KR102462579B1 - Zeolite-containing polyimide resin composite, zeolite-containing polyimide resin precursor composition, film, and electronic device - Google Patents

Abstract

An object of the present invention is to provide a polyimide resin composite material suitable for members such as electronic devices, which has all of high suppression properties against deformation such as warpage, high image clarity, and high transparency at low cost. A zeolite-containing polyimide resin composite comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin, and for use in an electronic material device.

Description

Zeolite-containing polyimide resin composite, zeolite-containing polyimide resin precursor composition, film, and electronic device

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

In recent years, development of the electronic device excellent in flexibility using a resin film is advancing actively. Specifically, OLED (organic electroluminescent element) using a polyimide resin film as a board|substrate is mentioned, It is further used for a display apparatus etc.

Generally, polyimide resin has a comparatively high glass transition temperature compared with other resin. However, since polyimide resins tend to have a large average coefficient of thermal expansion under high temperatures, deformation such as warpage of the polyimide resin film in the high-temperature treatment process at the time of manufacturing electronic devices satisfies the initial characteristics required for electronic devices. and the polyimide resin film is deformed such as warping due to heat generated by driving of the electronic device, which further causes peeling or disconnection of parts installed on the resin, so that the required durability characteristics of the electronic device cannot be satisfied. There is a possibility that there is a problem that there is no such thing. Therefore, it is calculated|required that the average coefficient of thermal expansion of polyimide resin is low.

Moreover, in the display apparatus using OLED, in order to observe the image displayed through a base material, image clarity and transparency are important characteristics. Therefore, it is calculated|required that the retardation value and haze rate of polyimide resin used as a board|substrate be low.

On the other hand, in order to prevent deformation such as warpage, it is preferable that the in-plane orientation of the polyimide resin is uniform, but for good image clarity and high transparency, it is preferable that the in-plane orientation of the polyimide resin is not uniform. There is a trade-off relationship between deformation prevention, good image clarity, and high transparency (Patent Documents 1-3).

As a technique that deviates from the above trade-off relationship, it is known to study the units constituting the resin and to add a filler. For example, Patent Documents 1 to 3 describe a polyimide resin having a relatively low average coefficient of thermal expansion, a relatively high image clarity, and/or a relatively high transparency by including a special component in the unit constituting the resin, have. In addition, Patent Documents 3 and 4 describe a polyimide resin composite material having a relatively low average coefficient of thermal expansion, a relatively high image clarity, and/or a relatively high transparency by adding silica fine particles to a polyimide resin.

International Publication No. 2015/125895 International Publication No. 2014/007112 Japanese Patent Laid-Open No. 2016-204569 International Publication No. 2014/051050

A film using a polyimide resin as described in Patent Documents 1 to 3 suppresses deformation such as warpage during a high-temperature treatment process, has good image clarity, and is a high-transparency film used for members such as electronic devices can be expected to However, since a special component is included in the unit which comprises resin, it is a subject that it is a special polyimide resin in which the problem that manufacturing cost is high exists newly.

On the other hand, a film of a polyimide resin composite material in which a filler is added to a polyimide resin as described in Patent Documents 3 and 4 suppresses deformation such as warpage during a high temperature treatment process, and has good image clarity and high transparency. As such, it can be expected to be used as a member of an electronic device or the like. Moreover, since there is no need for a special polyimide resin, it can be expected that it is generally cheaply used. However, according to the studies of the present inventors, in the case of the resin composites described in Patent Documents 3 and 4, since the silica fine particles added as a filler tend to agglomerate, cloudiness partially becomes noticeable with the passage of time, and the transparency decreases. It has been found that there are cases where In addition, if a large amount of silica fine particles is not added, it is difficult to lower the average coefficient of thermal expansion of the resin composite material. It was found that the reproducibility of the image clarity of the film was poor and brittle.

Therefore, an object of the present invention is to provide a polyimide resin composite suitable for members such as electronic devices, which has all of high suppression against deformation such as warpage, good image clarity, and high transparency, at an affordable price.

As a result of intensive studies in view of the above circumstances, the present inventors, by dispersing the zeolite of a specific structure in the polyimide resin, the average coefficient of thermal expansion (CTE) of the polyimide resin composite material is small, the haze rate is low, and the retardation value found to be small, and arrived at the present invention. Moreover, in this invention, it also discovered that an elasticity modulus could also be enlarged with the structure mentioned above, and this invention was reached.

That is, the summary of this invention is as follows.

[1] A zeolite-containing polyimide resin composite material for an electronic material device, comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin.

[2] A zeolite-containing polyimide resin composite comprising a zeolite and a polyimide resin,

The average coefficient of thermal expansion at 0 ° C. or higher and below the glass transition temperature of the polyimide resin is less than 50 ppm/K,

The retardation value is 150 nm or less, and

A haze ratio of 5% or less, a zeolite-containing polyimide resin composite.

[3] Structural Unit Composite Building Unit (CBU), a zeolite containing at least any of d6r and mtw, and a polyimide resin, and a transparent zeolite-containing polyimide resin composite.

[4] The zeolite-containing polyimide resin according to any one of [1] to [3], wherein the zeolite has any of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structures. composites.

[5] The zeolite-containing polyimide resin composite material according to any one of [1] to [4], wherein the elastic modulus at 25°C is 4.5 GPa or more.

[6] The zeolite-containing polyimide resin composite material according to any one of [1] to [5], wherein the zeolite is contained in an amount of 1 mass% or more and 80 mass% or less with respect to the zeolite-containing polyimide resin composite material.

[7] The zeolite-containing polyimide resin composite material according to any one of [1] to [6], wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound.

[8] A zeolite-containing polyimide resin precursor composition comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin precursor.

[9] A zeolite-containing polyimide resin composite, which is a cured product of the composition according to [8].

[10] A film containing the zeolite-containing polyimide resin composite according to any one of [1] to [7] or [9].

[11] An electronic device containing the zeolite-containing polyimide resin composite according to any one of [1] to [7] or [9].

[12] A zeolite-containing polyimide composite comprising a zeolite and a polyimide resin, comprising:

The average coefficient of thermal expansion at 0 ° C. or higher and below the glass transition temperature of the polyimide resin is less than 50 ppm/K,

The elastic modulus at 25°C is 4.5 GPa or more, and

A haze ratio of 5% or less, a zeolite-containing polyimide resin composite.

It is possible to provide a polyimide resin composite material suitable for members such as electronic devices, which has both high suppression properties against deformation such as warpage, high image clarity, and high transparency at low cost.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the resin composite material containing zeolite and resin as one Embodiment of this invention.
Fig. 2 is a cross-sectional view schematically showing the configuration of a field effect transistor element according to an embodiment of the present invention.
Fig. 3 is a cross-sectional view schematically showing the configuration of an electroluminescent device according to an embodiment of the present invention.
It is sectional drawing which shows typically the structure of the photoelectric conversion element as one Embodiment of this invention.
5 is a cross-sectional view schematically showing the configuration of a solar cell according to an embodiment of the present invention.
6 is a cross-sectional view schematically showing the configuration of a solar cell module according to an embodiment of the present invention.

Although embodiment of this invention is described in detail below, these description is an example of embodiment of this invention, and this invention is not limited to these content unless the summary is exceeded.

A first aspect of the zeolite-containing polyimide resin composite material according to one embodiment of the present invention is a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin, containing an electronic material device (Also called "electronic device") Yongin, a zeolite-containing polyimide resin composite material.

In addition, a second aspect of the zeolite-containing polyimide resin composite, which is another embodiment of the present invention, is a zeolite-containing transparent polyimide resin composite, comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU); , a polyimide resin-containing, transparent, zeolite-containing transparent polyimide resin composite material. "Transparency" in the present invention is a polyimide resin composite material having a haze ratio of 5% or less.

In the present specification, the zeolite-containing polyimide resin composite is also simply referred to as a “composite”, a “resin composite”, and a “polyimide resin composite”.

1 is a diagram schematically showing a resin composite material according to an embodiment of the present invention. Hereinafter, the resin composite material (1) will be described in detail.

<1. Resin Composite (1)>

As shown in FIG. 1 , the resin composite material 1 contains a zeolite 2 and a polyimide resin 3 .

<1.1 Zeolite>

The zeolite contained in the resin composite will be described. In addition, the zeolite is a TO ₄ unit (the T element is an element other than oxygen constituting the skeleton) composed of silicon or aluminum and oxygen as a basic unit, and specifically, crystalline porous alumina nosilicate, crystalline porous aluminophosphate (ALPO), or crystalline porous silicoaluminophosphate (SAPO). Moreover, this _TO4 unit consists of a structural unit called Composite Building Unit (CBU) which several (several - several dozen) connected. For that reason, it has regular channels (tubular pores) and cavities (cavities).

The resin composite material contains a zeolite containing at least one of d6r and mtw as a structural unit Composite Building Unit (CBU), and the zeolite is used as a filler. The said zeolite contains a polyimide resin, and has a structural unit which tends to form the cavity into which a part of the imide bond which the said polyimide resin has is easy to enter. Therefore, since the said zeolite has favorable compatibility with polyimide resin compared with fillers, such as a silica particle which have been used conventionally, aggregation is hard to generate|occur|produce.

In addition, in the resin composite material, since a small amount of zeolite can significantly lower the average coefficient of thermal expansion of the resin composite material, cloudiness can be prevented even over time, and high transparency can be maintained. Moreover, since content of the zeolite which is a filler is small, high flexibility can also be maintained, embrittlement, deformation, etc. are prevented, and it also leads to favorable image clarity.

Zeolites with d6r include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT , SAV, SBS, SBT, SFW, SSF, SZR, TSC, and -WEN-type zeolites.

In addition, as a zeolite having mtw, ^* BEA, BEC, CSV, GON, ISV, ITG, ^* -ITN, IWS, MSE, MTW, SFH, SFN, SSF, ^* -SSO, UOS, and UOV type zeolite structure can be heard

Moreover, since it has three-dimensional interaction with the part of imide bond contained in polyimide resin, it is more preferable that it is a zeolite which further has a three-dimensional channel. 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 these, from the viewpoint of easiness of microparticle formation, those further having a structure of an oxygen 8-membered ring or less are particularly preferable, and specifically, AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and and a zeolite having a TSC structure.

In addition, in the present specification, the structure having an oxygen 8-membered ring refers to the number of oxygen elements in the case of the largest number of oxygen among pores composed of oxygen forming a zeolite skeleton and a T element (an element other than oxygen constituting the skeleton). It means an 8-person structure.

(The content of zeolite in the resin composite material)

The content of zeolite contained in the resin composite is not particularly limited, but is usually 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, still more preferably 7 mass% or more, and particularly preferably Preferably it is 10 mass % or more, Most preferably 15 mass % or more, On the other hand, it is usually 80 mass % or less, Preferably it is 70 mass % or less, More preferably, it is 50 mass % or less, More preferably, it is 40 mass % or less. % or less, particularly preferably 30 mass% or less, and most preferably 20 mass% or less. As mentioned above, when a small amount of zeolite is added to resin, compared with the case where silica etc. are used as a filler, the average coefficient of thermal expansion obtained can be reduced significantly.

Therefore, when the zeolite content is 1 mass % or more and 80 mass % or less, the resin composite material can have both good image clarity and high transparency while suppressing embrittlement, deformation, and the like. Especially, when it is 10 mass % or more and 30 mass % or less, since the property of the said resin composite material is exhibited more clearly with a small content compared with silica etc., it is especially preferable.

The zeolite in the resin composite material may contain individually by 1 type, and may contain 2 or more types in arbitrary combinations and ratios. However, at least one of them is a zeolite in which either of d6r and mtw is contained in the structural unit Composite Building Unit (CBU) as described above.

Specifically, the zeolite is preferably an aluminosilicate from the viewpoint of ease of manufacture, but instead of silicon or aluminum, gallium, iron, boron, titanium, zirconium, or tin in a range not significantly impairing the effects of the present invention. , zinc and phosphorus may be used, and elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, and phosphorus may be included together with silicon and aluminum.

The structure of the zeolite can be represented by a code that prescribes the structure of a zeolite determined by the International Zeolite Association (IZA). In addition, the structure of the zeolite is based on the X-ray diffraction pattern obtained by the X-ray structure analysis apparatus (For example, the table-top X-ray diffraction apparatus D2PHASER manufactured by BRUKER), the zeolite structure database 2018 version (http://www This can be specified using .iza-structure.org/databases/) .

(average coefficient of thermal expansion of zeolite)

The average coefficient of thermal expansion of the zeolite is not particularly limited as long as the resin composite exhibits desirable performance, but is less than 0 ppm/K, preferably -2 ppm/K or less, more preferably -3 ppm/K or less, more preferably -5 ppm/K or less, particularly preferably -7 ppm/K or less, most preferably -10 ppm/K or less, and on the other hand, usually -1000 ppm/K or more. , preferably -900 ppm/K or more, more preferably -800 ppm/K or more, still more preferably -700 ppm/K or more, particularly preferably -500 ppm/K or more, most preferably and more than -300 ppm/K. When the average coefficient of thermal expansion of the zeolite is within the above range, the resin composite material has a low content of zeolite, can also maintain high flexibility, and suppress embrittlement and deformation, while having good image clarity and high transparency.

In addition, the average coefficient of thermal expansion of a zeolite can be measured by calculating a lattice constant using the BRUKER X-ray-diffraction apparatus D8ADVANCE and X-ray-diffraction analysis software JADE.

The average coefficient of thermal expansion of this zeolite measures the thermal expansion coefficient of 60 degreeC and 220 degreeC, and let the average be an average coefficient of thermal expansion.

In addition, the framework density of the zeolite is not particularly limited as long as the resin composite exhibits desirable performance, but is preferably 17.0T/1000 Å ³ or less, more preferably 16.0T/1000 Å ³ or less , more preferably 15.0T/1000 Å ³ or less, on the other hand, preferably 12.0T/1000 Å ³ or more, more preferably, 13.0T/1000 Å ³ or more, still more preferably, 14.0T/ 1000 Å ³ or more. When the framework density is within the above range, the zeolite tends to be finely divided so that it is difficult to aggregate, and while suppressing embrittlement, deformation, and the like, good image clarity and high transparency can be obtained.

In addition, the framework density represents the number of T atoms present per unit volume of the zeolite, and is a value determined by the structure of the zeolite. In this specification, the numerical value described in IZA's zeolite structure database 2018 edition (http://www.iza-structure.org/databases/) may be used.

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

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

Examples of the zeolite having a framework density of greater than 14.0T/1000 Å ³ and less than or equal to 15.0T/1000 Å ³ include zeolites having ISV, IWS, KFI, SAS, and SAV-type structures.

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

In addition, the silica/alumina molar ratio (SAR) of the zeolite is not particularly limited as long as the resin composite exhibits desirable performance, but is usually 0.1 or more, preferably 0.5 or more, more preferably 4 or more, still more preferably is 9 or more, particularly preferably 12 or more, and is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, still more preferably 100 or less. When the silica/alumina molar ratio (SAR) is within the above range, the amount of the counter cation can be appropriately controlled, and the production cost of the zeolite is also reduced.

In addition, when an element such as gallium, iron, boron, titanium, zirconium, tin, zinc, or phosphorus is used instead of silicon and aluminum constituting the TO ₄ unit, the molar ratio of the oxide of the element to be replaced is alumina or silica Convert it as a molar ratio of Specifically, when gallium is used instead of aluminum, the molar ratio of gallium oxide may be converted into the molar ratio of alumina.

In addition, the counter cation of the zeolite is not particularly limited as long as the resin composite material exhibits desirable performance, but is usually a structure defining agent, a proton, an alkali metal ion, or an alkaline earth metal ion, and preferably a structure defining agent. , a proton or an alkali metal ion, more preferably a structure defining agent, a proton, a Li ion, a Na ion, or a K ion, still more preferably a structure defining agent, a proton, or a Li ion, particularly preferably a proton to be. In the case of a structure-regulating agent, compared with an alkali metal ion or an alkaline-earth metal ion, since it has a softness|flexibility and since a zeolite tends to show the average coefficient of thermal expansion of less than 0 ppm/K, it is preferable. Moreover, since it is easy to show the average coefficient of thermal expansion of less than 0 ppm/K of a zeolite, so that the size of an alkali metal ion and alkaline-earth metal ion is small is preferable. Especially, the case of proton is preferable because it becomes easy to reduce the average coefficient of thermal expansion of a resin composite material.

That is, the zeolite is preferably as-made (structure-regulating agent-containing type), proton type, or alkali metal type, and more preferably as-made, proton type, Li type, Na type, or K type. , more preferably as-made, protonic, Li, and most preferably protonic.

In addition, a structure defining agent is a template used by manufacture of a zeolite.

The crystallinity of the zeolite is not particularly limited as long as the resin composite exhibits desirable performance. The reason for this is that it is estimated that the Composite Building Unit (CBU) is a factor leading to the average coefficient of thermal expansion of the resin composite material rather than the structure determined by the IZA code.

In addition, the crystallinity of the zeolite is determined by comparing any X-ray diffraction peak obtained with an X-ray diffraction apparatus (for example, a tabletop X-ray diffraction apparatus D2PHASER manufactured by BRUKER) with the X-ray diffraction peak of the zeolite as a reference. can As a specific example of calculation, the crystallinity of the LTA type zeolite of Scientific Reports 2016, 6, Article number: 29210 is mentioned.

The average primary particle diameter of the zeolite is not particularly limited as long as the resin composite exhibits desirable performance, but is usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm. or more, and most preferably 40 nm or more. On the other hand, it is usually 2000 nm or less, preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 100 nm or less. When the average primary particle diameter of the zeolite is within the above range, the zeolite tends to be uniformly dispersed in the resin composite material, and furthermore, the transparency of the resin composite material obtained increases, and it tends to lead to good image clarity.

The average primary particle diameter of the zeolite is obtained by measuring the particle diameter of 30 or more arbitrarily selected primary particles in the observation of the particles by a scanning electron microscope (SEM), and averaging the particle diameters of the primary particles. In that case, the particle diameter shall mean the diameter (equivalent circle diameter) of a circle which has the same area as the projected area of a particle and becomes a largest diameter.

The zeolite may be in a state of secondary or higher-order particles in which primary particles are aggregated, as long as the resin composite material exhibits desirable performance. The average particle diameter in that state is not particularly limited, but usually 15 nm or more, preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, particularly preferably 40 nm or more, and most Preferably 50 nm or more, on the other hand usually 3000 nm or less, preferably 2000 nm or less, more preferably 1000 nm or less, still more preferably 500 nm or less, particularly preferably 300 nm or less, most preferably 100 nm or less. If it is within the above range, the zeolite tends to be uniformly dispersed in the resin composite material, and furthermore, the transparency of the resin composite material obtained increases, and it tends to lead to good image clarity.

In addition, the average particle diameter of the secondary or higher order particles of the zeolite is the same as the primary particles, in the observation of the particles by a scanning electron microscope (SEM), the particle diameter is measured for 30 or more particles arbitrarily selected, and the particles may be obtained by averaging the particle diameters of In that case, the particle diameter shall mean the diameter (equivalent circle diameter) of a circle which has the same area as the projected area of a particle and becomes a largest diameter. Moreover, you may use the _D50 value measured using the particle size distribution measuring apparatus. As a particle size distribution analyzer, a laser diffraction type particle size distribution analyzer may be used according to a particle diameter, and a dynamic light scattering type particle size distribution analyzer may be used.

There is no restriction|limiting in particular as a manufacturing method of a zeolite, It can manufacture inexpensively by a well-known hydrothermal synthesis method. For example, when manufacturing a CHA type zeolite, it can manufacture with reference to the method of Unexamined-Japanese-Patent No. 4896110.

In the method for producing zeolite, a structure-regulating agent can be used as a template if necessary. In general, there is no particular limitation as long as the target zeolite structure is a manufacturable structure-regulating agent. You don't have to use the agent.

In the case of producing a zeolite having a small average particle diameter, the synthesis time may be shorter than usual, and the synthesis temperature may be controlled to a temperature lower than usual for hydrothermal synthesis, or the zeolite obtained by hydrothermal synthesis may be used as beads. What is necessary is just to grind|pulverize and/or grind|pulverize by wet grinding, such as a mill and a ball mill.

As the pulverizing device used for the pulverization and/or pulverization, for example, "OB Mill" manufactured by Freund Turbo, "Nano Getter" manufactured by Ashizawa Finetech, "Nano Getter Mini", "Star Mill" ', and "Love Star" and "Starburst" manufactured by Sugino Machinery Co., Ltd., and the like. Moreover, although the crystallinity of the zeolite after grinding|pulverization decreases generally, it can recrystallize in the solution containing alumina, silica, etc. like the method of Unexamined-Japanese-Patent No. 2014-189476.

From the viewpoint of suppressing reaggregation of the zeolite after pulverization and/or pulverization, it is preferable to perform wet grinding in a solvent to disperse the zeolite having a small average particle diameter in the solvent. Especially, it is especially preferable to perform a bead mill at the point which can make an average particle diameter small. Moreover, in order to suppress re-aggregation after dispersion|distribution, you may use a dispersing agent at the time of wet grinding. As said solvent and dispersing agent, the solvent and dispersing agent illustrated by the structural component of the ink mentioned later can be used.

Further, in order to further reduce the average particle diameter of the zeolite in the dispersion in which the pulverized and/or pulverized zeolite is dispersed, centrifugal separation may be performed to remove particles having a large average particle diameter. As a result, the zeolite can be more uniformly dispersed in the resin composite material, and furthermore, the transparency of the obtained resin composite material is increased, which is preferable. In addition, as a centrifuge used for centrifugation, a commercially available apparatus (For example, Kokusan Corporation Centrifuge H-36, and Hitachi Aircraft Hitachi micro high-speed centrifuge CF15RN) can be used.

<1.2. Polyimide resin>

Hereinafter, the polyimide resin used for the resin composite will be described.

The polyimide resin may be used without limitation, either as a curable resin or as a thermoplastic resin. Among them, a curable resin capable of crosslinking such as an active energy ray-curable resin and a thermosetting resin is preferable because the uniform distribution of the resin and the zeolite in the resin composite material becomes higher than that of the thermoplastic resin. In particular, if it is a thermosetting resin, so that an exposure machine is not used, it is preferable at a point with low manufacturing cost. In addition, the active energy ray-curable resin composite material is a resin that is cured by, for example, ultraviolet rays, visible light, infrared rays, electron beams, or the like.

In addition, the polyimide resin may be a polyimide resin having an aromatic compound subjected to nuclear hydrogenation (also referred to as “hydrogenation”) or a polyimide resin having an aromatic compound that is not nuclear-hydrogenated, but has good compatibility with zeolite; In other words, since adhesiveness with a zeolite improves, especially when using for an electronic device, it is preferable that it is a polyimide resin which has a nuclear-hydrogenated aromatic compound.

As a specific example of a polyimide resin having a nuclear-hydrogenated aromatic compound, "Shinjeong Latest Polyimide -Basics and Applications-" (Japanese Polyimide/Aromatic Polymer Research Society compilation, NTS (2010)), International Publication No. 2015/ The polyimide resins exemplified in No. 125895, International Publication No. 2014/98042, and Japanese Patent Application Laid-Open No. 2016-128555 are applicable.

About the compatibility of a polyimide resin and a zeolite, the following is considered. For example, (1) a dispersing function as if using a dispersing agent by exhibiting an interaction between (1) an imide bond contained in the polyimide resin, an unreacted derived carbonyl group, and an amino group, and a Si-OH group on the surface of the zeolite It is considered that this occurs, (2) that a part of the imide bond contained in the polyimide resin enters a cavity formed by either d6r or mtw in the zeolite structural unit Composite Building Unit (CBU). Therefore, the zeolite can be easily dispersed uniformly in the polyimide resin composite material, and while suppressing embrittlement and deformation, good image clarity and high transparency can be achieved. As a result, cloudiness can be prevented in the long term, and good image clarity and high transparency can also be maintained.

Especially, compatibility with a zeolite becomes favorable as for the polyimide resin which has a nuclear-hydrogenated aromatic compound, the nuclear-hydrogenated aromatic compound inhibits (pi)-(pi) stacking derived from the (pi)-pi bond between aromatic compounds. In particular, with zeolites having d6r or mtw, compatibility is better, but in addition to the above reasons, CBU called d6r or mtw takes on the role of filling the space of the inhibited π-π stacking, I think the sex will get better. As a result, cloudiness can be prevented in the long term, and good image clarity and higher transparency can also be maintained.

The molecular weight of the polyimide resin is not particularly limited as long as the resin composite exhibits desirable performance, but is a value of the mass average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC), usually 1000 or more , Preferably it is 3000 or more, More preferably, it is 5000 or more. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150000 or less. Since it becomes the tendency for solubility to a solvent, a viscosity, etc. to become easy to handle by normal manufacturing equipment by being in the said range, it is preferable.

The number average molecular weight (Mn) of the polyimide resin is also not particularly limited as long as the resin composite material exhibits desirable performance, but is usually 500 or more, preferably 1000 or more, and more preferably 2500 or more. Moreover, it is 100000 or less normally, Preferably it is 90000 or less, More preferably, it is 80000 or less. Since it becomes the tendency for solubility to a solvent, a viscosity, etc. to become easy to handle by normal manufacturing equipment by being in the said range, it is preferable. The number average molecular weight of polystyrene conversion can be calculated|required by the method similar to the said mass average molecular weight.

Moreover, the value (Mw/Mn) obtained by dividing Mw of the polyimide resin by Mn is usually 1.5 or more, preferably 2 or more, more preferably 2.5 or more, and on the other hand, usually 5 or less, preferably 4.5 or less, more Preferably it is 4 or less. When it falls within the above range, the uniformity of the zeolite in the resin composite material is increased, and a molded article of the resin composite material excellent in smoothness is obtained.

The glass transition temperature (Tg) of the polyimide resin is usually 80°C or higher, preferably 120°C or higher, more preferably 170°C or higher, still more preferably 220°C or higher, and particularly preferably 250°C or higher. Moreover, it is 700 degrees C or less normally, Preferably it is 500 degrees C or less, More preferably, it is 400 degrees C or less, More preferably, it is 350 degrees C or less, Especially preferably, it is 320 degrees C or less. By being within the above range, the resin composite material can have both good image clarity and high transparency while suppressing embrittlement, deformation, and the like.

Polyimide resin is a material which has an average coefficient of thermal expansion larger than 0 ppm/K normally. The average coefficient of thermal expansion of the polyimide resin is not particularly limited as long as the resin composite material exhibits desirable performance, but is usually 0 ppm in a temperature range of 0° C. or higher and below the glass transition temperature of the resin. larger than /K, preferably 10 ppm/K or more, more preferably 20 ppm/K or more, still more preferably 30 ppm/K or more, particularly preferably 50 ppm/K or more, and Usually 200 ppm/K or less, Preferably it is 150 ppm/K or less, More preferably, it is 125 ppm/K or less, More preferably, it is 100 ppm/K or less, Especially preferably, it is 75 ppm/K or less. . By being within the above range, the resin composite material can have both good image clarity and high transparency while suppressing embrittlement, deformation, and the like. Moreover, since a small amount of zeolite is sufficient, cloudiness can be decreased in the long term.

In addition, the average coefficient of thermal expansion of resin can be measured by thermomechanical analysis by the method based on JISK7197 (2012). For example, it can measure by stretching the resin composite material made into a sheet using the thermomechanical analysis apparatus TMA/SS6100 by SI Nanotechnology. Specifically, it can be calculated|required with the inclination of the thermal expansion coefficient in the temperature of 2 points|pieces, normally 60 degreeC and 220 degreeC. When a glass transition temperature is 220 degrees C or less, the average of the measured value in 60 degreeC and a glass transition temperature can be taken. In addition, the glass transition temperature of resin can be calculated|required from the inflection point measured by thermomechanical analysis.

In addition, as long as the resin composite material exhibits desirable performance, the manufacturing method of a polyimide resin is not specifically limited, What is necessary is just to manufacture by a well-known method. For example, it can manufacture by the method described in "Shinjeong latest polyimide -foundation and application-" (Edited by the Japanese Polyimide/Aromatic Polymer Research Society, NS (2010)).

<1.3. Other compounds>

The resin composite material may contain other compounds in addition to the zeolite and polyimide resin as long as the effects of the present invention are not significantly impaired. For example, as will be described later, when manufacturing a resin composite material, a dispersant, a surface treatment agent, a surfactant, an imidization accelerator, a solvent, etc. may be included in the ink or kneaded material, and residual components thereof are contained in the resin composite material. it may be

<1.4. Characteristics of zeolite-containing polyimide resin composites>

With the above-described configuration, a zeolite-containing polyimide resin composite material having properties not previously available can be obtained. Specifically, it is a third aspect of a zeolite-containing polyimide resin composite material according to another embodiment of the present invention, and a zeolite-containing polyimide resin composite material containing a zeolite and a polyimide resin having a nuclear-hydrogenated aromatic compound, 0 ° C. or higher The average coefficient of thermal expansion of the composite material at or below the glass transition temperature of the polyimide resin is less than 50 ppm/K, the retardation value of the composite material is 150 nm or less, and the haze rate of the composite material is 5% or less, containing zeolite A polyimide composite material, or a fourth aspect, a zeolite-containing polyimide composite containing a zeolite and a polyimide resin, wherein the average coefficient of thermal expansion at 0° C. or higher and below the glass transition temperature of the polyimide resin is 50 ppm/K less than, the elastic modulus in 25 degreeC is 4.5 GPa or more, and the haze rate is 5 % or less, The zeolite containing polyimide resin composite material is obtained.

The average coefficient of thermal expansion of the zeolite-containing polyimide resin composite material at 0°C or higher and below the glass transition temperature of the polyimide resin can be less than 50 ppm/K. Preferably it is 45 ppm/K or less, More preferably, it is 40 ppm/K or less, More preferably, it is 35 ppm/K or less, Especially preferably, it is 30 ppm/K or less. Moreover, it is 0 ppm/K or more normally, Preferably it is 5 ppm/K or more, More preferably, it is 10 ppm/K or more, More preferably, it is 15 ppm/K or more, Especially preferably, it is 20 ppm/K or more. More than that. In addition, the average coefficient of thermal expansion of the resin composite material can be measured by the method similar to the average coefficient of thermal expansion of the above-mentioned resin.

In addition, the retardation value of the zeolite-containing polyimide resin composite material can be 150 nm or less. Preferably it is 125 nm or less, More preferably, it is 100 nm or less, More preferably, it is 75 nm or less, Especially preferably, it is 50 nm or less. Moreover, since it is so preferable that it is close to zero, there is no preferable lower limit. In addition, a retardation value can be measured using retardation film and an optical material inspection apparatus. For example, it is computable as a value of wavelength 460nm with respect to a film|membrane with a film thickness of 10 micrometers using RETS-100 by Otsuka Electronics.

In addition, the haze ratio of the zeolite-containing polyimide resin composite material is a value with respect to D65 light, and can be usually 5% or less. Preferably it is 4 % or less, More preferably, it is 3 % or less, More preferably, it is 2 % or less, Especially preferably, it is 1 % or less. Moreover, since it is so preferable that it is close to zero, there is no preferable lower limit. In addition, a haze rate is measured by the method based on JISK7136 (2000) and JISK7361-1 (1997). Specifically, it can measure with a haze meter (for example, Suga Test Instruments TM double beam automatic haze computer HZ-2).

The light transmittance of the resin composite material at a wavelength of 450 nm is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, particularly preferably 85% or more, and most preferably In most cases, it is 90% or more. Since it is so preferable that it is close to 100 %, there is no preferable upper limit. By being in the said range, favorable image clarity and high transparency can be combined. In addition, the transmittance|permeability can be measured with the spectrophotometer (For example, Shimadzu Corporation spectrophotometer UV-2500PC).

The visible light transmittance of the resin composite material is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, particularly preferably 75% or more, and most preferably 80% or more. Since it is so preferable that it is close to 100 %, there is no preferable upper limit. By being in the said range, favorable image clarity and high transparency can be combined. In addition, the visible ray transmittance|permeability is computable by the method defined by JIS R3106 (1998) from the value measured with the spectrophotometer (For example, Shimadzu Corporation spectrophotometer UV-2500PC).

The yellow index (yellowness) value of the resin composite is preferably -20 or more, more preferably -10 or more, still more preferably -5 or more, particularly preferably -3 or more, and most preferably is greater than or equal to -1. On the other hand, Preferably it is 20 or less, More preferably, it is 10 or less, More preferably, it is 5 or less, Especially preferably, it is 3 or less, Most preferably, it is 1 or less. By being in the said range, favorable image clarity and high transparency can be combined. In addition, a yellow index value can be measured by the method based on JISK7373 (2006). Specifically, it can calculate with respect to the film|membrane with a film thickness of 10 micrometers using the color computer SM5 manufactured by Suga Test Instruments.

The elastic modulus of the resin composite material at 25°C (hereinafter, the storage elastic modulus of the resin composite material may be simply referred to as "elastic modulus" in this specification) is not particularly limited, but is usually 4.0 GPa or more, preferably 4.2 GPa or more. and more preferably 4.5 GPa or more, still more preferably 4.6 GPa or more, particularly preferably 4.7 GPa or more, on the other hand, usually 8.0 GPa or less, preferably 7.5 GPa or less, and more preferably 7.0 GPa or less, It is more preferable that it is 6.8 GPa or less, and it is especially preferable that it is 6.5 GPa or less. By being in the above range, it is possible to have high suppression properties against deformation such as warpage.

The storage elastic modulus of the resin composite is measured, for example, by the dynamic viscoelasticity measurement method described in JIS K-7244 method, using a dynamic viscoelasticity device DMS6100 manufactured by SI Nanotechnology Co., Ltd., in the measurement temperature range: -100°C to 150°C, Frequency: 1 Hz, temperature increase rate: 5°C/min, measurement can be performed in dual cantilever tension mode.

In the resin composite, the clouding accompanying the passage of time can be quantitatively quantified by the above-described haze rate in D65 light, light transmittance at a wavelength of 450 nm, or visible light transmittance, but can make an honest judgment.

In addition, the flexibility in the resin composite material can be quantitatively quantified by a bending resistance test or the like, but qualitative judgment can be made by counting the number of cracks or stripes caused by bending by hand.

<1.5. Manufacturing method of zeolite-containing polyimide resin composite>

The production method of the polyimide resin composite material is not particularly limited as long as the resin composite material exhibits desirable performance, and conventional methods such as molding and injection molding in a hot melt state can be used. In order to utilize the gas barrier property, etc., it is used in the form of a film in many cases. Therefore, in the following, a polyimide resin precursor, a zeolite, and a solvent are mixed with a polyimide resin precursor, a zeolite, and a solvent as a simple method, which is particularly suitable for producing a film-like composite material to produce a zeolite-containing polyimide resin precursor composition (also referred to as "ink"). Then, a method of applying the ink to a support or the like and then heating and drying will be described as an example. Therefore, the description of the polyimide resin, dispersing agent, solvent, etc. described below is not limited to ink and may be included in the composite material.

Since a polyimide resin is insoluble in many solvents, after shape|molding using the polyamic acid which is a polyimide precursor, it is converted into a polyimide resin by dehydration and cyclization (imidization). In that case, dehydration and cyclization may use heating or the imidation accelerator mentioned later, and the heating temperature which converts into polyimide resin corresponds to the hardening temperature mentioned later.

In addition, a polyimide resin precursor uses tetracarboxylic dianhydride and diamine as raw materials, and means the polyamic acid which superposed|polymerized in equimolar. In addition, as for a polyamic acid, the ink of the state superposed|polymerized with tetracarboxylic dianhydride and diamine is used as it is generally in ink.

<1.5.1. Composition of Ink>

The ink which is another embodiment of this invention is a zeolite containing polyimide resin precursor composition containing at least the above-mentioned zeolite and a polyimide resin precursor, These raw materials are mixed, or instead of a polyimide resin precursor, a polyimide It manufactures by mixing the composition containing resin or polyimide resin precursor raw material (tetracarboxylic dianhydride, and diamine), and a solvent.

The content of zeolite in the ink is usually 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, particularly preferably 7 mass% or more, and most preferably Preferably it is 10 mass % or more, on the other hand, it is usually 80 mass % or less, Preferably it is 70 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less, Especially preferably, it is 40 mass % or less. , most preferably 20 mass% or less. By being in the said range, a zeolite does not produce precipitation etc., and the ink which maintained the dispersed state for a long time can be manufactured. In addition, the amount of zeolite at the time of calculating the content rate of a zeolite is the total amount of a zeolite and the substance contained in a zeolite.

In addition, a zeolite may be used individually by 1 type in ink, and may use 2 or more types together by arbitrary combinations and a ratio.

As the polyimide resin used for the ink, the polyimide resin in the resin composite material according to the embodiment of the present invention described above can be used, and is usually 0.5 mass% or more, preferably 1 mass% or more, more preferably 3 Mass % or more, more preferably 5 mass % or more, particularly preferably 10 mass % or more, and on the other hand, usually 90 mass % or less, preferably 85 mass % or less, more preferably 80 mass % or less, still more preferably Preferably it is 75 mass % or less, Especially preferably, it is 70 mass % or less. By being in the said range, resin does not produce precipitation etc., and the ink which maintained the dispersed state for a long time can be manufactured.

In addition, polyimide resin may be used individually by 1 type in ink, and may use 2 or more types together by arbitrary combinations and a ratio.

Moreover, you may mix the polyamic acid which is a polyimide resin precursor instead of the polyimide resin mentioned above. In addition, the content rate of the polyimide resin precursor in ink should just be equivalent to the content rate of the above-mentioned resin which can be converted when it converts to polyimide resin.

Generally, the ink containing the polyamic acid which is a polyimide resin precursor uses the ink which added tetracarboxylic dianhydride and diamine equimolar, by superposing|polymerizing by heating, after forming a polyamic acid in an ink, and using it as an ink as it is.

Therefore, you may mix tetracarboxylic dianhydride and diamine instead of the polyimide resin mentioned above. In addition, the content rate of the polyimide resin precursor raw material (tetracarboxylic dianhydride and diamine) in ink should just correspond to the content rate of the above-mentioned resin which can be converted when it finally converts into polyimide resin.

In addition, as a specific example of tetracarboxylic dianhydride, there is no particular limitation as long as the resin composite material exhibits desirable performance. , NTS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042, and tetracarboxylic dianhydride exemplified in Japanese Patent Application Laid-Open No. 2016-128555 and the like. Especially, tetracarboxylic dianhydride which has a nuclear-hydrogenated aromatic compound is preferable.

In addition, as a specific example of diamine, there is no particular limitation as far as the resin composite material exhibits desirable performance, but "Shinjeong latest polyimide -foundation and application-" (Japanese Polyimide/Aromatic Polymer Research Society ed. )), International Publication No. 2015/125895, International Publication No. 2014/98042, and the diamine exemplified in Japanese Patent Application Laid-Open No. 2016-128555, and the like.

Moreover, as heating temperature for superposing|polymerizing equimolar of tetracarboxylic dianhydride and diamine, and forming a polyamic acid, it is preferable that it is less than the temperature at which this polyamic acid dehydrates and cyclizes further and converts into a polyimide.

The solvent is not particularly limited as long as the resin composite material exhibits desirable performance, and for example, water; aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, or decane; aromatic hydrocarbons such as toluene, xylene, chlorobenzene, or orthodichlorobenzene; alcohols such as methanol, ethanol, isopropanol, 2-butoxyethanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone, or cyclohexanone; esters such as ethyl acetate, butyl acetate, or methyl lactate; halogen hydrocarbons such as chloroform, methylene chloride, 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; and the like.

Especially, since the solubility of a polyimide resin precursor is high, aromatic hydrocarbons, such as toluene, xylene, chlorobenzene, or orthodichlorobenzene; halogen hydrocarbons such as chloroform, methylene chloride, 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, are preferable.

In particular, amides such as N-methylpyrrolidone, dimethylformamide or dimethylacetamide are preferable from the viewpoint of high solubility of the polyimide resin precursor having a nuclear-hydrogenated aromatic compound.

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

The content of the solvent in the ink is usually 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and on the other hand, usually 99 mass% or less, preferably 95 mass% or less, more preferably is 90 mass% or less. Those within the above range are preferable in that the ink has an appropriate viscosity and a resin composite material having an appropriate thickness after drying is obtained.

In addition, a solvent may be used individually by 1 type in an ink, and may use 2 or more types together by arbitrary combinations and a ratio.

In addition, the ink may contain other compounds other than zeolite, polyimide resin or polyimide resin precursor or polyimide resin precursor raw material, and solvent, for example, a dispersant, a surface treatment agent, a surfactant, an imidization accelerator, etc. may be included. As these dispersants, surface treatment agents, surfactants, and imidization accelerators, the dispersing agents, surface treatment agents, surfactants and imidization accelerators in the above-mentioned resin composite material can be used.

The other compounds used in the ink are usually 0.001 mass % or more, preferably 0.003 mass % or more, more preferably 0.005 mass % or more, still more preferably 0.01 mass % or more, particularly preferably 0.05 mass % or more in the ink. On the other hand, it is normally 10 mass % or less, Preferably it is 7 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 3 mass % or less, Especially preferably, it is 1 mass % or less. By being in the said range, also in an ink, a dispersed state can be maintained, without a zeolite, a polyimide resin, or a polyimide resin precursor causing precipitation, etc.

The dispersant means a compound for uniformly dispersing the zeolite in the ink and in the resin composite material after production. For example, polysiloxane compounds, such as methylhydrogenpolysiloxane, polymethoxysilane, dimethylpolysiloxane, or dimethicone PEG-7 succinate, and its salt; Silane compounds, etc. (methyldimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, dichlorophenylsilane, chlorotrimethylsilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxy Silane, dodecyltrimethoxysilane, dodecyltrichlorosilane, octadecyltrimethoxysilane, octadecyltrichlorosilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrime Toxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, hexamethyldisiloxane, 1,1,1,3, organosilicon compounds such as 3,3-hexamethyldisilazane or 3-carboxypropyltrimethyltrimethoxysilane); carboxylic acid compounds such as formic acid, acetic acid, butyric acid, lauric acid, stearic acid, oleic acid, and 6-hydroxyhexanoic acid; organic phosphorus compounds such as lauryl ether phosphoric acid or trioctylphosphine; and amine compounds such as dimethylamine, tributylamine, trimethylamine, cyclohexylamine, ethylenediamine or polyethyleneimine, carboxylic acid amine compounds, and phosphate amine compounds. In addition, a carboxylic acid amine compound means the compound which has functional groups of both a carboxyl group and an amino group, and a phosphoric acid amine compound means the compound which has both functional groups of a phosphoric acid group and an amino group.

Especially, the dispersing agent of a phosphoric acid amine compound is preferable from the reason that the affinity to a zeolite is especially high.

A dispersing agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, the surface treatment agent and surfactant mentioned later may function as a dispersing agent. Further, the dispersant may be completely decomposed, partially decomposed, or not decomposed after the resin composite is produced.

In order to prevent aggregation of the zeolite and to uniformly disperse the zeolite in the ink and in the resin composite material after production, the zeolite may be treated with a surface treatment agent.

The surface treatment agent is not particularly limited, and a known material may be used, and a binder resin such as one used as the dispersing agent described above or a binder resin such as polyimine, polyester, polyamide, polyurethane or polyurea may be used as the surface treatment agent. .

A surface treatment agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Further, the surface treatment agent may be completely decomposed, partially decomposed, or not decomposed after the resin composite material is produced.

In the case of manufacturing the resin composite material, the ink may contain a surfactant for the purpose of preventing denting or drying unevenness in the resin composite material due to adhesion of minute bubbles or foreign matter, or the like.

There is no restriction|limiting in particular as surfactant, Well-known surfactant (cationic surfactant, anionic surfactant, nonionic surfactant) can be used. Among them, silicon-based surfactants, fluorine-based surfactants, or acetylene glycol-based surfactants are preferable. Specific examples of the surfactant include Triton X100 (manufactured by Dow Chemical Corporation) as a nonionic surfactant, Zonyl FS300 (manufactured by DuPont) as a fluorine-based surfactant, BYK-310, BYK-320, and BYK-320 as a silicon-based surfactant, Examples of BYK-345 (manufactured by Bikchemi Co., Ltd.) and acetylene glycol-based surfactants include surfinol 104, surfinol 465 (manufactured by Air Products), olphin EXP4036, or olphin EXP4200 (manufactured by Nisshin Chemical Industry Co., Ltd.).

Surfactant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In addition, the surfactant may be completely decomposed, may be partially decomposed, or may not be decomposed after the resin composite material is produced.

Moreover, the wettability of the ink mentioned later can be improved with surfactant. Wettability can be evaluated by a contact angle other than actually apply|coating to a base material. As a contact angle of an ink, it is 45 degrees or less normally with respect to PET base material, Preferably it is 30 degrees or less, More preferably, it is 15 degrees or less. Moreover, since a contact angle is not detected when it spreads on one surface of a base material, it is a thing which is not detected especially preferably. By being 45 degrees or less, the ink can be apply|coated on all the base materials. In addition, a contact angle can be measured with a contact angle meter. For example, it can measure with DM-501 by the Kyowa Interface Science company.

The imidation accelerator may be selected according to the method for producing the polyimide resin in the polyimide resin composite material, since imidization from the polyamic acid, which is a polyimide resin precursor, to the polyimide may be accelerated. For example, "Shinjeong's Latest Polyimide -Basics and Applications-" (Edited by the Japan Polyimide and Aromatic Polymer Research Society, NS (2010)), International Publication No. 2015/125895, International Publication No. 2014/98042 described, and the imidation accelerator of Unexamined-Japanese-Patent No. 2016-128555 etc. are mentioned.

An imidation accelerator may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. In addition, the imidation accelerator may exist independently in a composition, and may form the complex with a solvent etc. Moreover, you may form a multimer. In addition, the imidation accelerator may be completely decomposed, may be partially decomposed, or may not be decomposed after the resin composite material is produced.

It is preferable that an ink is stable for 24 hours or more, and it is more preferable that it is stable for 1 week or more. The more stable, the more stable the ink can be synthesized or stored for a long time, and the manufacturing cost can be reduced.

In addition, the stability of the ink can be evaluated by the formation of a precipitate, a change in viscosity, or the like. The formation of a precipitate can be judged with the naked eye or a dynamic light scattering particle size measuring apparatus. In addition, the viscosity can be calculated|required by the rotational viscometer method ("Introduction to physical chemistry experiment" (Kinya Adachi, Yasutaka Ishii, edited by Yoshida Satohiro, described in Chemistry Dongin (1993)).

As described above, the example in which the resin composite material is produced by applying an ink is shown, but the method for producing the polyimide resin composite material is not limited thereto. For example, without using a solvent, a polyimide resin or a polyimide resin precursor and a zeolite may be kneaded and then heated to prepare a resin composite material.

As the zeolite used for the kneaded material, the zeolite in the resin composite material may be used, one type may be used alone, or two or more types may be used together in any combination and ratio.

Moreover, the polyimide resin in a resin composite material can be used for the resin used for a kneaded material, and may be used individually by 1 type, and may use 2 or more types together in arbitrary combinations and a ratio.

Moreover, you may contain other compounds other than the zeolite used for a kneaded material, and polyimide resin. For example, you may contain the above-mentioned dispersing agent, a surface treatment agent, surfactant, an imidation promoter, etc. Other compounds may be used individually by 1 type, respectively, and may use 2 or more types together by arbitrary combinations and a ratio.

The proportion of the zeolite, polyimide resin, and other compounds used in the kneaded material is not particularly limited as long as the resin composite material produced by heating from the kneaded material exhibits desirable performance.

However, among the above, it is preferable to prepare a polyimide resin composite by applying an ink, since it is possible to easily adjust the viscosity during the molding process of the resin composite film.

The ink and the kneaded material are not particularly limited, and can be combined by a conventionally known method, and can be produced by mixing the constituent components of the ink and the kneaded material. In addition, in that case, for the purpose of improving uniformity, defoaming, etc., a paint shaker, a bead mill, a planetary mixer, a stirring type disperser, a homogenizer, a self-revolution stirring mixer, three rolls, a kneader, a single screw or twin screw kneader It is preferable to mix using a general kneading apparatus, such as a stirrer, etc.

The mixing flow chart of each component is optional, unless there is a special problem such as reaction or sedimentation. Among the components of the ink and the kneaded material, any two or three or more components are mixed in advance, and then the remaining components are mixed You may do it, and you may mix all at once.

<1.5.2. Molding of Polyimide Resin Composite>

As the method for molding the resin composite material, a method generally used for molding the resin can be used. In that case, you may perform the heating required for manufacture of a resin composite material, and the heating for shaping|molding simultaneously.

For example, when the polyimide resin composite material has thermoplasticity, it can be molded by filling the resin composite material into a desired shape, for example, in a mold. As a manufacturing method of such a molded object, an injection molding method, an injection compression molding method, an extrusion molding method, a compression molding method, etc. can be used.

When the polyimide resin constituting the resin composite material is a thermoplastic resin, the molding can be performed under the conditions of a temperature equal to or higher than the melting temperature of the thermoplastic resin and a predetermined molding speed or pressure.

The melting temperature is preferably less than 400°C, more preferably 370°C or less, particularly preferably 340°C or less, on the other hand, preferably 80°C or more, more preferably 90°C or more, and still more preferably 100°C or more. And it is especially preferable that it is 120 degreeC or more. It is preferable that it is less than 400 degreeC at the point which can respond also in the manufacturing process using a flexible base material, such as a roll-to-roll method, at the point. In addition, 80 ° C or higher is preferable in that the resin can be uniformly melted, 100 ° C or higher is preferable in that the influence of moisture can be reduced, and when it is 120 ° C or higher, the influence of moisture can be made smaller. It is preferable that it is possible.

In addition, when the resin constituting the polyimide resin composite material is a thermosetting resin composite material, which is a cured product of the polyimide resin precursor composition described above (when a resin precursor is used), molding of the resin composite material, that is, curing, is performed according to the respective composition. It can be carried out under curing temperature conditions according to

The curing temperature is preferably less than 400°C, more preferably 370°C or less, particularly preferably 340°C or less, on the other hand, preferably 0°C or more, more preferably 80°C or more, and still more preferably 90°C or more. and 100°C or higher is particularly preferred, and 120°C or higher is most preferred. It is preferable that it is less than 400 degreeC at the point which can respond also in the manufacturing process using a flexible base material, such as a roll-to-roll method, at the point. In addition, the temperature of 80 ° C. or higher is preferable in that curing progresses to some extent and the elution of unreacted components from the resin composite is suppressed. It is preferable at the point which can make the influence of a water|moisture content smaller that it is more than degreeC.

In the case of a resin composite material having fluidity, the resin composite material can be molded by laminating it on a desired support (lamination step) and then performing heat treatment (heat treatment step). In addition, you may remove a desired support body after manufacture.

As a heat processing method, well-known drying methods, such as hot air drying and drying by an infrared heater, are employable, for example. Especially, hot air drying with a quick drying rate is preferable. If it can dry by air drying, you may omit the heat treatment method.

The temperature of the heat treatment is preferably less than 400°C, more preferably 370°C or less, particularly preferably 340°C or less, on the other hand, preferably 80°C or more, more preferably 90°C or more, and still more preferably 100°C or more. It is preferable, and it is especially preferable that it is 120 degreeC or more. It is preferable that it is less than 400 degreeC at the point which can respond also in the manufacturing process using a flexible base material, such as a roll-to-roll method, at the point. In addition, a temperature of 80°C or higher is preferable in that the residual solvent in the sheet can be removed, a temperature of 100°C or higher is preferable in that the influence of moisture can be reduced, and a temperature of 120°C or higher makes the influence of moisture smaller. It is preferable because it can be done.

Although the heating time is not particularly limited, it is usually 30 seconds or more, preferably 1 minute or more, more preferably 2 minutes or more, still more preferably 3 minutes or more, and on the other hand, usually 24 hours or less, preferably 12 hours. or less, more preferably 1 hour or less, still more preferably 15 minutes or less. Those in the above range are preferable from the viewpoint of being suitable for a practical manufacturing process such as a roll-to-roll method.

Although the material of a support body is not specifically limited, As a preferable example of the material of a base material, Inorganic materials, such as quartz, glass, sapphire, or titania; and flexible substrates.

A flexible base material is a base material whose curvature radius is 0.1 mm or more normally, and 10000 mm or less. Further, in the case of manufacturing a flexible electronic device, in order to achieve both flexibility and characteristics as a support, the radius of curvature is preferably 0.3 mm or more, more preferably 1 mm or more, and on the other hand, it is preferably 3000 mm or less, It is more preferably 1000 mm or less. In addition, the radius of curvature can be calculated|required with the confocal microscope (For example, the shape measuring laser microscope VK-X200 manufactured by Keyence Corporation) of the base material which was bent until destruction, such as a deformation|transformation or a crack, does not appear.

Although it does not limit as a specific example of a flexible base material, Resin, such as an epoxy resin; paper materials such as paper or synthetic paper; Composite materials, such as what coated or laminated the surface in order to provide insulation to metal foil, such as silver, copper, stainless steel, titanium, and aluminum, are mentioned.

Moreover, among these, if a flexible base material can be used, manufacture by a roll-to-roll system will become possible, and productivity will improve.

When using a resin base material, it is necessary to pay attention to gas-barrier property. That is, when the gas barrier property of the base material is too low, the resin composite material may deteriorate due to the external air passing through the base material, which is not preferable. For this reason, when using a resin base material, it is preferable to ensure gas-barrier property by the method of forming a dense silicon oxide film etc. on at least one plate surface.

As glass, a soda glass, a blue plate glass, an alkali free glass, etc. are mentioned. Since there are few ions elution from glass, an alkali free glass is preferable among these.

There is no restriction|limiting in the shape of a support body, For example, things, such as a plate form, a film form, or a sheet form, can be used.

Moreover, although there is no restriction|limiting in the film thickness of a support body, Usually, it is 5 micrometers or more, Preferably it is 20 micrometers or more, On the other hand, it is 20 mm or less normally, Preferably it is 10 mm or less. It is preferable that the film thickness of a support body is 5 micrometers or more, since the possibility that intensity|strength will become insufficient becomes low. It is preferable that the film thickness of a support body is 20 mm or less, since cost is suppressed and it does not become heavy.

When the material of the support is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and on the other hand, usually 10 mm or less, preferably 5 mm or less. It is preferable that the film thickness of a glass substrate is 0.01 mm or more, since mechanical strength increases and it becomes difficult to crack. Moreover, since it does not become heavy that the film thickness of a glass base material is 5 mm or less, it is preferable.

In addition, a roll-to-roll system is a system which feeds out the flexible base material wound in roll shape, and processes it while it is wound up with a take-up roll, conveying intermittently or continuously. According to the roll-to-roll method, since it is possible to batch-process long substrates of the order of km, it is a production method suitable for mass production compared to the sheet-to-sheet method.

The size of the roll that can be used in the roll-to-roll system is not particularly limited as long as it can be handled by the roll-to-roll system, but the outer diameter of the roll core is usually 5 m or less, preferably 3 m or less, more preferably Preferably it is 1 m or less, on the other hand, it is usually 1 cm or more, Preferably it is 3 cm or more, More preferably, it is 5 cm or more, More preferably, it is 10 cm or more, Especially preferably, it is 20 cm or more. If these diameters are below the above upper limit, it is preferable from the viewpoint of high handleability of the roll, and if it is above the above lower limit, it is preferable that the layer formed in the following steps is less likely to be destroyed by bending stress. The width of the roll is usually 5 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and on the other hand, usually 5 m or less, preferably 3 m or less, more preferably 2 m or less. If the width is equal to or less than the upper limit, it is preferable from the viewpoint of high handleability of the roll, and if the width is greater than the lower limit, the degree of freedom in the use of the resin composite material is increased.

Moreover, it is not necessarily necessary to use a support body, and a molded object can also be obtained by cutting into a desired shape from the solid resin composite material shape|molded by the shaping|molding method which includes heat processing.

<2. Uses of Resin Composites>

The first aspect of the resin composite material described above is used for an electronic material device. In addition, the second and third aspects can be used not only for electronic material devices, but also for, for example, catalyst modules, molecular sieve membrane modules, optical members, moisture absorption members, foodstuffs, building members, packaging members, and the like. Among them, it is preferable to use it as a constituent member of an electronic material device, for example, a base material, a getter material film, an encapsulant, etc., since the high properties of the resin composite material can be utilized.

In addition, the material containing the resin composite material can be used as a film, and by forming it into a film, not only can the gas barrier properties of the polyimide resin be utilized, but it is also advantageous in terms of high transparency, flexibility, image clarity, etc. do. The film thickness of the resin composite material when used in the form of a film is not particularly limited, and may be appropriately set according to the intended use, but is usually larger than 0.5 µm, preferably 1 µm or more, more preferably 2 µm or more, more preferably 3 µm or more, particularly preferably 5 µm or more, and on the other hand, from the viewpoint of the above-described transparency, flexibility, and image clarity, it is usually 5 mm or less, and preferably 1 mm or less. , More preferably, it is 0.5 mm or less, More preferably, it is 0.3 mm or less, Especially preferably, it is 0.1 mm or less.

The film thickness of the resin composite material can be measured with a conventional film thickness meter such as a non-contact type thickness meter or a contact type thickness meter. As a non-contact type, a confocal microscope (For example, Keyence Corporation shape measuring laser microscope VK-X200) etc. are mentioned.

Hereinafter, an example of using the polyimide resin composite material as an electronic device will be described.

<2.1. Electronic device>

An electronic device has two or more electrodes and controls a current flowing between the electrodes or a voltage generated by electricity, light, magnetism, or a chemical substance or the like, or by applying a voltage or current, light or electric field , a device that generates a magnetic field. Specific examples include a resistor, a rectifier (diode), a switching element (transistor, thyristor), an amplifying element (transistor), a memory element, or a chemical sensor, or a device in which these elements are combined or integrated. Moreover, photoelectric elements, such as a photodiode or a phototransistor which generate|occur|produces a photocurrent, an electroluminescent element which emits light by applying an electric field, and a photoelectric conversion element which generate|occur|produces electromotive force by light, or a solar cell are also mentioned. As a more specific example of an electronic device, the thing described in S. M. Sze's work, Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981) is mentioned.

Especially, as a preferable example of an electronic device, a field effect transistor (FET) element, an electroluminescent element (LED), a photoelectric conversion element, or a solar cell is mentioned. In these devices, the high properties of the resin composite can be effectively utilized.

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

<2.2. Field Effect Transistor (FET) Device>

A field effect transistor (FET) element has a resin composite material as a component. The field effect transistor (FET) element which concerns on one Embodiment has a semiconductor layer, an insulator layer, a source electrode, a gate electrode, and a drain electrode on a base material.

In one embodiment, the substrate has the resin composite material according to one embodiment of the present invention. Since the resin composite material has a low average coefficient of thermal expansion, it is preferably used as a material for a substrate.

Hereinafter, the FET element which concerns on one Embodiment is demonstrated in detail. Fig. 2 is a diagram schematically showing a structural example of a FET element. In Fig. 2, reference numeral 11 denotes a semiconductor layer, 12 an insulator layer, 13 and 14 a source electrode and a drain electrode, 15 a gate electrode, 16 a base material, and 17 a FET element. Although FET devices of different structures are described in Figs. 2A to 2D, all show structural examples of the FET devices. There is no particular limitation on these constituent members constituting the FET element and the manufacturing method thereof, and known techniques can be used. For example, the technique described in publicly known documents, such as International Publication No. 2013/180230 or Japanese Unexamined-Japanese-Patent No. 2015-134703, can be used.

In addition, in this specification, "semiconductor" is defined by the magnitude|size of the carrier mobility in a solid state. Carrier mobility is, as is well known, an indicator of how quickly (or much) an electric charge (electron or hole) can be moved. Specifically, the "semiconductor" in the present specification has a carrier mobility at room temperature of usually 1.0 × 10 ^-6 cm2/V·s or more, preferably 1.0 × 10 ^-5 cm2/V·s or more, It is more preferably 5.0 x 10 ^-5 cm2/V·s or more, and still more preferably 1.0 x 10 ^-4 cm2/V·s or more. In addition, carrier mobility can be measured by the measurement of IV characteristic of a field effect transistor, etc., for example.

<2.2.1. mention>

The FET element is usually produced on the base material 16 . The material of the base material 16 is not specifically limited, unless the effect of this invention is impaired remarkably. Preferable examples of the material of the base material 16 include inorganic materials such as quartz, glass, sapphire, or titania; Flexible base materials, such as the molded object of the above-mentioned resin composite material, are mentioned.

A flexible base material is a base material whose curvature radius is 0.1 mm or more normally and 10000 mm or less. Further, in the case of manufacturing a flexible electronic device, in order to achieve both flexibility and characteristics as a support, the radius of curvature is preferably 0.3 mm or more, more preferably 1 mm or more, and on the other hand, it is preferably 3000 mm or less, It is more preferably 1000 mm or less. In addition, the radius of curvature can be calculated|required with the confocal microscope (For example, the shape measuring laser microscope VK-X200 manufactured by Keyence Corporation) of the base material which was bent until destruction, such as a deformation|transformation or a crack, does not appear.

Although not limited as long as the resin composite material which is one Embodiment of this invention is contained as a specific example of a flexible base material, Resins, such as an epoxy resin; paper materials such as paper or synthetic paper; Composite materials, such as what coated or laminated the surface in order to provide insulation to metal foils, such as silver, copper, stainless steel, titanium, or aluminum; The molded object of the above-mentioned resin composite material is mentioned.

In addition, if the molded article of the resin composite material is a flexible substrate, it is preferable in terms of manufacturing such as a roll-to-roll method, but it can be used as the substrate 16 even if it is not a flexible substrate.

In addition, the characteristics of the FET can be improved by treating the substrate 16 . This is because the film quality of the semiconductor layer 11 to be formed is improved by adjusting the hydrophilicity/hydrophobicity of the substrate 16 , and in particular, by improving the characteristics of the interface portion between the substrate 13 and the semiconductor layer 11 . It is estimated. As such a base material treatment, hydrophobization treatment using hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane, etc.; acid treatment using acids such as hydrochloric acid, sulfuric acid, and acetic acid; Alkali treatment using sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc.; ozone treatment; fluoridation treatment; Plasma treatment using oxygen, argon, or the like; Langmuir Blotset Film Formation Treatment; Other insulator or semiconductor thin film formation processing, etc. are mentioned.

<2.3. Electroluminescent device (LED)>

An electroluminescent element (LED) has a component containing a resin composite material. The electroluminescent element is a self-luminous element using the principle that a fluorescent material emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field.

Hereinafter, an electroluminescent element is demonstrated, referring drawings. 3 is a cross-sectional view schematically showing an embodiment of an electroluminescent element. In FIG. 3 , reference numeral 31 denotes a substrate, 32 an anode, 33 a hole injection layer, 34 a hole transport layer, 35 a light emitting layer, 36 an electron transport layer, 37 an electron injection layer, 38 a cathode, 39 an electroluminescent device. is indicating In addition, it is not necessary for the electroluminescent element to have all these structural members, and a necessary structural member can be selected arbitrarily. For example, it is not necessarily necessary to form the hole injection layer 33 , the hole transport layer 34 , the electron transport layer 36 , and the electron injection layer 37 . There is no particular limitation on these constituent members constituting the electroluminescent element and the manufacturing method thereof, and known techniques can be used. For example, the technique described in publicly known documents, such as International Publication No. 2013/180230 or Japanese Unexamined-Japanese-Patent No. 2015-134703, can be used.

In one embodiment, the base material 31 has a resin composite material. The resin composite material is preferably used as the material of the base material 31 because of its properties.

<2.3.1. base (31)>

The base material 31 becomes a support body of the electroluminescent element 39, and the material is not specifically limited unless the effect of this invention is impaired remarkably. As a preferable example of the material of the base material 31, Inorganic materials, such as quartz, glass, sapphire, or titania; Flexible base materials, such as the molded object of the above-mentioned resin composite material, are mentioned.

Although not limited as long as the resin composite material which is one Embodiment of this invention is contained as a specific example of a flexible base material, Resins, such as an epoxy resin; paper materials such as paper or synthetic paper; Composite materials, such as what coated or laminated the surface in order to provide insulation to metal foil, such as silver, copper, stainless steel, titanium, and aluminum; and a molded article of a resin composite material.

In addition, if the molded article of the resin composite material is a flexible substrate, it is preferable in terms of manufacturing such as a roll-to-roll method, but it can be used as the substrate 31 even if it is not a flexible substrate.

When using a resin base material, it is necessary to pay attention to gas-barrier property. That is, when the gas barrier property of a base material is too low, since an electroluminescent element may deteriorate by the external air which passes through a base material, it is unpreferable. For this reason, when using a resin base material, it is preferable to ensure gas-barrier property by methods, such as forming a dense silicon oxide film, a resin composite material, etc. on at least one plate surface.

As glass, a soda glass, a blue plate glass, an alkali free glass, etc. are mentioned. Since there are few ions elution from glass, an alkali free glass is preferable among these.

There is no restriction|limiting in the shape of the base material 31, For example, things, such as a plate shape, a film shape, or a sheet shape, can be used.

Moreover, although there is no restriction|limiting in the film thickness of the base material 31, Usually, it is 5 micrometers or more, Preferably it is 20 micrometers or more, On the other hand, it is 20 mm or less normally, Preferably it is 10 mm or less. It is preferable that the film thickness of a base material is 5 micrometers or more, since the possibility that the intensity|strength of an electroluminescent element will become insufficient becomes low. It is preferable that the film thickness of a base material is 20 mm or less, since cost is suppressed and mass does not become heavy.

When the material of the base material 31 is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and on the other hand, usually 1 cm or less, preferably 0.5 cm or less. It is preferable that the film thickness of the glass base material 31 is 0.01 mm or more, since mechanical strength increases and it becomes difficult to crack. Moreover, since mass does not become heavy that the film thickness of the glass base material 31 is 0.5 cm or less, it is preferable.

In addition, FIG. 3 only shows one Embodiment of an electroluminescent element, and an electroluminescent element is not limited to the illustrated structure. For example, a layered structure opposite to that shown in FIG. 3 , that is, on the substrate 31 , the cathode 38 , the electron injection layer 37 , the electron transport layer 36 , the light emitting layer 35 , and the hole transport layer (34), the hole injection layer 33, and the anode 32 may be laminated in this order.

The structure of the electroluminescent element is not specifically limited, A single element may be sufficient, the element which consists of a structure arrange|positioned in the form of an array may be sufficient, and the element of the structure in which the anode and the cathode are arrange|positioned in X-Y matrix form may be sufficient.

<2.4. Photoelectric conversion element>

A photoelectric conversion element has a component containing a resin composite material. The photoelectric conversion element which concerns on one Embodiment has at least 1 pair of electrodes, and the active layer which exists between the electrodes. Moreover, the photoelectric conversion element which concerns on one Embodiment may have the other component containing a base material, an electron extraction layer, and a hole extraction layer.

4 : is sectional drawing which shows typically one Embodiment of a photoelectric conversion element. Although the photoelectric conversion element shown in FIG. 4 is a photoelectric conversion element used for a general thin film solar cell, a photoelectric conversion element is not limited to what is shown in FIG. The photoelectric conversion element 57 according to the embodiment includes a substrate 56 , a cathode (electrode) 51 , an electron extraction layer (buffer layer) 52 , an active layer 53 , and a hole extraction layer (buffer layer) 54 . and an anode (electrode) 55 formed in this order. In addition, it is not necessarily necessary to form the electron extraction layer 52 and the hole extraction layer 54. As shown in FIG. There is no particular limitation on these constituent members constituting the photoelectric conversion element and the manufacturing method thereof, and known techniques can be used. For example, the technique described in publicly known documents, such as International Publication No. 2013/180230 or Japanese Unexamined-Japanese-Patent No. 2015-134703, can be used.

In the photoelectric conversion element which concerns on one Embodiment, the base material 56 has a resin composite material. The resin composite material is preferably used as the material of the base material 56 because of its properties.

<2.4.1. base (56)>

The photoelectric conversion element 57 normally has the base material 56 used as a support body.

The material of the base material 56 is not specifically limited, unless the effect of this invention is impaired remarkably. Preferable examples of the material of the base material 56 include inorganic materials such as quartz, glass, sapphire or titania; and flexible substrates such as a molded product of a resin composite material.

Although not limited as long as the resin composite material which is one Embodiment of this invention is contained as a specific example of a flexible base material, Resins, such as an epoxy resin; paper materials such as paper or synthetic paper; Composite materials, such as what coated or laminated the surface in order to provide insulation to metal foils, such as silver, copper, stainless steel, titanium, or aluminum; The molded object of the above-mentioned resin composite material is mentioned.

In addition, if the molded article of the resin composite material is a flexible substrate, it is preferable in terms of manufacturing such as a roll-to-roll method, but it can be used as the substrate 56 even if it is not a flexible substrate.

When using a resin base material, it is necessary to pay attention to gas-barrier property. That is, when the gas barrier property of the substrate is too low, the active layer may be deteriorated by the external air passing through the substrate, which is not preferable. For this reason, when using a resin base material, it is preferable to ensure gas-barrier property by methods, such as forming a dense silicon oxide film, a resin composite material, etc. on at least one plate surface.

As glass, a soda glass, a blue plate glass, an alkali free glass, etc. are mentioned. Since there are few ions elution from glass, an alkali free glass is preferable among these.

There is no restriction|limiting in the shape of the base material 56, For example, things, such as a plate shape, a film shape, or a sheet shape, can be used.

Moreover, although there is no restriction|limiting in the film thickness of the base material 56, Usually, it is 5 micrometers or more, Preferably it is 20 micrometers or more, on the other hand, it is 20 mm or less normally, Preferably it is 10 mm or less. It is preferable that the film thickness of the base material 56 is 5 micrometers or more, since the possibility that the intensity|strength of a photoelectric conversion element will run short becomes low. It is preferable that the film thickness of the base material 56 is 20 mm or less, since cost is suppressed and mass does not become heavy.

When the material of the base material 56 is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and on the other hand, usually 1 cm or less, preferably 0.5 cm or less. It is preferable that the film thickness of the glass base material 31 is 0.01 mm or more, since mechanical strength increases and it becomes difficult to crack. Moreover, since mass does not become heavy that the film thickness of the glass base material 56 is 0.5 cm or less, it is preferable.

<2.5. Solar cell>

It is preferable that the photoelectric conversion element 57 is used as a solar cell element of a solar cell, especially a thin film solar cell. 5 is a cross-sectional view schematically showing the configuration of a thin film solar cell which is a solar cell according to an embodiment of the present invention. As shown in FIG. 5 , the thin film solar cell 111 according to the present embodiment includes a weather resistant protective film 101 , an ultraviolet cut film 102 , a gas barrier film 103 , and a getter material film 104 . And, the sealing material 105, the solar cell element 106, the sealing material 107, the getter material film 108, the gas barrier film 109, and the back sheet 110 are provided in this order. do. The thin film solar cell 111 according to the present embodiment includes a photoelectric conversion element as the solar cell element 106 . And light is irradiated from the side (lower side in FIG. 5) in which the weather-resistant protective film 101 was formed, and the solar cell element 106 is designed to generate electricity. In addition, the thin film solar cell 111 does not need to have all these structural members, and a necessary structural member can be arbitrarily selected.

There is no particular limitation on these constituent members constituting the thin film solar cell and the manufacturing method thereof, and known techniques can be used. For example, the technique described in publicly known documents, such as International Publication No. 2013/180230 or Japanese Unexamined-Japanese-Patent No. 2015-134703, can be used.

In addition, the weather resistant protective film, back sheet, ultraviolet cut film, gas barrier film, getter material film, and encapsulant can be used for the above-mentioned electronic devices such as field effect transistor elements (FETs) and electroluminescent elements (LEDs). have.

Although there is no restriction|limiting in the manufacturing method of the thin film solar cell 111 of this embodiment, For example, in the solar cell manufacturing method of the form of FIG. 6, after producing the laminated body shown in FIG. A method of carrying out is mentioned. Since the solar cell element 106 of this embodiment is excellent in heat resistance, it is preferable at the point which deterioration by a lamination sealing process is reduced.

Preparation of the laminated body shown in FIG. 5 can be performed using a well-known technique. The lamination encapsulation process method is not particularly limited as long as the effect of the present invention is not impaired, but for example, wet lamination, dry lamination, hot melt lamination, extrusion lamination, coextrusion lamination, extrusion coating, lamination with a light curing adhesive, A thermal lamination etc. are mentioned. Among them, a lamination method with a photocuring adhesive, which has a track record in sealing organic electroluminescent devices, and a hot melt laminate or thermal laminate with a track record in solar cells are preferable, and the hot melt laminate or thermal laminate can use a sheet-like sealing material. It is more preferable in that point.

The heating temperature of the lamination 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 a lamination sealing process is 10 minutes or more normally, Preferably it is 20 minutes or more, and is 100 minutes or less normally, Preferably it is 90 minutes or less. The pressure of a lamination sealing process is 0.001 MPa or more normally, Preferably it is 0.01 MPa or more, and is 0.2 MPa or less normally, Preferably it is 0.1 MPa or less. By setting the pressure within this range, sealing is performed reliably, and the film thickness reduction due to the protrusion of the sealing materials 105 and 107 from the end portion and the reduction of the film thickness due to overpressure can be suppressed, and dimensional stability can be ensured. . Moreover, the thing which connected two or more solar cell elements 106 in series or parallel can carry out similarly to the above, and can manufacture it.

There is no restriction|limiting in the use of the solar cell, especially the thin film solar cell 111 mentioned above, It can be used for arbitrary uses. For example, a solar cell according to an embodiment is a solar cell for building materials, a solar cell for an automobile, a solar cell for an interior, a solar cell for a railway, a solar cell for a ship, a solar cell for an airplane, a solar cell for a space aircraft, and a solar cell for home appliances. It can be used as a battery, a solar cell for cell phones, or a solar cell for toys.

<2.6. Solar cell module>

As a solar cell, especially, the thin film solar cell 111 mentioned above may be used as it is, and may be used as a component of a solar cell module. For example, as shown in FIG. 6 , a solar cell, particularly, a solar cell module 113 including the above-described thin film solar cell 111 on a substrate 112 is produced, and the solar cell module ( 113) can be installed and used at the place of use.

As the base material 112, a well-known technique can be used, for example, as a material of the base material 112, the material described in International Publication No. 2013/180230 or Japanese Unexamined Patent Publication No. 2015-134703, etc. can be used. In addition, a polyimide resin composite material may be used for the base material 112 . For example, when a building material plate is used as the base material 112, by installing the thin film solar cell 111 on the surface of the plate material, as the solar cell module 113, a solar cell panel for the exterior wall of a building can be produced. have.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by the following Example, unless the summary is exceeded. In addition, evaluation of the zeolite obtained in the Example mentioned later, and a film was performed by the following method.

<Evaluation of zeolite>

(Average primary particle size of zeolite)

With the JEOL Auto Fine Coater JFC-1600, the distance between the zeolite and the platinum target was set to 30 mm, and by sputtering for 60 seconds, it was deposited so that the platinum thickness on the surface of the zeolite sample was about 9 nm, followed by observation by SEM. carried out. The working distance in the SEM was 10 to 11 mm, the acceleration voltage of 10 kV, and the spot size were 30 mm. The average primary particle diameter was determined by measuring the particle diameter of 30 arbitrarily selected primary particles in the observation of the particles with a JEOL scanning electron microscope JSM-6010LV, and averaging the particle diameters of the primary particles. In addition, the particle diameter was made into the diameter (circle equivalent diameter) of the circle which has the same area as the projected area of particle|grains.

(average coefficient of thermal expansion of zeolite)

The average coefficient of thermal expansion at 60-220 degreeC of the zeolite was measured by calculating the lattice constant using the X-ray-diffraction apparatus D8ADVANCE by BRUKER, and X-ray-diffraction analysis software JADE.

<Evaluation of the film>

(average coefficient of thermal expansion of the film)

The average coefficient of thermal expansion (CTE) of the temperature range of 60 degreeC - 220 degreeC was measured using the thermomechanical analyzer TMA/SS6100 by the SI Nanotechnology company. In addition, the sample shape was made into 4 mm width|variety and the distance between chuck|zippers 20 mm, and it heated up at the temperature increase rate of 10 degree-C/min.

(Retardation value of film)

The retardation value (Rth) of the film was computed as a value of wavelength 460nm with respect to the film|membrane with a film thickness of 10 micrometers using the Otsuka Electronics Co., Ltd. retardation film optical material inspection apparatus RETS-100.

(Haze rate of film)

The haze rate of the film was measured using TM double beam automatic haze computer HZ-2 manufactured by Suga Test Instruments. The haze rate used this time is a value with respect to D65 light.

(Storage modulus of film)

The storage modulus of the resin composite film at each temperature was measured in the dual cantilever tension mode by the dynamic viscoelasticity measurement method described in JIS K-7244 using a dynamic viscoelasticity device DMS6100 manufactured by SI Nanotechnology Co., Ltd. (Measurement) Temperature range: -100 °C to 150 °C, frequency: 1 Hz, temperature increase rate: 5 °C/min). The elastic modulus shown in Table 1 is the elastic modulus in 25 degreeC of measurement temperature.

<Synthesis method of zeolite>

(Synthesis Example 1: Synthesis method of zeolite C1)

In the container, sodium hydroxide manufactured by Kishida Chemical Co., Ltd., as a structural regulator (SDA), N,N,N-trimethyl-1-adamanthaammonium hydroxide (TMAdaOH) manufactured by Seychem, aluminum hydroxide manufactured by Aldrich, manufactured by Nikki Catalyst Chemical Co., Ltd. Cataloid SI-30 was added sequentially. The composition of the obtained mixture was 1.0SiO2/0.033Al2O3/ _0.1NaOH / _0.06KOH / _0.07TMAdaOH / _20H2O . Then, as a seed crystal, ₂ mass % of CHA type zeolite with respect to SiO2 was added to a mixture, and after mixing well, the obtained mixture is put into a pressure-resistant container, and in 160 degreeC oven, rotating at 15 rpm, 48 Time-sequential synthesis was performed. After suction filtration and washing|cleaning, zeolite C1 which is a CHA-type zeolite (as-made) was obtained by drying.

When the obtained zeolite C1 was observed by SEM, the average primary particle diameter was 1000 nm. Moreover, as a result of measuring the average coefficient of thermal expansion in 60-220 degreeC of zeolite C1, the average coefficient of thermal expansion of zeolite C1 was -10 ppm/K.

(Synthesis Example 2: Synthesis method of zeolite C2)

In the container, water, potassium hydroxide by Kishida Chemical, and FAU zeolite USY7 by Shokubai Chemicals were sequentially added. The composition of the obtained mixture was 1.0SiO2/0.143Al2O3/0.582KOH/36.2H2O. After mixing well, the obtained mixture was put into the pressure-resistant container, it left still in 100 degreeC oven, and performed hydrothermal synthesis for 7 days. After suction filtration and washing|cleaning, zeolite C2 which is a CHA-type zeolite was obtained by drying.

When the obtained zeolite C2 was observed by SEM, the average primary particle diameter was 200 nm. Moreover, as a result of measuring the average coefficient of thermal expansion in 60-220 degreeC of zeolite C2, the average coefficient of thermal expansion of zeolite C2 was -10 ppm/K.

(Synthesis Example 3: Synthesis method of zeolite T1)

The following synthesis was performed with reference to Chemical Engineering Journal, 230, 380, 2013. In the container, water, sodium hydroxide manufactured by Kishida Chemical, potassium hydroxide manufactured by Kishida Chemical, tetramethylammonium hydroxide (TMAOH) manufactured by Seychem as a structural regulator (SDA), sodium aluminate manufactured by Asada Chemical Industries, Ltd. (Aluminum oxide 20.13%) , sodium oxide 18.9%) and AS-40 colloidal silica manufactured by Aldrich were sequentially added. The composition of the obtained mixture was 1.0SiO2/ _0.025Al2O3 / _0.3NaOH / _0.3KOH / _0.06TMAOH /10H2O. After mixing well, the obtained mixture was put into a pressure-resistant container, and hydrothermal synthesis was performed for 5 days, rotating at 15 rpm in 130 degreeC oven. After suction filtration and washing|cleaning, it dried and obtained the Linde T-type zeolite (as-made) which is an OFF type|mold and ERI type|mold combined crystal. Zeolite T1 was obtained by calcining this powder at 600C for 6 hours under air circulation.

When the obtained zeolite T1 was observed by SEM, the average primary particle diameter was 300 nm. Moreover, as a result of measuring the average coefficient of thermal expansion in 60-220 degreeC of zeolite T1, the average coefficient of thermal expansion of zeolite T1 was -12 ppm/K.

(Synthesis Example 4: Synthesis method of aluminophosphate A1)

Within the container, 69 g of 85% phosphoric acid manufactured by Kishida Chemical and 130 g of water were mixed. To this, 40.8 g of pseudo-boehmite (75% Al2O3) was added and stirred. After stirring for 2 hours, a mixture of 27.3 g of triethylamine and 120 g of water was added, followed by stirring for 1 hour. After mixing well, the obtained mixture was put into a pressure-resistant container, and hydrothermal synthesis was performed for 12 hours, rotating at 15 rpm in 190 degreeC oven. After suction filtration and washing|cleaning, APC type aluminophosphate was obtained by drying. Aluminophosphate A1 was obtained by calcining the obtained APC-type aluminophosphate at 600°C for 6 hours under air circulation.

(Synthesis Example 5: Synthesis method of silicalite 1)

In the container, tetrapropylammonium hydroxide (TPAOH) manufactured by Seychem Co., Ltd. and Snowtex-40 colloidal silica manufactured by Nissan Chemical Co., Ltd. were sequentially added as water and a structural modifier (SDA). The composition of the obtained mixture was 1.0SiO2/ _0.4TPAOH / _11.8H2O . After mixing well, the obtained mixture was put into a pressure-resistant container, and hydrothermal synthesis was performed for 20 hours, rotating at 15 rpm in 100 degreeC oven. After suction filtration and washing, drying was performed to obtain a silicalite-1 zeolite having MFI crystals. Silicalite 1 was obtained by calcining the obtained silicalite-1 zeolite at 600°C for 6 hours under air circulation.

(Synthesis Example 6: Synthesis method of zeolite R1)

In a container, 0.93 g of crown ether (18-crown-6) was dissolved in 6.3 g of water, and in this, 0.45 g of sodium hydroxide manufactured by Kishida Chemical, 1.74 g of 70% sodium aluminate, and cesium hydroxide monohydrate manufactured by Kishida Chemical Co., Ltd. 0.71 g was added, and it heat-stirred at 80 degreeC for 3 hours. 10.5 g of Snowtex-40 colloidal silica manufactured by Nissan Chemical Co., Ltd. was added thereto, mixed well, and left to stand at room temperature for 1 day. The resulting mixture was placed in a pressure-resistant container, hydrothermal synthesized at 110°C for 96 hours, filtered and washed with water to obtain an RHO-type zeolite. Zeolite R1 was obtained by calcining the obtained RHO type|mold under air circulation at 600 degreeC for 6 hours.

<The manufacturing method of a resin composition>

(Resin composition preparation example 1: manufacturing method of polyimide precursor containing composition M1)

3,3',4,4'-biphenyltetracarboxylic dianhydride 311 g (1.06 mol), 3,3',4,4' in a 4-neck flask equipped with a nitrogen gas inlet tube, a cooler, and a stirrer -bicyclohexyltetracarboxylic dianhydride 324 g (1.06 mol) 2,2'-bis (trifluoromethyl) benzidine 340 g (1.06 mol), 4,4'-bis (diaminodiphenyl) sulfone 263 g (1.06 mol) and 2890 g of N-methylpyrrolidone were added, and the polyimide precursor containing composition M1 containing 30 mass % of polyimide precursors was obtained by heating and stirring at 80 degreeC for 8 hours. The polyimide precursor has a nuclear-hydrogenated (hydrogenated) aromatic compound.

<Example 1: Preparation of resin composite film using polyimide precursor-containing composition M1>

(Comparative Example 1-1: Manufacturing method of polyimide resin film 1)

Polyimide precursor containing composition M1 was diluted with N-methylpyrrolidone, and it adjusted so that a polyimide precursor might be set to 20 mass %. The polyimide resin film 1 was obtained by apply|coating the obtained ink on alkali glass (made by Corning) using the tester industrial company applicator, and performing drying and baking at 330 degreeC for 30 minute(s). When the film thickness was measured by THICKNESS METER B-1 by Toyo Seiki Seisakusho, the film thickness of the film was 10 micrometers. In addition, the glass transition temperature (Tg) of the polyimide resin film 1 calculated|required from the inflection point when the average coefficient of thermal expansion of the film was measured was 320 degreeC. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Example 1-1: Manufacturing method of polyimide resin composite film 1)

Zeolite C1 was added to N-methylpyrrolidone, and the zeolite dispersion liquid D1 whose content of zeolite C1 was 4 mass % was obtained by bead milling with the Ravstar Mini by Ashizawa Finetech company.

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 Air Co., 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 mass %. Moreover, the D50 value measured with the dynamic light scattering type particle size distribution analyzer (Microtrac Bell Corporation Nanotrac _WaveII -EX150) was 35 nm.

Next, 19.2 g of the obtained zeolite dispersion liquid after centrifugation and 4 g of polyimide precursor containing composition M1 were mixed, and the ink which mixed the zeolite and polyimide precursor containing composition M1 was obtained by stirring with a stirrer. The obtained ink was apply|coated with the applicator manufactured by Tester Industries, Ltd., and the polyimide resin composite material film 1 was obtained by drying and baking at 330 degreeC for 30 minute(s). In addition, the film thickness of the film was 19 micrometers, and content of the zeolite in the obtained film was 28.6 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Example 1-2: Manufacturing method of polyimide resin composite film 2)

A polyimide resin composite film 2 was obtained in the same manner as in Example 1 except that 4.8 g of the zeolite dispersion D1 and 4 g of the polyimide precursor-containing composition M1 were mixed. The film thickness of the film was 6 micrometers, and content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Example 2-1: Manufacturing method of polyimide resin composite film 3)

A polyimide resin composite film 3 was obtained in the same manner as in Example 1-1 except that zeolite C2 was used instead of zeolite C1. The film thickness of the film was 21 micrometers, and content of the zeolite in the obtained film was 28.6 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Example 2-2: Manufacturing method of polyimide resin composite film 4)

A polyimide resin composite film 4 was obtained in the same manner as in Example 1-2 except that zeolite C2 was used instead of zeolite C1. The film thickness of the film was 21 micrometers, and content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Example 3-1: Manufacturing method of polyimide resin composite film 5)

The ink was obtained by mixing zeolite T1 so that it might become 0.24 g, polyimide precursor 0.6g, and NMP 2.4g, and stirring with a stirrer. The obtained ink was apply|coated with the tester industrial company applicator, and the polyimide resin composite material film 5 was obtained by drying and baking at 330 degreeC for 30 minute(s). Moreover, the film thickness of the film was 44 micrometers, and content of the zeolite in the obtained film was 28.6 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion and haze ratio of the obtained film.

(Example 3-2: Manufacturing method of polyimide resin composite film 6)

The ink was obtained by mixing zeolite T1 so that it might become 0.06g, the polyimide precursor 0.6g, and NMP2.4g, and stirring with a stirrer. The obtained ink was apply|coated with the applicator manufactured by Tester Industries, Ltd., and the polyimide resin composite material film 6 was obtained by drying and baking at 330 degreeC for 30 minutes. In addition, the film thickness of the film was 21 micrometers, and content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, the retardation value, and the haze ratio of the obtained film.

(Example 4-1: Manufacturing method of polyimide resin composite film 7)

A polyimide resin composite film 7 was produced in the same manner as in Example 3-2 except that FAU zeolite HY(5) (silica/alumina molar ratio = 40) manufactured by Shokubai Chemical Industry Co., Ltd. was used instead of zeolite T1. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion and haze ratio of the obtained film.

(Example 5-1: Manufacturing method of polyimide resin composite film 8)

A polyimide resin composite film 8 was produced in the same manner as in Example 3-2, except that a proton type ^* BEA type zeolite HSZ-940 HOA (silica/alumina molar ratio = 40) manufactured by Tosoh Corporation was used instead of zeolite T1. . Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion of the obtained film.

(Comparative Example 1-2: Manufacturing method of polyimide resin composite film 9)

A polyimide resin composite film 9 was produced in the same manner as in Example 1-1 except that Silica SC2500-SQ (average primary particle diameter of 200 nm) manufactured by Admatex Co., Ltd. was used instead of zeolite T1. In addition, the film thickness of the film was 18 micrometers, and content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, haze rate, and elastic modulus of the obtained film.

(Comparative Example 1-3: Manufacturing method of polyimide resin composite film 10)

A polyimide resin composite film 10 was produced in the same manner as in Example 1-1 except that ZWO-01, a zirconium tungstate fine manufactured by Puruchi Co., Ltd., was used instead of the zeolite C1 as a negative expansion material. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Comparative Example 1-4: Manufacturing method of polyimide resin composite film 11)

A polyimide resin composite film 11 was produced in the same manner as in Example 3-1 except that zeolite A1 was used instead of zeolite T1. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion of the obtained film.

(Comparative Example 1-5: Manufacturing method of polyimide resin composite film 12)

A polyimide resin composite film 12 was produced in the same manner as in Example 3-1, except that silicalite 1 was used instead of zeolite T1. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion, retardation value, haze ratio, and elastic modulus of the obtained film.

(Comparative Example 1-6: Manufacturing method of polyimide resin composite film 13)

A polyimide resin composite film 13 was produced in the same manner as in Example 3-1 except that ZeoalZ4A-005 (average primary particle diameter of 50 nm, LTA-type zeolite) manufactured by Nakamura Carbide Co., Ltd. was used instead of zeolite T1. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion of the obtained film.

(Comparative Example 1-7: Manufacturing method of polyimide resin composite film 14)

A polyimide resin composite film 14 was produced in the same manner as in Example 3-1 except that zeolite R1 was used instead of zeolite T1. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion of the obtained film.

(Resin composition preparation example 2: preparation method of non-hydrogenated polyimide precursor containing composition M2)

635 g (2.16 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl in a 4-necked flask equipped with a nitrogen gas inlet tube, a cooler, and a stirrer Polyimide precursor containing composition M2 containing 25 mass % of polyimide precursors was obtained by adding 445 g (2.22 mol) of ethers and 3240 g of N,N- dimethylacetamides, and heating-stirring at 80 degreeC for 6 hours. The polyimide precursor does not have a nuclear-hydrogenated (hydrogenated) aromatic compound.

(Comparative example 1-8: manufacturing method of polyimide resin film 2)

Instead of the polyimide precursor containing composition M1, except having used M2, the polyimide resin film 2 was produced by the method similar to the comparative example 1-1. Table 1 shows the average coefficient of thermal expansion of the obtained film.

(Example 6-1: Manufacturing method of polyimide resin composite film 15)

A polyimide resin composite film 15 was obtained in the same manner as in Example 1-1 except for using the zeolite C1 and the polyimide precursor-containing composition M2. Content of the zeolite in the obtained film was 9.1 mass % with respect to the film mass. Table 1 shows the average coefficient of thermal expansion of the obtained film.

In Table 1, in the zeolite-containing polyimide resin composite material according to the embodiment of the present invention, the average coefficient of thermal expansion of the resin composite material is less than 50 ppm, and the retardation value of the resin composite material is 150 nm or less, and the polyimide resin composite material is 150 nm or less. It is as low as the mid resin, and the haze ratio of the resin composite material is 5% or less, and it can be seen that it is as low as that of the polyimide resin.

Compared to the polyimide resin composite containing silica, which is a general inorganic filler, or zirconium tungstate, which is a filler having a negative coefficient of thermal expansion, the zeolite-containing polyimide resin composite according to the embodiment of the present invention has a large decrease in the average coefficient of thermal expansion. The average coefficient of thermal expansion of the polyimide resin composite containing silica having a positive coefficient of thermal expansion and zirconium tungstate having a negative coefficient of thermal expansion is the same, and the average coefficient of thermal expansion of the filler itself is the average coefficient of thermal expansion of the resin composite. does not determine

The average coefficient of thermal expansion of the polyimide resin composite material containing a specific zeolite is falling significantly. The average coefficient of thermal expansion of the polyimide resin composite containing a zeolite (CHA, ERI) containing d6r and/or a zeolite containing mtw (BEA) is large compared to a zeolite containing polyimide resin composite not containing them, and these Since CBU is included, it is estimated that the average coefficient of thermal expansion became smaller.

The reduction rate of the average coefficient of thermal expansion by 9.1 mass% of zeolite is 14.0% when hydrogenated polyimide is used compared to 12.0% when non-hydrogenated polyimide is used, and hydrogenated polyimide has a more remarkable effect seemed Although the cause of this is not certain, it is thought that it is a result of the interaction with a zeolite becoming strong while the pi-pi stack of resins became weak by hydrogenation.

From the above results, by the zeolite-containing polyimide resin composite material according to an embodiment of the present invention, a zeolite suitable for members such as electronic devices, which has both high suppression properties against deformation such as warpage, good image clarity, and high transparency It turns out that the containing polyimide resin composite material can be provided inexpensively.

By the polyimide resin composite according to an embodiment of the present invention, a zeolite-containing polyimide resin composite suitable for members such as electronic devices, which has all of high suppression against deformation such as warpage, high image clarity, and high transparency can be provided inexpensively.

1: Resin Composite
2: Zeolite
3: Resin
11: semiconductor layer
12: insulator layer
13, 14: source electrode and drain electrode
15: gate electrode
16: description
17: FET device
31: description
32: positive electrode
33: hole injection layer
34: hole transport layer
35: light emitting 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: description
57: photoelectric conversion element
101: weather resistant protective film
102: UV cut film
103, 109: gas barrier film
104, 108: getter material film
105, 107: encapsulant
106: solar cell element
110: back seat
111: thin film solar cell
112: description
113: solar cell module

Claims (50)

A zeolite-containing polyimide resin composite comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin, and for use in an electronic material device. A zeolite-containing polyimide resin composite comprising a zeolite and a polyimide resin, comprising:
The average coefficient of thermal expansion at 0 ° C. or higher and below the glass transition temperature of the polyimide resin is less than 50 ppm/K,
The retardation value is 150 nm or less, and
A haze ratio of 5% or less, a zeolite-containing polyimide resin composite. A zeolite-containing polyimide resin composite comprising a zeolite containing at least any of d6r and mtw as a structural unit Composite Building Unit (CBU), and a polyimide resin, and being transparent. 4. The method according to any one of claims 1 to 3,
A zeolite-containing polyimide resin composite material, wherein the zeolite has any of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structures. 4. The method according to any one of claims 1 to 3,
A zeolite-containing polyimide resin composite material having an elastic modulus at 25°C of 4.5 GPa or more. 5. The method of claim 4,
A zeolite-containing polyimide resin composite material having an elastic modulus at 25°C of 4.5 GPa or more. 4. The method according to any one of claims 1 to 3,
With respect to the zeolite-containing polyimide resin composite, the zeolite is contained in an amount of 1 mass% or more and 80 mass% or less. 5. The method of claim 4,
With respect to the zeolite-containing polyimide resin composite, the zeolite is contained in an amount of 1 mass% or more and 80 mass% or less. 6. The method of claim 5,
With respect to the zeolite-containing polyimide resin composite, the zeolite is contained in an amount of 1 mass% or more and 80 mass% or less. 7. The method of claim 6,
With respect to the zeolite-containing polyimide resin composite, the zeolite is contained in an amount of 1 mass% or more and 80 mass% or less. 4. The method according to any one of claims 1 to 3,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 5. The method of claim 4,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 6. The method of claim 5,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 7. The method of claim 6,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 8. The method of claim 7,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 9. The method of claim 8,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 10. The method of claim 9,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. 11. The method of claim 10,
The zeolite-containing polyimide resin composite material, wherein the polyimide resin is a polyimide resin having a nuclear-hydrogenated aromatic compound. A film containing the zeolite-containing polyimide resin composite material according to any one of claims 1 to 3. A film containing the zeolite-containing polyimide resin composite according to claim 4. A film containing the zeolite-containing polyimide resin composite according to claim 5. A film containing the zeolite-containing polyimide resin composite according to claim 6. A film containing the zeolite-containing polyimide resin composite according to claim 7. A film containing the zeolite-containing polyimide resin composite according to claim 8. A film containing the zeolite-containing polyimide resin composite according to claim 9. A film containing the zeolite-containing polyimide resin composite according to claim 10. A film containing the zeolite-containing polyimide resin composite according to claim 11. A film containing the zeolite-containing polyimide resin composite according to claim 12. A film containing the zeolite-containing polyimide resin composite according to claim 13. A film containing the zeolite-containing polyimide resin composite according to claim 14. A film containing the zeolite-containing polyimide resin composite according to claim 15. A film containing the zeolite-containing polyimide resin composite according to claim 16. A film containing the zeolite-containing polyimide resin composite according to claim 17. A film containing the zeolite-containing polyimide resin composite according to claim 18. An electronic device comprising the zeolite-containing polyimide resin composite according to any one of claims 1 to 3. An electronic device containing the zeolite-containing polyimide resin composite according to claim 4. An electronic device containing the zeolite-containing polyimide resin composite according to claim 5. An electronic device containing the zeolite-containing polyimide resin composite according to claim 6 . An electronic device comprising the zeolite-containing polyimide resin composite according to claim 7. An electronic device containing the zeolite-containing polyimide resin composite according to claim 8. An electronic device containing the zeolite-containing polyimide resin composite according to claim 9. An electronic device containing the zeolite-containing polyimide resin composite according to claim 10. An electronic device containing the zeolite-containing polyimide resin composite according to claim 11. An electronic device containing the zeolite-containing polyimide resin composite according to claim 12. An electronic device containing the zeolite-containing polyimide resin composite according to claim 13. An electronic device comprising the zeolite-containing polyimide resin composite according to claim 14. An electronic device containing the zeolite-containing polyimide resin composite according to claim 15. An electronic device comprising the zeolite-containing polyimide resin composite according to claim 16. An electronic device comprising the zeolite-containing polyimide resin composite according to claim 17. An electronic device containing the zeolite-containing polyimide resin composite according to claim 18.

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