater than 0.5 μm, preferably 1 μm or more, more preferably 2 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more. On the other hand, from the perspective of the aforementioned transparency, flexibility, and image clarity, it is usually less than 5 mm, preferably less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.3 mm, and particularly preferably less than 0.1 mm.

The film thickness of the resin composite can be measured using a general film thickness gauge such as a non-contact film thickness gauge or a contact film thickness gauge. Examples of non-contact types include conjugate focus microscopes (e.g., KEYENCE's shape measurement laser microscope VK-X200). The following is an example of using a polyimide resin composite as an electronic device.

<2.1. Electronic devices> Electronic devices are devices that have two or more electrodes and control the current flowing between the electrodes or the voltage generated by using electricity, light, magnetism or chemical substances, or devices that generate light, electric field or magnetic field by applying voltage or current. Specifically, they include resistors, rectifiers (diodes), switching elements (transistors, gates), amplifier elements (transistors), memory elements or chemical sensors, or devices that combine or integrate these elements. In addition, they include photodiodes or phototransistors that generate photocurrents, electroluminescent elements that emit light by applying an electric field, and photoelectric converters or solar cells that generate electromotive force using light. A more systematic example of electronic devices can be found in Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981) by S.M.Sze.

Preferred examples of electronic devices include field effect transistor (FET) devices, electroluminescent devices (LED), photoelectric converters or solar cells. These devices can effectively utilize the high properties of resin composites.

Hereinafter, with respect to another embodiment of the present invention, as an example of an electronic device having the above-mentioned resin composite as a constituent element (also referred to as an "electronic device containing a resin composite"), a field effect transistor element, an electroluminescent element, a photoelectric conversion element and a solar cell are described in detail as follows.

<2.2. Field Effect Transistor (FET) Component> Field Effect Transistor (FET) components have a resin composite material as a component. One embodiment of the field effect transistor (FET) component has a semiconductor layer, an insulator layer, a source electrode, a gate electrode, and a drain electrode on a substrate.

In one embodiment, the substrate is a resin composite material of one embodiment of the present invention. Since the average thermal expansion coefficient of the resin composite material is low, it is suitable for use as a substrate material.

The following is a detailed description of an implementation form of a FET element. FIG2 is a schematic diagram of an example of a FET element structure. In FIG2 , 11 represents a semiconductor layer, 12 represents an insulating layer, 13 and 14 represent a source electrode and a drain electrode, 15 represents a gate electrode, 16 represents a substrate, and 17 represents a FET element. FIG2 (A) to (D) respectively represent FET elements of different structures, but all are examples of structures of FET elements. There are no special restrictions on the components and manufacturing methods of the related FET elements, and known technologies can be used. For example: technologies described in known documents such as International Publication No. 2013/180230 or Japanese Patent Publication No. 2015-134703.

In this specification, the so-called "semiconductor" is defined by the size of the carrier mobility in the solid state. As is well known, the so-called "carrier mobility" is an indicator of how fast (or how much) electric charges (electrons or holes) can move. Specifically, the carrier mobility of the "semiconductor" in this specification at room temperature is usually 1.0× ^{10-6 cm2} /V·s or more, preferably 1.0× ^{10-5 cm2} /V·s or more, more preferably 5.0× ^{10-5 cm2} /V·s or more, and even more preferably 1.0× ^{10-4 cm2} /V·s or more. In addition, the carrier mobility can be measured, for example, by measuring the IV characteristics of a field effect transistor.

<2.2.1. Substrate> FET elements are usually made on a substrate 16. The material of the substrate 16 is not particularly limited as long as it does not significantly damage the effect of the present invention. Preferred examples of the material of the substrate 16 include inorganic materials such as quartz, glass, sapphire or titanium dioxide; flexible substrates such as the above-mentioned resin composite moldings.

The so-called "flexible substrate" refers to a substrate with a curvature radius of usually 0.1 mm or more and 10,000 mm or less. In addition, in order to take into account both the bendability and the support characteristics when manufacturing flexible electronic devices, the curvature radius is preferably 0.3 mm or more, more preferably 1 mm or more, and on the other hand, it is preferably 3,000 mm or less, more preferably 1,000 mm or less. In addition, the curvature radius is obtained by using a conjugate focus microscope (e.g., KEYENCE VK-X200 shape measurement laser microscope) for a substrate that is bent without strain, cracking, etc.

Specific examples of flexible substrates are resin composites containing an embodiment of the present invention, and are not limited to the rest. Examples include: resins such as epoxy resins; paper materials such as paper or synthetic paper; composite materials used to impart insulation to metal foils such as silver, copper, stainless steel, titanium or aluminum by coating or laminating the surface; and molded bodies of the above-mentioned resin composites.

In addition, if the resin composite molded body is a flexible substrate, it is suitable for manufacturing by the roller-on-roller method, etc., but even if it is not a flexible substrate, it can still be used as the substrate 16.

Furthermore, the characteristics of FET can be improved by treating the substrate 16. The reason is presumed to be that the film quality of the formed semiconductor layer 11 is improved by adjusting the hydrophilicity/hydrophobicity of the substrate 16, especially the characteristics of the interface between the substrate 13 and the semiconductor layer 11 are improved. Such substrate treatments include, for example: hydrophobic treatment using hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane, etc.; acid treatment using acids such as hydrochloric acid, sulfuric acid and acetic acid; alkaline treatment using sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia; ozone treatment; fluorination treatment; plasma treatment using oxygen, argon, etc.; treatment to form a Langmuir-Blodegett film; treatment to form other insulators or semiconductor films, etc.

<2.3. Electroluminescent element (LED)> An electroluminescent element (LED) is a component that contains a resin composite material. An electroluminescent element is a self-luminescent element that uses the principle that fluorescent substances emit light by applying an electric field and utilizing the recombination energy of holes injected from the anode and electrons injected from the cathode.

The electroluminescent element is described below with reference to the drawings. FIG3 is a schematic cross-sectional view of an embodiment of the electroluminescent element. In FIG3 , element symbol 31 represents a substrate, 32 represents an anode, 33 represents a hole injection layer, 34 represents a hole transport layer, 35 represents a luminescent layer, 36 represents an electron transport layer, 37 represents an electron injection layer, 38 represents a cathode, and 39 represents an electroluminescent element. In addition, the electroluminescent element does not necessarily have all of these components, and the necessary components can be arbitrarily selected. For example, the hole injection layer 33, the hole transport layer 34, the electron transport layer 36, and the electron injection layer 37 do not necessarily have to be provided. The components and manufacturing methods of the electroluminescent element are not particularly limited, and known techniques can be used, such as those described in International Publication No. 2013/180230 or Japanese Patent Publication No. 2015-134703.

In one embodiment, the substrate 31 is a resin composite material. The resin composite material is suitable as a material for the substrate 31 due to its properties.

<2.3.1. Substrate (31)> The substrate 31 is a support for the electroluminescent element 39. The material thereof is not particularly limited as long as it does not cause significant damage and the effects of the present invention are achieved. Preferred examples of the material of the substrate 31 include inorganic materials such as quartz, glass, sapphire or titanium dioxide; and flexible substrates such as the molded body of the above-mentioned resin composite material.

Specific examples of flexible substrates are resin composites containing an embodiment of the present invention, and are not limited to the rest. Examples include: resins such as epoxy resins; paper materials such as paper or synthetic paper; composite materials whose surfaces are coated or laminated in order to impart insulation to metal foils such as silver, copper, stainless steel, titanium, and aluminum; and molded bodies of resin composites.

In addition, if the resin composite molded body is a flexible base material, it is suitable for manufacturing by the roller-on-roller method, etc., but even if it is not a flexible base material, it can still be used as the base material 31.

When using a resin substrate, attention must be paid to the gas barrier properties. That is, if the gas barrier properties of the substrate are too low, the electroluminescent element may be degraded by the external air passing through the substrate, so it is best to avoid this. Therefore, when using a resin substrate, it is best to ensure the gas barrier properties by providing a dense silicon oxide film, resin composite material, etc. on at least one of the board surfaces.

Examples of glass include sodium glass, blue plate glass, and alkali-free glass. Among these, alkali-free glass is preferred because of the small amount of dissolved ions in the glass.

The shape of the substrate 31 is not limited, and for example, a plate, a film, or a sheet may be used.

Furthermore, the film thickness of the substrate 31 is not limited, and is usually 5 μm or more, preferably 20 μm or more, and is usually 20 mm or less, preferably 10 mm or less. If the film thickness of the substrate is 5 μm or more, the possibility of insufficient strength of the electroluminescent element can be reduced, which is preferred. If the film thickness of the substrate is 20 mm or less, the cost can be reduced and the weight does not increase, which is preferred.

When the material of the substrate 31 is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and is usually 1 cm or less, preferably 0.5 cm or less. If the film thickness of the glass substrate 31 is 0.01 mm or more, the mechanical strength is increased and cracking is not likely to occur, which is preferred. If the film thickness of the glass substrate 31 is 0.5 cm or less, the weight does not increase, which is preferred.

In addition, FIG3 shows only one embodiment of the electroluminescent element, and the electroluminescent element is not limited to the structure shown in the figure. For example, a layered structure opposite to that shown in FIG3 may be used, that is, on the substrate 31, the cathode 38, the electron injection layer 37, the electron transport layer 36, the luminescent layer 35, the hole transport layer 34, the hole injection layer 33 and the anode 32 are layered in the order of.

The structure of the electroluminescent element is not particularly limited, and it may be a single element, an element formed by a structure arranged in an array, or an element with an anode and a cathode arranged in an X-Y matrix.

<2.4. Photoelectric conversion element> The photoelectric conversion element has a constituent element containing a resin composite material. In one embodiment, the photoelectric conversion element has at least one pair of electrodes and an active layer between the electrodes. In addition, the photoelectric conversion element in one embodiment may also have other constituent elements including a substrate, an electron extraction layer, and a hole extraction layer.

FIG4 is a schematic cross-sectional view of an embodiment of a photoelectric conversion element. The photoelectric conversion element shown in FIG4 is a photoelectric conversion element used in a general thin-film solar cell, but the photoelectric conversion element is not limited to that shown in FIG4. A photoelectric conversion element 57 in an embodiment has a layer structure formed in sequence: a substrate 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. In addition, the electron extraction layer 52 and the hole extraction layer 54 are not necessarily required. There are no special restrictions on the components and manufacturing methods of the relevant photoelectric conversion element, and well-known technologies can be used. For example, the technology described in the known documents such as International Publication No. 2013/180230 and Japanese Patent Application Laid-Open No. 2015-134703 can be used.

In one embodiment of the photoelectric conversion element, the substrate 56 includes a resin composite material. The resin composite material is suitable as a material for the substrate 56 due to its properties.

<2.4.1. Substrate (56)> The photoelectric conversion element 57 usually has a substrate 56 serving as a support.

The material of the substrate 56 is not particularly limited as long as it does not cause significant damage and the effect of the present invention is achieved. Preferred examples of the material of the substrate 56 include inorganic materials such as quartz, glass, sapphire or titanium dioxide, and flexible substrates such as molded bodies of resin composite materials.

Specific examples of flexible substrates are resin composites containing an embodiment of the present invention, and are not limited to the rest. Examples include: resins such as epoxy resins; paper materials such as paper or synthetic paper; composite materials whose surfaces are coated or laminated in order to impart insulation to metal foils such as silver, copper, stainless steel, titanium, and aluminum; and molded bodies of the above-mentioned resin composites.

In addition, if the resin composite molded body is a flexible base material, it is suitable for use in manufacturing such as the roller-on-roller method, but even if it is not a flexible base material, it can still be used as the base material 56.

When using a resin substrate, you must pay attention to the gas barrier properties. That is, if the gas barrier properties of the substrate are too low, the active layer will be degraded due to the external air passing through the substrate, so it is best to avoid this. Therefore, when using a resin substrate, it is best to ensure the gas barrier properties by setting a dense silicon oxide film, resin composite material, etc. on at least one of the board surfaces.

Examples of glass include sodium glass, blue plate glass, and alkali-free glass. Among these, alkali-free glass is preferred because of the small amount of dissolved ions in the glass.

The shape of the substrate 56 is not limited, and for example, a plate, a film, or a sheet may be used.

Furthermore, the film thickness of the substrate 56 is not limited, and is usually 5 μm or more, preferably 20 μm or more, and is usually 20 mm or less, preferably 10 mm or less. If the film thickness of the substrate 56 is 5 μm or more, the possibility of insufficient intensity of the photoelectric conversion element can be reduced, which is preferred. If the film thickness of the substrate 56 is 20 mm or less, the cost can be reduced and the weight does not increase, which is preferred.

When the material of the substrate 56 is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and is usually 1 cm or less, preferably 0.5 cm or less. If the film thickness of the glass substrate 56 is 0.01 mm or more, the mechanical strength can be increased and cracking is not easy to occur, which is preferred. In addition, if the film thickness of the glass substrate 56 is 0.5 cm or less, the weight does not increase, which is preferred.

<2.5. Solar cell> The photoelectric conversion element 57 is preferably a solar cell, especially a thin film solar cell. FIG5 is a schematic cross-sectional view of the structure of a thin film solar cell of a solar cell in an embodiment of the present invention. As shown in FIG5, the thin film solar cell 111 of this embodiment has: a weather-resistant protective film 101, an ultraviolet blocking film 102, a gas barrier film 103, a gas collecting material film 104, a sealing material 105, a solar cell element 106, a sealing material 107, a gas collecting material film 108, a gas barrier film 109 and a backing film 110. In the thin film solar cell 111 of this embodiment, the solar cell element 106 has a photoelectric conversion element. Therefore, light is irradiated from one side (the lower side in FIG. 5) where the weather-resistant protective film 101 is formed, so that the solar cell element 106 generates electricity. In addition, the thin-film solar cell 111 does not necessarily have all of these components, and the necessary components can be arbitrarily selected.

The components and manufacturing methods of the thin film solar cell are not particularly limited, and known technologies can be used, such as those described in International Publication No. 2013/180230 or Japanese Patent Publication No. 2015-134703.

Furthermore, the weather-resistant protective film, backing film, UV blocking film, gas barrier film, gas collecting material film and sealing material can also be used in the above-mentioned electronic devices such as field effect transistor elements (FET) and electroluminescent elements (LED).

The manufacturing method of the thin film solar cell 111 of this embodiment is not limited. For example, the manufacturing method of the solar cell shown in FIG6 is a method of performing a lamination and sealing step after manufacturing the laminated body shown in FIG5. The solar cell element 106 of this embodiment is preferred because it has excellent heat resistance and can reduce the deterioration caused by the lamination and sealing step.

The production of the laminate shown in FIG5 can be implemented using known techniques. The method of the lamination and sealing step is not particularly limited as long as the effect of the present invention is not impaired. Examples thereof include wet lamination, dry lamination, hot melt lamination, extrusion lamination, co-extrusion lamination, extrusion coating, lamination using a photocurable adhesive, and heat pressing. Among them, the lamination method using a photocurable adhesive that has been practically effective in the sealing of organic electroluminescent elements and the hot melt lamination or heat pressing that has been practically effective in the sealing of solar cells are preferred. In addition, in the case where a sheet-shaped sealing material can be used, hot melt lamination or heat pressing is more preferred.

The heating temperature of the lamination and sealing step is usually 130°C or higher, preferably 140°C or higher, and usually 180°C or lower, preferably 170°C or lower. The heating time of the lamination and sealing step is usually 10 minutes or higher, preferably 20 minutes or higher, and usually 100 minutes or lower, preferably 90 minutes or lower. The pressure of the lamination and sealing step is usually 0.001MPa or higher, preferably 0.01MPa or higher, and usually 0.2MPa or lower, preferably 0.1MPa or lower. By setting the pressure within this range, sealing can be surely performed, and the sealing materials 105 and 107 can be suppressed from seeping out from the ends, or the film thickness reduction caused by over-pressurization can be suppressed, thereby ensuring dimensional stability. In addition, two or more solar cell elements 106 may be connected in series or in parallel in the same manner as described above.

The use of solar cells, especially the thin film solar cells 111, is not limited and can be used for any purpose. For example, the solar cells in one embodiment can be used as solar cells for building materials, solar cells for automobiles, solar cells for interior decoration, solar cells for railways, solar cells for ships, solar cells for airplanes, solar cells for spacecraft, solar cells for household appliances, solar cells for mobile phones, or solar cells for toys.

<2.6. Solar cell module> The solar cell, especially the thin film solar cell 111, can be used directly or as a component of a solar cell module. For example, as shown in FIG6, a solar cell module 113 is prepared in which a solar cell, especially the thin film solar cell 111, is provided on a substrate 112, and the solar cell module 113 can be installed at a place of use.

The substrate 112 can be made of known technology. For example, the material of the substrate 112 can be made of materials described in International Publication No. 2013/180230 or Japanese Patent Publication No. 2015-134703. In addition, the substrate 112 can also be made of a polyimide resin composite. For example, when a building material board is used as the substrate 112, a thin-film solar cell 111 is provided on the surface of the board to form a solar cell module 113, and a solar cell board for a building exterior wall can be manufactured. [Example]

The present invention is described in more detail below using examples, but the present invention is not limited to the following examples without exceeding the scope of the present invention. In addition, the evaluation of the zeolite and the membrane obtained in the examples described below is carried out according to the following method.

<Evaluation of Zeolite> (Average Primary Particle Size of Zeolite) Using Auto Fine Coater JFC-1600 manufactured by JEOL, sputtering was performed for 60 seconds at a distance of 30mm between zeolite and platinum target. After the platinum thickness on the surface of the zeolite sample was evaporated to about 9nm, it was observed using SEM. The SEM operation distance was set to 10~11mm, the acceleration voltage was set to 10kV, and the spot size was set to 30mm. The average primary particle size was obtained by particle observation using a scanning electron microscope JSM-6010LV manufactured by JEOL. The particle size of 30 randomly selected primary particles was measured and the particle size of the primary particles was averaged. In addition, the particle size is the diameter of a circle with an area equal to the projected area of the particle (equivalent circle diameter).

(Average thermal expansion coefficient of zeolite) The average thermal expansion coefficient of zeolite at 60~220℃ was measured by calculating the lattice constant using the X-ray diffraction device D8ADVANCE manufactured by BRUKER and the X-ray diffraction analysis software JADE.

<Film evaluation> (Average thermal expansion coefficient of film) The average thermal expansion coefficient (CTE) in the temperature range of 60℃~220℃ was measured using the thermal mechanical analysis device TMA/SS6100 manufactured by SII NanoTechnology. In addition, the sample shape was set to 4mm in width and 20mm in distance between the fixtures, and the temperature was raised at a rate of 10℃/min.

(Retardation value of film) The retardation value (Rth) of the film is calculated at a wavelength of 460nm for a film with a thickness of 10μm using the phase difference film and optical material inspection device RETS-100 manufactured by Otsuka Electronics Co., Ltd.

(Haze rate of film) The haze rate of film is measured using the TM double beam automatic haze computer HZ-2 manufactured by SUGA Testing Instruments Co., Ltd. The haze rate used this time is the value for D65 light.

(Storage elastic modulus of film) The storage elastic modulus of the resin composite film at various temperatures is measured according to the dynamic viscoelasticity measurement method described in JIS K-7244, using the dynamic viscoelasticity device DMS6100 manufactured by SII NanoTechnology, in double-sided tensile mode (measurement temperature range: -100℃~150℃, frequency: 1Hz, heating rate: 5℃/min). The elastic modulus shown in Table 1 is the elastic modulus measured at a temperature of 25℃.

<Synthesis method of zeolite> (Synthesis example 1: Synthesis method of zeolite C1) Sodium hydroxide manufactured by Kishida Chemical Co., Ltd., N,N,N-trimethyl-1-adamantane ammonium hydroxide (TMAdaOH) manufactured by SACHEM Co., Ltd. as a structure-directing agent (SDA), aluminum hydroxide manufactured by Aldrich Co., Ltd., and Cataloid SI-30 manufactured by Heliotrope Catalyst Chemicals Co., Ltd. were added in sequence into a container. The composition of the obtained mixture was 1.0SiO2 _{/ 0.033Al2O3} /0.1NaOH/ _0.06KOH /0.07TMAdaOH _/20H2O . Then, 2 mass % of CHA zeolite as seed crystals relative to _SiO2 was added to the mixture, and after thorough mixing, the obtained mixture was placed in a pressure-resistant container and subjected to hydrothermal synthesis for 48 hours in a 160°C oven at 15 rpm. After suction filtration, washing, and drying, zeolite C1 belonging to CHA zeolite (as-made) was obtained.

The obtained zeolite C1 was observed by SEM, and the average primary particle size was 1000nm. In addition, the average thermal expansion coefficient of zeolite C1 was measured at 60-220℃, and the average thermal expansion coefficient of zeolite C1 was -10ppm/K.

(Synthesis Example 2: Synthesis Method of Zeolite C2) In a container, water, potassium hydroxide produced by Kishida Chemical Co., Ltd., and FAU type zeolite USY7 produced by Catalyst Chemical Industry Co., Ltd. were added in sequence. The composition of the obtained mixture was 1.0SiO ₂ /0.143Al ₂ O ₃ /0.582KOH/36.2H ₂ O. After being fully mixed, the obtained mixture was placed in a pressure-resistant container and placed in an oven at 100°C for 7 days of hydrothermal synthesis. After suction filtration, washing, and drying, zeolite C2 belonging to CHA type zeolite was obtained.

The obtained zeolite C2 was observed by SEM, and the average primary particle size was 200nm. In addition, the average thermal expansion coefficient of zeolite C2 was measured at 60-220℃, and the average thermal expansion coefficient of zeolite C2 was -10ppm/K.

(Synthesis Example 3: Synthesis method of zeolite T1) The following synthesis was performed with reference to Chemical Engineering Journal, 230, 380, 2013. In a container, water, sodium hydroxide produced by Kishida Chemical Co., Ltd., potassium hydroxide produced by Kishida Chemical Co., Ltd., tetramethylammonium hydroxide (TMAOH) produced by SACHEM Co., Ltd. as a structure-directing agent (SDA), sodium aluminate (20.13% alumina, 18.9% sodium oxide) produced by Asada Chemical Co., Ltd., and AS-40 colloidal silica produced by Aldrich Co. were added in order. The composition of the obtained mixture was 1.0SiO ₂ /0.025Al ₂ O ₃ /0.3NaOH/0.3KOH/0.06TMAOH/10H ₂ O. After thorough mixing, the obtained mixture was placed in a pressure-resistant container and subjected to hydrothermal synthesis for 5 days in a 130°C oven at 15 rpm. After suction filtration, washing, and drying, Linde T-type zeolite (as-made) with OFF-type and ERI-type intercrystalline was obtained. The powder was calcined at 600°C for 6 hours in air circulation to obtain zeolite T1.

The obtained zeolite T1 was observed by SEM, and the average primary particle size was 300nm. In addition, the average thermal expansion coefficient of zeolite T1 was measured at 60-220℃, and the average thermal expansion coefficient of zeolite T1 was -12ppm/K.

(Synthesis Example 4: Synthesis method of aluminum phosphate A1) In a container, mix 69 g of 85% phosphoric acid manufactured by Kishida Chemical Co., Ltd. and 130 g of water. Add 40.8 g of pseudo-soft alumina (75% Al ₂ O ₃ ) and stir. After stirring for 2 hours, add a mixture of 27.3 g of triethylamine and 120 g of water, and stir for another hour. After thorough mixing, the obtained mixture is placed in a pressure-resistant container and subjected to hydrothermal synthesis for 12 hours in a 190°C oven with rotation at 15 rpm. After suction filtration and washing, it is dried to obtain APC-type aluminum phosphate. The obtained APC-type aluminum phosphate is calcined at 600°C for 6 hours in air circulation to obtain aluminum phosphate A1.

(Synthesis Example 5: Synthesis Method of Silica 1) In a container, add water, structure-directed reagent (SDA) tetrapropylammonium hydroxide (TPAOH) manufactured by SACHEM, and Snowtex-40 colloidal silica manufactured by Nissan Chemical Co., Ltd. in sequence. The composition of the obtained mixture is 1.0SiO ₂ /0.4TPAOH/11.8H ₂ O. After thorough mixing, the obtained mixture is placed in a pressure-resistant container and subjected to hydrothermal synthesis for 20 hours in a 100°C oven at 15 rpm. After suction filtration, washing, and drying, Silica 1 type zeolite with MFI type crystals is obtained. The obtained silicalite-1 type zeolite was calcined at 600°C for 6 hours under air circulation to obtain silicalite 1.

(Synthesis Example 6: Synthesis method of zeolite R1) In a container, 0.93 g of cyclic crown ether (18-crown-6) was dissolved in 6.3 g of water, and 0.45 g of sodium hydroxide, 1.74 g of 70% sodium aluminate, and 0.71 g of cesium hydroxide monohydrate manufactured by Kishida Chemical Co., Ltd. were added thereto, and heated and stirred at 80°C for 3 hours. 10.5 g of Snowtex-40 colloidal silica manufactured by Nissan Chemical Co., Ltd. was added thereto, and after thorough mixing, it was left at room temperature for 1 day. The obtained mixture was placed in a pressure-resistant container, and left at 110°C for 96 hours for hydrothermal synthesis. After filtering and washing with water, RHO-type zeolite was obtained. The obtained RHO type was calcined at 600℃ for 6 hours under air circulation to obtain zeolite R1.

<Manufacturing method of resin composition> (Resin composition manufacturing example 1: Manufacturing method of composition M1 containing polyimide precursor) In a four-necked flask equipped with a nitrogen inlet tube, a cooler and a stirrer, 311 g (1.06 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 324 g (1.06 mol) of 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, 340 g (1.06 mol) of 2,2'-bis(trifluoromethyl)benzidine, 263 g (1.06 mol) of 4,4'-bis(diaminodiphenyl)sulfone and 2890 g of N-methylpyrrolidone were added, and the mixture was heated and stirred at 80° C. for 8 hours to obtain a polyimide precursor-containing composition M1 containing 30% by mass of the polyimide precursor. The polyimide precursor is a nuclear hydrogenated (hydrogenated) aromatic compound.

<Example 1: Production of a resin composite film using a composition M1 containing a polyimide precursor> (Comparative Example 1-1: Method for producing a polyimide resin film 1) The composition M1 containing a polyimide precursor was diluted with N-methylpyrrolidone to adjust the polyimide precursor to 20% by mass. The obtained ink was applied to alkaline glass (made by Corning) using a dripper manufactured by TESTER Industries, Ltd., and dried and calcined at 330°C for 30 minutes to obtain a polyimide resin film 1. The film thickness was measured using THICKNESS METER B-1 manufactured by Toyo Seiki Seisakusho Co., Ltd., and the film thickness of the film was 10μm. In addition, the glass transition temperature (Tg) of the polyimide resin film 1 obtained from the turning point when measuring the average thermal expansion coefficient of the film is 320°C. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Example 1-1: Method for manufacturing polyimide resin composite film 1) Zeolite C1 was added to N-methylpyrrolidone and bead milled using LABSTAR MINI manufactured by Ashizawa Finetech to obtain a zeolite dispersion D1 containing 4% by mass of zeolite C1.

Next, about 20 g of the obtained zeolite dispersion D1 was centrifuged at 5000 rpm for 30 minutes using a Hitachi micro high-speed centrifuge CF15RN manufactured by Hitachi Industries, Ltd., and the supernatant was collected to obtain a zeolite dispersion after centrifugation. The amount of zeolite in the zeolite dispersion after centrifugation was 2.5% by mass. In addition, the D ₅₀ value measured by a dynamic light scattering particle size distribution measuring device (MicrotracBEL Nanotrac WaveII-EX150) was 35 nm.

Next, 19.2 g of the centrifugally separated zeolite dispersion was mixed with 4 g of the polyimide precursor-containing composition M1, and stirred with a stirrer to obtain an ink mixed with zeolite and the polyimide precursor-containing composition M1. The obtained ink was applied using a dripper manufactured by TESTER Industries, Ltd., and dried and calcined at 330°C for 30 minutes to obtain a polyimide resin composite film 1. In addition, the film thickness was 19 μm, and the zeolite content in the obtained film was 28.6% by mass relative to the film mass. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Example 1-2: Method for manufacturing polyimide resin composite film 2) Except for mixing 4.8g of zeolite dispersion D1 and 4g of composition M1 containing polyimide precursor, the rest is carried out in the same manner as in Example 1 to obtain polyimide resin composite film 2. The film thickness is 6μm, and the zeolite content in the obtained film is 9.1% by mass relative to the film mass. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Example 2-1: Method for manufacturing polyimide resin composite film 3) Except for replacing zeolite C1 with zeolite C2, the rest is carried out in the same manner as in Example 1-1 to obtain a polyimide resin composite film 3. The film thickness is 21 μm, and the zeolite content in the obtained film is 28.6% by mass relative to the film mass. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Example 2-2: Method for manufacturing polyimide resin composite film 4) Except for replacing zeolite C1 with zeolite C2, the rest is carried out in the same manner as in Example 1-2 to obtain a polyimide resin composite film 4. The film thickness is 21 μm, and the zeolite content in the obtained film is 9.1% by mass relative to the film mass. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Example 3-1: Method for manufacturing polyimide resin composite film 5) 0.24 g of zeolite T1, 0.6 g of polyimide precursor, and 2.4 g of NMP were mixed and stirred with a stirrer to obtain ink. The obtained ink was applied using a dripper manufactured by TESTER Industries, Ltd., and dried and calcined at 330°C for 30 minutes to obtain a polyimide resin composite film 5. In addition, the film thickness was 44 μm, and the zeolite content in the obtained film was 28.6% by mass relative to the film mass. The average thermal expansion coefficient and haze rate of the obtained film are shown in Table 1.

(Example 3-2: Method for manufacturing polyimide resin composite film 6) Zeolite T1 0.06g, polyimide precursor 0.6g, and NMP 2.4g were mixed and stirred with a stirrer to obtain ink. The obtained ink was applied using a dripper manufactured by TESTER Industries, Ltd., and dried and calcined at 330°C for 30 minutes to obtain a polyimide resin composite film 6. In addition, the film thickness was 21μm, and the zeolite content in the obtained film was 9.1% by mass relative to the film mass. The average thermal expansion coefficient, retardation value, and haze rate of the obtained film are shown in Table 1.

(Example 4-1: Method for manufacturing polyimide resin composite film 7) Except that zeolite T1 was replaced with FAU type zeolite HY(5) (silicon dioxide/alumina molar ratio = 40) manufactured by Catalytic Chemical Industries, Ltd., the rest was prepared in the same manner as in Example 3-2 to manufacture polyimide resin composite film 7. The zeolite content in the obtained film was 9.1% by mass relative to the film mass. The average thermal expansion coefficient and haze rate of the obtained film are shown in Table 1.

(Example 5-1: Method for manufacturing polyimide resin composite film 8) Except for replacing zeolite T1 with proton type ^* BEA type zeolite HSZ-940HOA (silicon dioxide/alumina molar ratio = 40) manufactured by Tosoh Corporation, the same method as in Example 3-2 was followed to manufacture polyimide resin composite film 8. The zeolite content in the obtained film was 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient of the obtained film is shown in Table 1.

(Comparative Example 1-2: Method for manufacturing polyimide resin composite film 9) Except that zeolite T1 was replaced with silica SC2500-SQ (average primary particle size 200nm) manufactured by Admatechs, the polyimide resin composite film 9 was manufactured in the same manner as in Example 1-1. In addition, the film thickness was 18μm, and the zeolite content in the obtained film was 9.1% by mass relative to the film mass. The average thermal expansion coefficient, haze rate, and elastic modulus of the obtained film are shown in Table 1.

(Comparative Example 1-3: Method for manufacturing polyimide resin composite film 10) Except for replacing zeolite C1 with negative expansion material FINE ZWO-01 made by Furuuchi Co., Ltd., the polyimide resin composite film 10 was manufactured in the same manner as in Example 1-1. The zeolite content in the obtained film was 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Comparative Example 1-4: Method for manufacturing polyimide resin composite film 11) Except for using zeolite A1 instead of zeolite T1, the polyimide resin composite film 11 was manufactured in the same manner as in Example 3-1. The zeolite content in the obtained film was 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient of the obtained film is shown in Table 1.

(Comparative Example 1-5: Method for manufacturing polyimide resin composite film 12) Except for replacing zeolite T1 with silicalite 1, the polyimide resin composite film 12 was manufactured in the same manner as in Example 3-1. The zeolite content in the obtained film was 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient, retardation value, haze rate and elastic modulus of the obtained film are shown in Table 1.

(Comparative Example 1-6: Method for manufacturing polyimide resin composite film 13) Except for replacing zeolite T1 with Zeoal Z4A-005 (average primary particle size 50nm, LTA type zeolite) manufactured by Nakamura Superhard Co., Ltd., the rest is made in the same way as in Example 3-1 to manufacture polyimide resin composite film 13. The zeolite content in the obtained film is 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient of the obtained film is shown in Table 1.

(Comparative Example 1-7: Method for manufacturing polyimide resin composite film 14) Except for using zeolite R1 instead of zeolite T1, the polyimide resin composite film 14 was manufactured in the same manner as in Example 3-1. The zeolite content in the obtained film was 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient of the obtained film is shown in Table 1.

(Resin composition preparation example 2: Preparation method of non-hydrogenated polyimide precursor-containing composition M2) In a four-necked flask equipped with a nitrogen inlet tube, a cooler and a stirrer, add 635g (2.16mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 445g (2.22mol) of 4,4'-diaminodiphenyl ether and 3240g of N,N-dimethylacetamide, and heat and stir at 80°C for 6 hours to obtain a polyimide precursor-containing composition M2 containing 25% by mass of the polyimide precursor. The polyimide precursor is an aromatic compound that is not nuclear hydrogenated (hydrogenated).

(Comparative Example 1-8: Method for producing polyimide resin film 2) Except for replacing the polyimide precursor-containing composition M1 with M2, the polyimide resin film 2 was produced in the same manner as in Comparative Example 1-1. The average thermal expansion coefficient of the obtained film is shown in Table 1.

(Example 6-1: Method for manufacturing polyimide resin composite film 15) Except for using zeolite C1 and composition M2 containing polyimide precursor, the rest is carried out in the same manner as Example 1-1 to obtain polyimide resin composite film 15. The zeolite content in the obtained film is 9.1% by mass relative to the mass of the film. The average thermal expansion coefficient of the obtained film is shown in Table 1.

[Table 1] Table 1 Base film filler Zeolite structure Filler mass fraction in the film (mass %) Average thermal expansion coefficient (ppm/℃) Delay value(nm) Fog rate(%) Elastic modulus(GPa) thickness Embodiment 1-1 M1 (Hydrogenated PI) Polyimide resin composite film 1 Zeolite C1 CHA 28.6 32 48 0.7 6.5 19 Embodiment 1-2 Polyimide resin composite film 2 Zeolite C1 CHA 9.1 43 97 0.5 5.5 6 Example 2-1 Polyimide resin composite film 3 Zeolite C2 CHA 28.6 27 - 40.1 6.3 twenty one Example 2-2 Polyimide resin composite film 4 Zeolite C2 CHA 9.1 45 - 32.9 4.7 twenty one Example 3-1 Polyimide resin composite film 5 Zeolite T1 ERI/OFF 28.6 32 - 82.6 - 44 Example 3-2 Polyimide resin composite film 6 Zeolite T1 ERI/OFF 9.1 43 - 44.8 4.8 20 Example 4-1 Polyimide resin composite film 7 HY(5) FAU 9.1 44 - 65.7 - twenty one Example 5-1 Polyimide resin composite film 8 HSZ-940HOA BEA 9.1 44 - - - 20 Comparison Example 1-1 Polyimide resin film 1 No fillers - 0 50 40 0.3 4.1 10 Comparison Example 1-2 Polyimide resin composite film 9 Silicon dioxide particles SC2500-SQ - 9.1 46 - 76.3 4.2 18 Comparison Example 1-3 Polyimide resin composite film 10 Negative expansion material ZrW2O8 - 9.1 46 - - - - Comparison Example 1-4 Polyimide resin composite film 11 Aluminum phosphate A1 APC 9.1 49 - - - - Comparison Examples 1-5 Polyimide resin composite film 12 Silica 1 MFI 9.1 46 - - - - Comparison Example 1-6 Polyimide resin composite film 13 Zeoal Z4A-005 LTA 9.1 46 - - - - Comparison Examples 1-7 Polyimide resin composite film 14 Zeolite R1 RHO 9.1 49 - - - - Example 6-1 M2 (Non-hydrogenated PI) Polyimide resin composite film 15 Zeolite C1 CHA 9.1 46 - - - - Comparison Examples 1-8 Polyimide resin film 2 No fillers - 0 52 - - - -

From Table 1, it can be seen that in the polyimide resin composite material containing zeolite in the embodiment of the present invention, the average thermal expansion coefficient of the resin composite material is less than 50ppm, the retardation value of the resin composite material is less than 150nm, which is as low as that of polyimide resin, and the haze rate of the resin composite material is less than 5%, which is as low as that of polyimide resin. Compared with the polyimide resin composite material containing silicon dioxide, which is a general inorganic filler, and zirconium tungstate, which is a filler with a negative thermal expansion coefficient, the average thermal expansion coefficient of the polyimide resin composite material containing zeolite in the embodiment of the present invention has a greater decrease. The average thermal expansion coefficient of polyimide resin composites containing silica with a positive thermal expansion coefficient and zirconium tungstate with a negative thermal expansion coefficient is the same, indicating that the average thermal expansion coefficient of the filler itself does not determine the average thermal expansion coefficient of the resin composite. The average thermal expansion coefficient of polyimide resin composites containing specific zeolites is greatly reduced. The average thermal expansion coefficient of polyimide resin composites containing d6r-containing zeolites (CHA, ERI) and/or mtw-containing zeolites (BEA) is greater than that of polyimide resin composites containing zeolites without these. It is speculated that the average thermal expansion coefficient becomes smaller because of the inclusion of these CBUs. The average thermal expansion coefficient reduction rate caused by the 9.1 mass% zeolite content is 14.0% when using hydrogenated polyimide, compared to 12.0% when using non-hydrogenated polyimide. It is known that the effect is more obvious when using hydrogenated polyimide. Although the reason has not been clarified, it is believed that it is the result of weakening the π-π stacking between resins through hydrogenation and strengthening the interaction with zeolite.

From the above results, it can be seen that the polyimide resin composite containing zeolite in one embodiment of the present invention can provide a polyimide resin composite containing zeolite that has high suppression of deformation such as warping, good image clarity, and high transparency, and can be used in components such as electronic devices at a low cost. (Industrial applicability)

By using the polyimide resin composite material of one embodiment of the present invention, a polyimide resin composite material containing zeolite which has high resistance to deformation such as warping, high image clarity and high transparency, and can be used for components such as electronic devices can be provided at a low cost.

1: Resin composite 2: Zeolite 3: Resin 11: Semiconductor layer 12: Insulator layer 13, 14: Source electrode and drain electrode 15: Gate electrode 16: Substrate 17: FET element 31: Substrate 32: Anode 33: Hole injection layer 34: Hole transport layer 35: Luminescent layer 36: Electron transport layer 37: Electron injection layer 38: Cathode 39: Electroluminescent element 51: Cathode 52: Electron extraction layer 53: Active layer 54: Hole extraction layer 55: Anode 56: Substrate 57: Photoelectric conversion element 101: Weather-resistant protective film 102: UV blocking film 103, 109: Gas barrier film 104, 108: Gas collector film 105, 107: Sealing material 106: Solar cell element 110: Backing sheet 111: Thin-film solar cell 112: Substrate 113: Solar cell module

FIG. 1 is a schematic diagram of a resin composite material containing zeolite and resin in an embodiment of the present invention. FIG. 2 (A) to (D) are schematic cross-sectional views of a field effect transistor element in an embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of an electroluminescent element in an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a photoelectric conversion element in an embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of a solar cell in an embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of a solar cell module in an embodiment of the present invention.

1: Resin composite material

2: Zeolite

3: Resin

Claims (10)

A polyimide resin composite material containing zeolite is used for electronic material devices, comprising: a composite building unit (CBU) is a zeolite containing at least one of d6r and mtw; and a polyimide resin; The average particle size of the zeolite is greater than 15nm and less than 100nm; The fog rate is less than 5%. The polyimide resin composite material containing zeolite as claimed in claim 1, wherein the average thermal expansion coefficient at a temperature above 0°C and below the glass transition temperature of the polyimide resin is less than 50 ppm/K. A polyimide resin composite material containing zeolite as claimed in claim 1, wherein the retardation value is less than 150 nm. A polyimide resin composite containing zeolite as claimed in claim 1, wherein the zeolite has any one of the structures of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW and TSC. The polyimide resin composite material containing zeolite as claimed in claim 1, wherein the elastic modulus at 25°C is greater than or equal to 4.5 GPa and less than or equal to 8.0 GPa. The polyimide resin composite material containing zeolite as claimed in claim 1, wherein the zeolite is contained in an amount of 1 mass % or more and 80 mass % or less relative to the polyimide resin composite material containing zeolite. The polyimide resin composite material containing zeolite as claimed in claim 1, wherein the polyimide resin is a core hydrogenated aromatic compound. The polyimide resin composite material containing zeolite as claimed in claim 1, wherein the polyimide resin is a thermosetting polyimide resin. A film comprises the polyimide resin composite material containing zeolite according to any one of claims 1 to 8. An electronic device comprises the polyimide resin composite material containing zeolite according to any one of claims 1 to 8.