JP2016164899A - Method for manufacturing organic transistor element - Google Patents

Abstract

Kind Code: A1 An insulating film formed of a photosensitive resin can be formed by a wet coating method on a fluorine resin film having high liquid repellency, and the insulating film and the fluorine are formed from the photosensitive resin film through a photolithography process. To provide a manufacturing method capable of easily manufacturing an organic transistor element having a finely processed insulating film which has high adhesion to an insulating film made of resin. A substrate 1, a gate electrode 2, a gate insulating film 3, a source electrode 4, a drain electrode 5, an organic semiconductor layer 6, and a fluorine resin (F) are included, and the water contact angle of the surface is 105. A photosensitive resin composition is applied on the laminate having the first insulating film 7 having a temperature of 10° C. or more to form a photosensitive resin film, and the photosensitive resin film is partially exposed and developed to form a first film. 2, an insulating film 8 is formed to obtain an organic transistor element 10. Next, as shown in FIG. The photosensitive resin composition contains a fluororesin (A) having a crosslinkable group and a radical polymerization initiator (C), and has a fluorine atom content of 10 to 45% by mass in solid content. [Selection drawing] Fig. 1

Description

  The present invention relates to a method for manufacturing an organic transistor element including an organic semiconductor layer.

  In the organic transistor element, when the relative dielectric constant of the gate insulating film in contact with the organic semiconductor layer is high, it has been reported that carrier delocalization occurs at the interface with the organic semiconductor layer and the mobility of the carrier is reduced. (Non-Patent Document 1). Therefore, proposals have been made to use a fluorine resin such as Cytop (registered trademark) having a low relative dielectric constant for the gate insulating film (for example, Patent Documents 1 and 2).

On the other hand, in the manufacture of an organic transistor element in which a source electrode, a drain electrode, and an organic semiconductor layer are provided on a gate insulating film and an interlayer insulating film is provided thereon, the interlayer insulating film is finely processed to form a contact hole or the like. May be provided.
As a method for finely processing the interlayer insulating film, for example, there is a method of forming the interlayer insulating film with a photosensitive resin composition. By applying a liquid photosensitive resin composition in a wet manner to form a photosensitive resin film, and finely processing the photosensitive resin film by photolithography, a desired interlayer insulating film can be formed.
However, the organic semiconductor layer is easily damaged in the manufacturing process. For example, when the photosensitive resin composition is applied, the organic semiconductor layer may be damaged by a solvent, a polymerization initiator, or the like contained in the photosensitive resin composition.

In order to protect the organic semiconductor layer, it has been proposed to form a sealing layer with a resin composition in which a fluorine resin such as Cytop (registered trademark) is dissolved in a fluorine-containing solvent (for example, Patent Documents 1 and 3).
The fluorine-containing solvent hardly damages the organic semiconductor layer. Therefore, the sealing layer can be formed without damaging the organic semiconductor layer by a simple method in which the resin composition is applied wet and dried. Further, by providing the sealing layer, it is possible to prevent the organic semiconductor layer from being damaged in the subsequent steps.

  However, since the sealing layer as described above does not have photosensitivity, when an interlayer insulating film having a contact hole or the like is formed, it is formed from a photosensitive resin film that can be finely processed on the sealing layer. It is necessary to provide an insulating film. However, since the sealing layer contains a fluororesin, the surface energy is low and the liquid repellency (water repellency / oil repellency) is high. Therefore, without surface treatment such as plasma treatment, ozone treatment, and ashing, it is difficult to form a photosensitive resin film on the sealing layer by a wet coating method, and even if it can be formed, adhesion between the sealing layer and the sealing layer is difficult. It will be low. If the adhesion is low, the problem that the insulating film is peeled off occurs during fine processing by photolithography, for example, development with a developer.

In order to form an insulating film on a fluororesin film by a wet coating method, a method of previously forming a vapor deposition film on the fluororesin film surface has also been proposed (for example, Patent Documents 1 and 2).
However, it takes time and effort to form the surface treatment and the deposited film. Further, depending on the type of surface treatment, the organic semiconductor layer may be damaged. Therefore, in order to efficiently manufacture the organic transistor element, without performing the surface treatment or the formation of the vapor deposition film, only by the treatment by the wet coating method, directly on the surface of the highly liquid-repellent fluororesin film, There is a need for a technique capable of forming a photosensitive resin film and having excellent adhesion between an insulating film formed from the photosensitive resin film and a fluororesin film.

Veres et al., Advanced Functional Materials, Vol. 13, No. 3, pp. 199-204 (2003)

JP 2010-278173 A JP 2010-283240 A Japanese Patent No. 5098153

  The present invention has been made in view of the above circumstances. A photosensitive resin film can be formed on an insulating film formed of a highly liquid-repellent fluororesin by a wet coating method, and photolithography can be performed from the photosensitive resin film. To provide a manufacturing method that can easily manufacture an organic transistor element having an insulating film that has a high degree of adhesion between an insulating film formed through a process and an insulating film formed from the fluororesin and that has been subjected to microfabrication. Objective.

The present invention provides a method for producing an organic transistor element and an electronic device having the following configurations [1] to [7].
[1] A method for producing an organic transistor element having a gate electrode, a source electrode, a drain electrode, and an organic semiconductor layer on a substrate,
On the first insulating film covering the organic semiconductor layer,
Applying a photosensitive resin composition to form a photosensitive resin film at least partially in contact with the first insulating film;
A step of partially exposing and developing the photosensitive resin film to form a second insulating film,
The first insulating film contains a fluororesin (F), and the water contact angle of the surface of the first insulating film is 105 ° or more;
The said photosensitive resin composition contains the fluororesin (A) which has a crosslinkable group, and a radical polymerization initiator (C), and the fluorine atom content rate in solid content of this photosensitive resin composition is 10-45. The manufacturing method of the organic transistor element characterized by the above-mentioned.
[2] The method for producing an organic transistor element according to [1], wherein the photosensitive resin composition further contains a non-fluorinated solvent.
[3] The method for producing an organic transistor element according to [1] or [2], wherein the photosensitive resin composition further includes a compound (B) having two or more crosslinkable functional groups and having no fluorine atom.
[4] The method for producing an organic transistor element according to any one of [1] to [3], wherein the fluororesin (A) is a fluorine-containing polyarylene prepolymer.
[5] The fluororesin (F) is a fluorinated polymer (F1) having an aliphatic ring structure in the main chain, and a fluorinated heavy polymer having no ring structure in the main chain and having a perfluoroalkyl group in the side chain. The manufacturing method of the organic transistor element in any one of [1]-[4] containing any one or both of unification (F2).
[6] The organic transistor according to any one of [1] to [5], wherein the first insulating film is a film formed from a resin composition containing the fluororesin (F) and a fluorine-containing solvent. Device manufacturing method.
[7] An electronic apparatus having an organic transistor element obtained by the manufacturing method according to any one of [1] to [6].

  According to the present invention, a photosensitive resin film can be formed by a wet coating method on an insulating film formed of a highly liquid-repellent fluororesin, and the insulating film is formed from the photosensitive resin film through a photolithography process. It is possible to provide a manufacturing method that can easily manufacture an organic transistor element having an insulating film subjected to microfabrication and having high adhesion between the insulating film formed from the fluororesin and the insulating film.

It is sectional drawing which shows schematic structure of the organic transistor element 10 in 1st embodiment of this invention. It is sectional drawing which shows schematic structure of the organic transistor element 20 in 2nd embodiment of this invention. It is sectional drawing which shows schematic structure of the organic transistor element 30 in 3rd embodiment of this invention. It is sectional drawing which shows schematic structure of the organic transistor element 40 in 4th embodiment of this invention.

An “insulating film” in the present invention is an insulating film. “Having insulation” means having the property of not allowing electricity (electric current) to pass through. Specifically, the volume resistivity measured by the double ring electrode method is 10 ¹⁰ Ω · cm or more. It shows that.
The “coating film” in the present specification is a film obtained by applying a liquid material (photosensitive resin composition, curable composition, etc.), and the “dry film” is a liquid material containing no solvent. In the case, it is synonymous with a coating film, and when the liquid material contains a solvent, it means a film from which the solvent has been removed, and the “cured film” means that the dried film is cured by one or both of light and heat. Refers to the film.
The “fluoroalkyl group” in the present invention is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the “perfluoroalkyl group” means that all of the hydrogen atoms of the alkyl group are fluorine atoms. Is a group substituted.
In the present specification, the compound represented by the formula (1) is also referred to as “compound (1)”. The same applies to units, compounds and the like represented by other formulas.
In this specification, a methacryloyl group and a methacryloyloxy group are collectively referred to as a “methacryloyl (oxy) group”. The acryloyl group and the methacryloyl group are collectively referred to as “(meth) acryloyl group”. In addition, vinyl group and vinyloxy group are collectively referred to as “vinyl (oxy) group”, allyl group and allyloxy group are collectively referred to as “allyl (oxy) group”, trifluorovinyl group and trifluorovinyloxy group. Collectively, it is called “trifluorovinyl (oxy) group”.

The method for producing an organic transistor element of the present invention is a method for producing an organic transistor element having a gate electrode, a source electrode, a drain electrode, and an organic semiconductor layer on a substrate,
On the first insulating film covering the organic semiconductor layer,
Applying a photosensitive resin composition to form a photosensitive resin film at least partially in contact with the first insulating film;
A step of partially exposing and developing the photosensitive resin film to form a second insulating film,
The first insulating film contains a fluororesin (F), and the water contact angle of the surface of the first insulating film is 105 ° or more;
The said photosensitive resin composition contains the fluororesin (A) which has a crosslinkable group, and a radical polymerization initiator (C), and the fluorine atom content rate in solid content of this photosensitive resin composition is 10-45. It is characterized by mass%.
Hereinafter, the present invention will be described with reference to the accompanying drawings.

[First embodiment]
FIG. 1 is a cross-sectional view showing a schematic configuration of an organic transistor element 10 manufactured by the manufacturing method of the first embodiment of the present invention.
The organic transistor element 10 includes a substrate 1, a gate electrode 2, a gate insulating film 3 formed on the gate electrode 2, a source electrode 4 and a drain electrode 5 formed on the gate insulating film 3, and a gate insulating film. 3, an organic semiconductor layer 6 formed between the source electrode 4 and the drain electrode 5, a first insulating film 7 covering the organic semiconductor layer 6, and the first insulating film 7. And a second insulating film 8.

In the organic transistor element 10, the second insulating film 8 covers the gate electrode 2, the gate insulating film 3, the source electrode 4, the drain electrode 5, the organic semiconductor layer 6, and the first insulating film 7 on the substrate 1. Is formed. The second insulating film 8 is in direct contact with the substrate 1, the gate insulating film 3, the source electrode 4, the drain electrode 5, and the first insulating film 7. Since the periphery of the organic semiconductor layer 6 is covered with the gate insulating film 3, the source electrode 4, the drain electrode 5, and the first insulating film 7, the second insulating film 8 is not in contact with the organic semiconductor layer 6. .
In the second insulating film 8, a hole 9 that reaches the drain electrode 5 from the upper surface (the surface opposite to the substrate 1 side) of the second insulating film 8 is formed.

The second insulating film 8 is a stacked body (hereinafter referred to as a stacked body) having a gate electrode 2, a gate insulating film 3, a source electrode 4, a drain electrode 5, an organic semiconductor layer 6, and a first insulating film 7 on a substrate 1. (Also referred to as (X))) a step of applying the photosensitive resin composition to form a photosensitive resin film (hereinafter also referred to as an application step), and partially exposing the photosensitive resin film. The step of developing and forming the second insulating film 8 (hereinafter also referred to as a lithography step) is performed.
When the photosensitive resin film is partially exposed in the lithography process, the crosslinking (curing) of the fluororesin (A) proceeds in the exposed portion, and the solubility in the developer is lowered. On the other hand, the solubility of the unexposed area in the developer does not change. For this reason, when the exposed photosensitive resin film is developed with a developer, only the unexposed portions are removed. This removed portion becomes the hole 9. Thereby, the 2nd insulating film 8 is obtained as a cured film in which the hole 9 was formed.
Thus, the organic transistor element 10 is obtained by forming the 2nd insulating film 8 on laminated body (X).
Details of each component will be described below.

(Substrate 1)
Examples of the material forming the substrate 1 include glass; plastics such as polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, and polyimide; fiber reinforced composite materials such as glass fiber reinforced plastic; and silicon.
The substrate 1 may be one in which an insulating film is formed on the surface (the side where the gate electrode 2 is provided) of the substrate made of the above material. The material for forming the insulating film is not particularly limited, and known materials can be used.
The thickness of the substrate 1 is preferably 10 to 2,000 μm, particularly preferably 50 to 1,000 μm.

(Gate electrode 2)
The gate electrode 2 is formed from a conductor.
Conductors include platinum, gold, silver, copper, chromium, aluminum, calcium, barium, indium tin oxide, indium zinc oxide, zinc oxide, carbon black, fullerenes, carbon nanotubes, polythiophene, polyethylenedioxythiophene, polystyrene sulfone. Acid, polyaniline, polypyrrole, polyfluorene and the like are preferable. These conductors may be used alone or in combination of a plurality of materials.
The thickness of the gate electrode 2 is usually about 5 to 100 nm, and preferably 10 to 50 nm.
As a formation method of the gate electrode 2, it can select suitably from well-known methods, such as a sputter | spatter, vacuum evaporation, a spin coat, spray coat, printing, and an inkjet.

(Gate insulation film 3)
The gate insulating film 3 is a layer that is provided between the gate electrode 2 and the source electrode 4 and the drain electrode 5, and holds these electrodes in an electrically insulated state.
The thickness of the gate insulating film 3 is preferably 1 nm to 10 μm, more preferably 2 nm to 5 μm, and particularly preferably 5 nm to 1 μm at the portion where the gate electrode 2 does not exist. If the thickness of the gate insulating film 3 is too thin, a leakage current tends to occur between the gate electrode 2 and the source electrode 4, and if it is too thick, the drive voltage tends to increase.

In this embodiment, the gate insulating film 3 consists of a cured film obtained by curing a curable composition containing a fluororesin (A) having a crosslinkable group and a radical polymerization initiator (C).
If necessary, the curable composition comprises a compound (B) having two or more crosslinkable functional groups and having no fluorine atom, a liquid repellent compound (D) that can be lyophilic by irradiation with ultraviolet rays, An agent (E), a solvent, etc. may further be included.
As this curable composition, the thing similar to the photosensitive resin composition which forms the 2nd insulating film 8, for example is mentioned. However, in the formation of the gate insulating film 3, the curable composition may be cured only by heat. In that case, the curable composition only needs to have thermosetting properties, and has photosensitivity (photocurability). You do not have to. Moreover, the fluorine atom content rate in solid content of a curable composition may not be 10-45 mass%.

  The gate insulating film 3 is formed by applying a curable composition on the substrate 1 to form a coating film, removing the solvent in the coating film as necessary, and curing the resulting dried film to form a cured film. Can be formed. At this time, fine processing by photolithography or the like may be performed as necessary.

As a method for applying the curable composition on the substrate 1, a known wet coating method can be used, and a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an inkjet method. Method, flow coating method, roll coating method, casting method, slit coating method, screen printing method, Langmuir-Blodgett method or gravure coating method. From the viewpoint of productivity, a spin coating method, an ink jet method, and a slit coating method are preferable.
Examples of the method for removing the solvent in the coating film include heating, reduced pressure, and a combination of heating and reduced pressure. Heating at normal pressure is preferable from the viewpoint that defects in the dry film are less likely to occur and the operation is simple. At this time, the heating temperature is preferably 30 to 150 ° C, particularly preferably 40 to 100 ° C.
Curing of the dry film can be performed by heating or light irradiation. Heating and light irradiation may be combined.

In the case of heat curing in which curing is performed by heating, the cured film is formed by, for example, applying a curable composition, heating (pre-baking) for the purpose of removing the solvent, and then performing heating (curing) for the purpose of curing. Can be formed.
The prebaking temperature is preferably 40 to 200 ° C, particularly preferably 60 to 200 ° C. The curing temperature is preferably from 100 to 200 ° C, particularly preferably from 120 to 200 ° C. The prebaking time is preferably 1 to 120 minutes, more preferably 1 to 60 minutes, and particularly preferably 1 to 30 minutes. The curing time is preferably 1 to 10 minutes, particularly preferably 1 to 5 minutes.
The prebaking or curing temperature of 200 ° C. or lower means that the temperature of the article subjected to heating does not exceed 200 ° C. Essentially, the set temperature of a heating device such as a hot plate or oven may be set to 200 ° C. or lower. In the case of forming a cured film by thermosetting, the curing can also serve as a pre-bake and can be processed without dividing the process.

In the case of photocuring in which curing is performed by light irradiation (exposure), for example, the cured film is applied with a curable composition, heated (prebaked) for the purpose of removing the solvent, and then irradiated with light (exposure) It can be formed by a method of heating (curing) as necessary.
The light to be irradiated for curing is not particularly limited as long as the radical polymerization initiator (C) contained in the curable composition has a wavelength with sensitivity. Usually, the light used for curing is ultraviolet, but is not limited thereto. When the curable composition contains the liquid repellent compound (D), at the time of curing, the light having a wavelength at which the lyophilic property of the liquid repellent compound (D) occurs and the radical polymerization having sensitivity to the light having the wavelength are used. It is preferable not to use the initiator (C).
In the case of photocuring, the prebaking temperature is preferably 30 to 100 ° C, particularly preferably 40 to 100 ° C, and the curing temperature is preferably 60 to 200 ° C, particularly preferably 100 to 200 ° C. The prebaking time is preferably 1 to 20 minutes, particularly preferably 1 to 10 minutes. The curing time is preferably 1 to 20 minutes, particularly preferably 1 to 10 minutes.

  The formation of the gate insulating film 3 that has been finely processed by photolithography can be performed in the same procedure as the formation of the second insulating film 8.

(Source electrode 4, drain electrode 5)
The source electrode 4 and the drain electrode 5 are each formed from a conductor.
Examples of the conductor are the same as those described in the description of the gate electrode 2.
The materials of the gate electrode 2, the source electrode 4, and the drain electrode 5 may be the same or different from each other.
The thickness of the source electrode 4 and the drain electrode 5 is usually about 5 to 100 nm, and preferably 10 to 50 nm.
A method for forming the source electrode 4 and the drain electrode 5 can be appropriately selected from known methods such as sputtering, vacuum deposition, spin coating, spray coating, printing, and inkjet.

When the curable composition for forming the gate insulating film 3 contains the liquid repellent compound (D), the film has a uniform thickness at a desired position on the gate insulating film 3 by a coating method such as spin coating or spray coating. It is easy to form the source electrode 4 and the drain electrode 5.
That is, a cured film formed from the curable composition is excellent in liquid repellency. When a desired portion of the cured film is irradiated with ultraviolet rays, the liquid repellent compound (D) becomes lyophilic at the irradiated portion, and a pattern of liquid repellent areas and lyophilic areas is formed on the surface of the cured film. When a liquid electrode forming material, for example, a dispersion liquid in which a conductor is dispersed in a solvent, is applied to the surface, it selectively adheres to the lyophilic region. Therefore, an electrode having a shape corresponding to the lyophilic region is formed by heating the electrode forming material and removing the solvent. In the lyophilic process, the dried film formed from the curable composition is made lyophilic by irradiating with ultraviolet rays to obtain a dried film having a pattern of lyophobic regions and lyophilic regions. The dried film may be cured using heat or light.

As a method of forming a pattern composed of a liquid repellent region and a lyophilic region, the surface of the dried film or cured film is irradiated with ultraviolet rays through a photomask, or the surface of the dried film or cured film is lasered. And a method of selectively irradiating with ultraviolet rays using.
As the ultraviolet light source, a light source capable of irradiating ultraviolet light having a wavelength of 300 nm or more, such as a high-pressure mercury lamp (i-line 365 nm), a YAG laser (third harmonic wave 355 nm), or the like can be used. In addition, since the surface of the dried film or the cured film can be lyophilic even by ultraviolet rays having a wavelength of less than 300 nm, a light source capable of irradiating ultraviolet rays having a wavelength of less than 300 nm may be used.

(Organic semiconductor layer 6)
The organic semiconductor layer 6 is provided on the surface of the gate insulating film 3 at a position between the source electrode 4 and the drain electrode 5 in contact with the source electrode 4 and the drain electrode 5. This position is a position facing the gate electrode 2 with the gate insulating film 3 interposed therebetween, and is for ensuring the conduction between the source electrode 4 and the drain electrode 5 when a voltage is applied to the gate electrode 2.
The film thickness of the organic semiconductor layer 6 is not particularly limited, but is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and particularly preferably 10 nm to 1 μm.

As the organic semiconductor constituting the organic semiconductor layer 6, various low molecular compounds, oligomers, and polymers can be used, and there is no particular limitation.
Examples of the low molecular weight compound include pentacene, rubrene, phthalocyanine, perylene, fullerene, derivatives thereof, and sulfur-containing compounds.
Examples of the oligomer include oligothiophene or a derivative thereof.
Examples of the polymer include poly-p-phenylene vinylene (PPV), polyfluorene, fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, fluorene-dithiophene copolymer, polythiophene, polyaniline, polyacetylene, polypyrrole, or these And the like.

Examples of the method for forming the organic semiconductor layer 6 include a method in which an organic semiconductor is vacuum-deposited, a method in which an organic semiconductor is dissolved in a solvent, a coating film is formed by spin coating, spray coating, printing, inkjet, or the like, and then dried. .
Further, as a method for forming the organic semiconductor layer 6, a method may be used in which a layer made of a precursor of an organic semiconductor is first formed and then the precursor is converted into an organic semiconductor by applying light or heat. Examples of such a convertible precursor material include silylethyne-substituted pentacene and tetrabicycloporphyrin derivatives. Since these materials can be converted into pentacene or a tetrabenzoporphyrin derivative by heating, they can be used as precursor materials for the organic semiconductor layer 6.

(First insulating film 7)
In the organic transistor element 10, the first insulating film 7 is provided on the source electrode 4, the drain electrode 5, and the organic semiconductor layer 6, and is not covered with the source electrode 4 and the drain electrode 5 of the organic semiconductor layer 6. The part is covered. The first insulating film 7 functions as a sealing layer for the organic semiconductor layer 6, and the photosensitive resin composition for forming the second insulating film 8 is formed on the organic semiconductor layer 6 when the second insulating film 8 is formed. The contact is prevented and the organic semiconductor layer 6 is prevented from being damaged by the radical polymerization initiator (C) or the solvent in the photosensitive resin composition.
The thickness of the first insulating film 7 is preferably 50 to 5,000 nm as the thickness of the upper portion of the organic semiconductor layer 6 (the side opposite to the substrate 1 side).

The first insulating film 7 contains a fluororesin (F) and has a water contact angle of 105 ° or more on the surface.
As the fluororesin (F), a fluorine-containing polymer (F1) having an aliphatic ring structure in the main chain and a ring structure in the main chain in that it can be dissolved in a fluorine-containing solvent and a film can be formed by a wet coating method. One or both of the fluoropolymer (F2) having a perfluoroalkyl group in the side chain is preferred.
In the first insulating film 7, the fluororesin (F) preferably has no carboxy group and no hydroxyl group. By not having a carboxy group and a hydroxyl group, the performance of the organic transistor element 10 is improved. For example, there is almost no hysteresis of the voltage-current characteristic when the gate voltage is applied with positive and negative reversed, and the stability is excellent.
The fluororesin (F) will be described in detail later.

The first insulating film 7 is preferably formed by a wet coating method in terms of simplicity.
When the first insulating film 7 is formed by a wet coating method, the material used for forming the first insulating film 7 is a resin composition containing the fluororesin (F) and a fluorinated solvent (hereinafter referred to as a “fluorinated solvent”). , Also referred to as a coating composition).
The fluororesin (F) capable of forming an insulating film having a water contact angle of 105 ° or more on the surface is usually insoluble in non-fluorinated solvents and soluble in fluorine-containing solvents because of its high fluorine atom content. is there. If the solvent is a fluorine-containing solvent, the organic semiconductor layer 6 is not easily damaged when the coating composition is applied onto the organic semiconductor layer 6.
The coating composition will be described in detail later.

For example, the first insulating film 7 is formed by a wet coating method on the substrate 1 on which the gate electrode 2, the gate insulating film 3, the source electrode 4, the drain electrode 5, and the organic semiconductor layer 6 are formed. Is applied to form a coating film, and the solvent in the coating film is removed.
The application method of the coating composition and the method of removing the solvent in the coating film are the same as the application method of the curable composition for forming the gate insulating film 3 and the method of removing the solvent in the coating film as well as the exemplified and preferred methods. It is.

(Second insulating film)
As described above, the second insulating film 8 is a cured film formed from a specific photosensitive resin composition through a coating process and a lithography process.
The photosensitive resin composition used for forming the second insulating film 8 will be described in detail later.

<Application process>
In the coating step, the photosensitive resin composition is coated on the laminate (X). When the photosensitive resin composition contains a solvent, the solvent in the formed coating film is removed after application of the photosensitive resin composition to obtain a dry film. Thereby, a photosensitive resin film is formed.

Examples of the method for applying the photosensitive resin composition and the method for removing the solvent in the coating film include both the exemplified method and the preferable method. It is the same.
The heating condition is preferably a temperature at which the solvent evaporates and the crosslinkable functional group of the fluororesin (A) or compound (B) and the radical polymerization initiator (C) do not substantially react. For example, the heating temperature is preferably 30 to 150 ° C, particularly preferably 40 to 100 ° C. The heating time is preferably about 30 seconds to 10 minutes.

<Lithography process>
In the lithography process, the photosensitive resin film formed in the coating process is partially exposed and developed to form the second insulating film 8.
When a region other than the position where the hole 9 is formed in the photosensitive resin film is partially exposed, the exposed portion is cured. Thereby, the solubility with respect to the developing solution of an exposure part falls, on the other hand, the solubility with respect to the developing solution of an unexposed part (part corresponding to the hole 9) does not change. Therefore, when the exposed photosensitive resin film is developed with a developer, the unexposed portion is removed by dissolution or dispersion in the developer, and a cured film (second insulating film 8) in which holes 9 are formed is obtained. .

For the exposure, X-rays, electron beams, ultraviolet rays, visible rays and the like including wavelengths absorbed by the radical polymerization initiator (C) can be used. As a light source used for exposure, ultraviolet rays or visible rays are preferable, and an ultrahigh pressure mercury arc is particularly preferable.
The dose is set according to the film thickness of the photosensitive resin film and the type of the radical polymerization initiator (C) used. For example, for a 10 μm thick film, a suitable dose is 100 to 2,000 mJ / cm ² .
Examples of the exposure method include a method of exposing through a mask using an exposure apparatus such as an aligner or a stepper in a pressure mode, a vacuum contact mode, a proximity mode, or the like.

  Baking (post-exposure baking) may be performed after exposure and before development. By baking, the reaction rate of the photochemically generated intermediate having a long lifetime can be increased. Since these intermediates increase mobility during baking, they can move to increase the probability of contact with the reaction site and increase the reaction rate. As another method for increasing the mobility of these reactive intermediates, heating can be performed during exposure. Such a technique increases the sensitivity of the photosensitizer and the like. The baking temperature varies depending on the type of intermediate, but is preferably 50 to 250 ° C.

Development can be performed by a known method such as spraying, paddle, dipping, or ultrasonic waves.
As the developer used for development, the resin in the exposed area is insoluble or only slightly soluble, and the resin in the unexposed area uses a soluble solvent. That is, it is preferable to dissolve the resin in the unexposed area. Examples of the developer include non-fluorinated solvents such as ketone-based solvents, ester-based solvents, ether-based solvents, amide-based solvents, and aromatic hydrocarbon-based solvents mentioned as solvents for photosensitive resin compositions.

When the resin in the unexposed area is dissolved after the development, the resin is rinsed with a rinsing liquid as necessary, and is spun (rotated) at high speed for drying.
The rinsing solution is not particularly limited as long as it is the same as the developing solution, or the developing solution is not as highly soluble as the resin in the unexposed area, and is compatible with the developing solution. Specific examples include alcohols, the aforementioned ketone solvents, and ester solvents.

  After development or rinsing, baking may be performed to remove the developer or rinse liquid remaining in the exposed area. The baking can be performed by a hot plate, an oven or the like, and the baking condition is desirably 80 to 200 ° C. and 0.5 to 60 minutes.

After development or rinsing, heating for thermally curing the exposed portion may be performed. The heating conditions are preferably about 150 to 450 ° C. for about 1 to 300 minutes, particularly preferably about 160 to 400 ° C. for about 2 to 180 minutes.
As the heating device, a hot plate, an oven, and a furnace (furnace) are preferable, and examples of the heating atmosphere include an inert gas atmosphere such as nitrogen and argon, an atmosphere such as air and oxygen, a reduced pressure, and the like. Is preferred.

Depending on the exposure and development conditions, some resin may be observed in the unexposed areas, and descum may be performed after development.
The descum is performed by dry etching. Examples of the descum etching gas include oxygen gas, argon gas, and fluorocarbon gas.

As described above, the organic transistor element 10 is obtained by forming the second insulating film 8 on the stacked body (X).
Thereafter, if necessary, a pixel electrode may be formed on the second insulating film 8 so as to be connected to the drain electrode 5 to form an organic transistor element suitable for a liquid crystal display or the like. In such an organic transistor element, the second insulating film 8 functions as an interlayer insulating film, and the hole 9 functions as a contact hole.
The pixel electrode can be formed, for example, by filling the hole 9 formed in the second insulating film 8 with an electrode material and further forming an electrode pattern on the surface of the second insulating film 8. The pixel electrode can be formed in the same manner as the gate electrode 2, the source electrode 4, the drain electrode 5, and the like.

[Photosensitive resin composition]
The photosensitive resin composition used for forming the second insulating film 8 includes a fluororesin (A) having a crosslinkable group and a radical polymerization initiator (C), and if necessary, two or more crosslinks. It may further contain a compound (B) having a functional functional group and having no fluorine atom, a liquid repellent compound (D) that can be lyophilic by irradiation with ultraviolet rays, an additive (E), a solvent, and the like. Moreover, the fluorine atom content rate in solid content of this photosensitive resin composition is 10-45 mass%.

The crosslinkable functional group in the present invention is a functional group that can undergo radical polymerization reaction when external energy is applied. As a result, the compound having a crosslinkable functional group undergoes reactions such as polymerization, crosslinking, and chain extension.
In the photosensitive resin composition, radicals are generated from the radical polymerization initiator (C) by the action of external energy, and the radicals cause a polymerization reaction in the crosslinkable functional group. Even if the radical polymerization initiator (C) is not contained, the crosslinkable functional group can cause a polymerization reaction by being given external energy. However, by containing the radical polymerization initiator (C), it is efficient. Thus, a cured film can be produced, and the solvent resistance of the cured film is improved.
In the present invention, at least light is used as the external energy. As the external energy, only light may be used, or light and heat may be used in combination.

(Fluororesin (A))
The crosslinkable functional group of the fluororesin (A) causes a radical polymerization reaction by applying external energy, and causes crosslinkage or chain extension between the fluororesin (A) molecules. Moreover, when the photosensitive resin composition contains a compound (B) to be described later, it reacts with the crosslinkable functional group of the compound (B) to form a cured film together with these.

Examples of the crosslinkable functional group include a carbon-carbon unsaturated double bond that can be polymerized by a radical, a carbon-carbon unsaturated triple bond that can be polymerized by a radical, a ring that is opened by a radical, and a group containing them.
Specifically, vinyl (oxy) group, allyl (oxy) group, isopropenyl group, 3-butenyl group, (meth) acryloyl (oxy) group, trifluorovinyl (oxy) group, ethynyl group, 1-oxo Examples thereof include a cyclopenta-2,5-dien-3-yl group, a diarylhydroxymethyl group, a hydroxyfluorenyl group, a cyclobutalene ring, and an oxirane ring.
As the crosslinkable functional group in the present invention, a vinyl (oxy) group, an allyl (oxy) group, an ethynyl group, and a (meth) acryloyl (oxy) are highly reactive and easily obtain a cured film having a high crosslink density. At least one crosslinkable functional group selected from the group consisting of groups is preferred.

Since the fluororesin (A) has a fluorine atom, the dielectric constant and dielectric loss of the cured film are likely to be low, so that it is preferable as a material for forming the insulating film. When the dielectric constant and dielectric loss of the insulating film are low, a delay in signal propagation speed can be suppressed between multilayer wirings manufactured using the insulating film, and an element having excellent electrical characteristics can be obtained.
Having a fluorine atom is preferable as a material for forming the insulating film from the viewpoint of lowering the water absorption of the cured film. The low water absorption rate of the insulating film is excellent in that it is possible to suppress changes in the bonding state of the electrode bonded to the insulating film and the surrounding wiring portions, or in that metal deterioration (such as rust) can be suppressed. The effect is great in terms of improving the reliability.

  The fluorine atom content of the fluororesin (A) may be an amount that allows the fluorine atom content in the solid content of the photosensitive resin composition to be 10 to 45% by mass or less, and is included in the photosensitive resin composition. 20-50% by mass is preferable, and 25-48% by mass is particularly preferable. When the fluorine atom content of the fluororesin (A) is not more than the upper limit of the above range, the solubility in a non-fluorinated solvent is excellent.

When the fluororesin (A) is a homopolymer composed of one type of structural unit, the fluorine atom content (mass%) of the one type of structural unit is the fluorine atom content of the fluororesin (A). .
When the fluororesin (A) is a copolymer composed of a plurality of types of structural units, the total of all the structural units in the copolymer is calculated as the fluorine atom content (% by mass) of each of the multiple types of structural units. A value obtained by multiplying the ratio (molar ratio) of each structural unit when set to 1 and summing those values is defined as the fluorine atom content of the fluororesin (A).
The fluorine atom content (% by mass) of the structural unit is obtained from the following formula from the number Fn of fluorine atoms contained in the structural unit and the formula amount Fw of the structural unit.
Fluorine atom content (% by mass) = (Fn × 19) × 100 / Fw

  More specifically, the fluorine resin (A) includes fluorine-containing aromatic resins such as fluorine-containing polyarylene prepolymers and fluorine-containing phenol resins; fluorine-containing acrylic (methacrylic) resins; fluorine-containing epoxy resins; fluorine-containing polyimides and the like. It is done. Of these, fluorine-containing aromatic resins are preferable, and fluorine-containing polyarylene prepolymers are particularly preferable in terms of low dielectric constant, high heat resistance, photosensitivity, and the like.

The fluorine-containing polyarylene prepolymer (hereinafter also referred to as “prepolymer (A1)”) has a polyarylene structure in which a plurality of aromatic rings are bonded via a single bond or a linking group, and a fluorine atom. And has a crosslinkable functional group.
The crosslinkable functional group of the prepolymer (A1) does not substantially react at the time of producing the prepolymer (A1), and causes a radical polymerization reaction by applying external energy. Those that cause is preferred.
As the crosslinkable functional group in the prepolymer (A1), a vinyl group or an ethynyl group is preferable because the reactivity at the time of production of the prepolymer (A1) is low and the reactivity when external energy is applied is good. Is particularly preferred.
The prepolymer (A1) may have two or more types of crosslinkable functional groups per molecule.

The linking group in the polyarylene structure includes, for example, an ether bond (—O—), a sulfide bond (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), these bonds in the carbon chain, and Examples include an alkylene group containing any of the groups.
Among the fluorinated polyarylene prepolymers, a polymer having a structure in which aromatic rings are bonded with a linking group containing an ether bond is referred to as “fluorinated polyarylene ether prepolymer”. Specific examples of the linking group containing an ether bond include an ether bond consisting only of an etheric oxygen atom and an alkylene group containing an etheric oxygen atom in the carbon chain.
Since the fluorine-containing polyarylene ether prepolymer has an etheric oxygen atom, the molecular structure is flexible and the flexibility of the cured film is favorable.
The prepolymer (A1) preferably includes a fluorinated polyarylene ether prepolymer, and the prepolymer (A1) is particularly preferably only a fluorinated polyarylene ether prepolymer.

  Specific examples of the prepolymer (A1) include one of a compound (Y-1) having a crosslinkable functional group and a phenolic hydroxyl group and a compound (Y-2) having a crosslinkable functional group and a fluorine atom-substituted aromatic ring. Or both, a fluorine-containing aromatic compound (Z1) represented by the following formula (Z1) and a compound (Z2) having three or more phenolic hydroxyl groups are subjected to a condensation reaction in the presence of a deHF agent. , A polymer having a crosslinkable functional group and an ether bond (hereinafter also referred to as “prepolymer (A1-1)”).

In formula (Z1), n1 represents an integer of 0 to 3, a and b each independently represents an integer of 0 to 3, and Rf ¹ and Rf ² each independently represents a fluorine-containing alkyl group having 1 to 8 carbon atoms. F in the aromatic ring represents that all hydrogen atoms in the aromatic ring are substituted with fluorine atoms. When a is 2 or more, the plurality of Rf ¹ may be the same or different. When b is 2 or more, the plurality of Rf ² may be the same or different.

  By using the compound (Z2) having 3 or more phenolic hydroxyl groups, the prepolymer (A1-1) can introduce a branched structure into the polymer chain, make the molecular structure three-dimensional, and increase the free volume of the polymer. Thus, a reduction in density, that is, a reduction in dielectric constant is achieved. In general, a linear polymer having an aromatic ring is likely to undergo molecular orientation due to stacking of aromatic rings, but in a cured film formed from a prepolymer (A1-1), a branched structure is introduced. Molecular orientation is suppressed, and as a result, birefringence is reduced.

The prepolymer (A1-1) can be produced by either or both of the following methods (i) and (ii).
(I) A method in which a fluorine-containing aromatic compound (Z1), a compound (Z2), and a compound (Y-1) are subjected to a condensation reaction in the presence of a deHF agent.
(Ii) A method of subjecting the fluorine-containing aromatic compound (Z1), the compound (Z2), and the compound (Y-2) to a condensation reaction in the presence of a deHF agent.
In addition, when manufacturing prepolymer (A1) by both said (i) and (ii), a fluorine-containing aromatic compound (Z1), a compound (Z2), a compound (Y-1), and a compound (Y -2) are subjected to a condensation reaction in the presence of a deHF agent.

  In any of the methods (i) and (ii), the condensation reaction may be carried out in one step or in multiple steps. Moreover, after reacting a specific compound preferentially among the reaction raw materials, another compound may be subsequently reacted. When the condensation reaction is performed in multiple stages, the intermediate product obtained in the middle may be separated from the reaction system and purified, and then used for the subsequent reaction (condensation reaction). In the reaction field, the raw material compounds may be charged all at once, may be charged continuously, or may be charged intermittently.

As the compound (Y-1) used in the production method (i), a compound having one phenolic hydroxyl group (Y-1-1) and a compound having two phenolic hydroxyl groups (Y-1-2) are preferable. .
Specific examples of the compound (Y-1-1) include phenols having a reactive double bond such as 4-hydroxystyrene; 3-ethynylphenol, 4-phenylethynylphenol, 4- (4-fluorophenyl) ethynyl. Examples include ethynylphenols such as phenol. These may be used alone or in combination of two or more. Aromatic compounds having a vinyl group or an ethynyl group as the crosslinkable functional group are particularly preferred.
Specific examples of the compound (Y-1-2) include 2,2′-bis (phenylethynyl) -5,5′-dihydroxybiphenyl, 2,2′-bis (phenylethynyl) -4,4′-dihydroxy. Bis (phenylethynyl) dihydroxybiphenyls such as biphenyl; and dihydroxydiphenylacetylenes such as 4,4′-dihydroxytolane and 3,3′-dihydroxytolane. These may be used alone or in combination of two or more.

  The compound (Y-2) used in the production method (ii) is preferably a compound having a crosslinkable functional group and a perfluoroaromatic ring such as perfluorophenyl or perfluorobiphenyl. Specific examples include pentafluorostyrene, pentafluorobenzyl acrylate, pentafluorobenzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3- (pentafluorophenyl) pentafluoropropene- Fluorinated aryls having a reactive double bond such as 1; fluorinated aryls having a cyano group such as pentafluorobenzonitrile; fluorinated aryl acetylenes such as pentafluorophenylacetylene and nonafluorobiphenylacetylene; phenylethynylpenta Fluorine-containing diarylacetylenes such as fluorobenzene, phenylethynyl nonafluorobiphenyl, decafluorotolane, etc. It is. These may be used alone or in admixture of two or more. Since the crosslinking reaction proceeds at a relatively low temperature and the heat resistance of the cured film formed from the resulting prepolymer is increased, the compound (Y-2) is a fluorine-containing aryl having a double bond, a triple bond. Fluorine-containing arylacetylenes having the formula:

  As the deHF agent used when producing the prepolymer (A1-1), a basic compound is preferable, and an alkali metal carbonate, hydrogencarbonate or hydroxide is particularly preferable. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.

In the production methods (i) and (ii), the condensation reaction is preferably performed in a polar solvent. Examples of polar solvents include amides such as N, N-dimethylacetamide, N, N-dimethylformamide, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; diethyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether Aprotic polar solvents such as ethers such as diethylene glycol diethyl ether and triethylene glycol dimethyl ether are preferred.
The polar solvent contains toluene, xylene, benzene, tetrahydrofuran, benzotrifluoride, xylene hexafluoride and the like as long as the solubility of the prepolymer to be produced is not lowered and the condensation reaction is not adversely affected. Also good. By containing these, the polarity (dielectric constant) of the solvent changes, and the reaction rate can be controlled.
The condensation reaction conditions are preferably 10 to 200 ° C. and 1 to 80 hours. 2 to 60 hours are more preferable at 20 to 180 ° C, and 3 to 24 hours are particularly preferable at 50 to 160 ° C.

  The production method of the prepolymer (A1-1) is appropriately selected from the production methods (i) and (ii) according to the physical properties such as heat resistance, relative dielectric constant, birefringence and flexibility of the cured film to be formed. it can. For example, when the production method (ii) is used, the produced prepolymer (A1-1) tends to generally have a low dielectric constant and birefringence value of the cured film. That is, in order to obtain a cured film having a low relative dielectric constant and low birefringence value, it is preferable to produce the prepolymer (A1) by the production method (ii).

  The prepolymer (A1-1) is purified by a method such as neutralization, reprecipitation, extraction, or filtration after the condensation reaction or solution. It is preferable to sufficiently purify the metal, such as potassium and sodium, which is a condensation reaction catalyst, and free halogen atoms, which may cause malfunction of the transistor and corrosion of the wiring.

  Suitable examples of the prepolymer (A1-1) include fluorine-containing aromatic compounds such as perfluoro (1,3,5-triphenylbenzene) and perfluorobiphenyl, 1,3,5-trihydroxybenzene, 1, Potassium carbonate, etc., including phenolic compounds such as 1,1-tris (4-hydroxyphenyl) ethane and crosslinkable functional group-containing aromatic compounds such as pentafluorostyrene, acetoxystyrene, chloromethylstyrene, and pentafluorophenylacetylene And a polymer obtained by reacting in the presence of a dehydrohalogenating agent.

  The number average molecular weight (Mn) of the fluororesin (A) is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 5,000 to 20,000. When the number average molecular weight (Mn) is not less than the lower limit of the above range, the flexibility of the cured film is hardly lowered, and when it is not more than the upper limit of the above range, the photosensitive resin composition is easily purified.

The fluororesin (A) contained in the photosensitive resin composition may be one type or two or more types.
40-90 mass% is preferable with respect to solid content (100 mass%) of the photosensitive resin composition, and, as for content of the fluororesin (A) in the photosensitive resin composition, 50-80 mass% is more preferable, 55-70 mass% is especially preferable. When it is at least the lower limit of the above range, the dielectric constant of the formed cured film is sufficiently low. Since it will become easy to harden | cure at low temperature as it is below the upper limit of the said range, the solvent resistance of a cured film becomes high enough.

(Compound (B))
When the photosensitive resin composition contains the compound (B), the molecules can be cross-linked and the curability at low temperature is improved. Moreover, the hardness and solvent resistance of the cured film formed from the photosensitive resin film are improved.
In addition, when a liquid compound is included as the compound (B), the compound (B) has a function as a solvent, and the photosensitive resin composition does not include a solvent that does not correspond to the compound (B). Wet application of the resin composition becomes possible. The more the compound (B) is a low-viscosity compound and the more the compound (B) is added, the lower the viscosity of the photosensitive resin composition and the easier the wet application.

The compound (B) preferably has 2 to 20 crosslinkable functional groups, and particularly preferably 2 to 8 crosslinkable functional groups.
The crosslinkable functional group of the compound (B) is preferably a group that reacts in the same step as the step in which the crosslinkable functional group of the fluororesin (A) causes a radical polymerization reaction.
The crosslinkable functional group of the compound (B) reacts with each other to cause crosslinking or chain extension. Moreover, it reacts with the crosslinkable functional group of the fluororesin (A) and forms a cured film together with these.

As the crosslinkable functional group of the compound (B), a (meth) acryloyl (oxy) group is preferable. A (meth) acryloyloxy group is more preferable from the viewpoint of high reactivity and availability, and an acryloyl group and an acryloyloxy group are particularly preferable from the viewpoint of higher reactivity.
The compound (B) may have two or more kinds of crosslinkable functional groups in one molecule.
The crosslinkable functional groups in the fluororesin (A) and the compound (B) coexisting in the photosensitive resin composition may be the same or different.

  140-5,000 are preferable, as for the number average molecular weight (Mn) of a compound (B), 200-3,000 are more preferable, and 250-2,500 are especially preferable. It is hard to volatilize by heating as it is more than the lower limit of the above-mentioned range. When the amount is not more than the upper limit of the above range, the viscosity of the compound (B) is kept low, and a uniform photosensitive resin composition is easily obtained when mixed with the fluororesin (A).

Specific examples of the compound (B) include dipentaerythritol triacrylate triundecylate, dipentaerythritol pentaacrylate monoundecylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl). Isocyanurate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxy Bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A dimethacrylate 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, hydroxypivalin Acid neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylation Trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, triallyl cyanurate, triallyl isocyanurate, trimeta ali Luisocyanurate, 1,4-butanediol divinyl ether, 1,9-nonanediol divinyl ether, cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, acrylic acid 2- ( 2-vinyloxyethoxy) ethyl, 2- (2-vinyloxyethoxy) ethyl methacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, with the following formula (4) Ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate represented by the following formula (5) , Ditrimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol methacrylate, compounds represented by the following formula (6).
Further, polyester acrylate (compound obtained by modifying both ends of a condensate of dihydric alcohol and dibasic acid with acrylic acid: manufactured by Toagosei Co., Ltd., trade name Aronix (M-6100, M-6200, M-6250, M- 6500): Compound obtained by modifying the hydroxyl terminal of the condensate of polyhydric alcohol and polybasic acid with acrylic acid: manufactured by Toagosei Co., Ltd., trade name Aronix (M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050)) can also be used. These can be obtained from commercial products.

  As the compound (B), ethoxylated isocyanuric acid triacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate from the viewpoint of availability and reactivity. , Trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, and tricyclodecane dimethanol diacrylate are preferred.

  When the photosensitive resin composition contains the compound (B), the content is preferably 10 to 60 parts by mass in the total (100 parts by mass) of the fluororesin (A) and the compound (B), and 20 -50 mass parts is more preferable, and 30-45 mass parts is especially preferable. When the proportion of the compound (B) is not less than the lower limit of the above range, the effect of containing the compound (B) can be sufficiently obtained. Moreover, the dielectric constant of the insulating film formed as the ratio of a compound (B) is below the upper limit of the said range becomes low enough.

(Radical polymerization initiator (C))
As the radical polymerization initiator (C), a photopolymerization initiator (C1) that generates a radical by light is preferably used from the viewpoint of photosensitivity (photocurability).
As a photoinitiator (C1), a well-known thing can be used in a photocurable composition, and it can select suitably according to the kind (wavelength etc.) of the light used for exposure. Although it does not specifically limit as light irradiated in order to harden the photosensitive resin composition, An ultraviolet-ray is used suitably.
Specific examples of the photopolymerization initiator (C1) having sensitivity in the ultraviolet region include 1,2-octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime)] (for example, product name: IRGACURE OXE01), oximes such as ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime) (for example, product name: IRGACURE OXE02) Ester derivatives; α-aminoalkylphenone compounds such as IRGACURE 369 (product name), IRGACURE 907 (product name); acylphosphine oxide compounds such as DAROCUR TPO (product name) (all manufactured by Ciba Specialty Chemicals), etc. Is mentioned.
IRGACURE OXE01 and IRGACURE OXE02 are preferable in that the reactivity of the generated radicals is good.
When the photopolymerization initiator (C1) is contained in the photosensitive resin composition, the content thereof is 1 to 20 parts by mass with respect to the total (100 parts by mass) of the fluororesin (A) and the compound (B). Is preferably 3 to 15 parts by mass. When it is at least the lower limit of the above range, the effect of improving the curability when cured at a low temperature is sufficiently obtained, and the solvent resistance of the cured film is sufficiently improved. The storage stability of the photosensitive resin composition will become favorable as it is below the upper limit of the said range.

When using heat together as external energy for curing the photosensitive resin composition, the photosensitive resin composition contains a thermal polymerization initiator (C2) that generates radicals by heat as the radical polymerization initiator (C). May be.
Since the reaction temperature at the time of thermosetting the photosensitive resin composition is too low, stability during storage of a compound having a crosslinkable functional group and a composition containing the same cannot be ensured, and therefore, preferably 40 ° C or higher, 60 ° C. The above is more preferable, and 70 ° C. or higher is particularly preferable. The upper limit of the reaction temperature is not more than the upper limit of the heating temperature allowed in the production process of the cured film, for example, not more than the heat resistant temperature of the substrate. For example, the reaction temperature is preferably 250 ° C. or less, and particularly preferably 200 ° C. or less because the lower the reaction temperature, the lower the reaction temperature.
Specific examples of the thermal polymerization initiator (C2) include azobisisobutyronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, and dicumyl peroxide. These may be used alone or in combination of two or more. In view of the decomposition temperature, azobisisobutyronitrile and benzoyl peroxide are preferred.
When the photopolymerization initiator (C2) is contained in the photosensitive resin composition, the content is 1 to 20 parts by mass with respect to the total (100 parts by mass) of the fluororesin (A) and the compound (B). Is preferable, and 5 to 15 parts by mass is particularly preferable. When it is at least the lower limit of the above range, the effect of improving the curability when cured at a low temperature is sufficiently obtained, and the solvent resistance of the cured film is sufficiently improved. It is excellent in the storage stability of the photosensitive resin composition as it is below the upper limit of the said range.

(Liquid repellent compound (D) that can be made lyophilic by UV irradiation)
When the liquid repellent compound (D) is contained, the surface of the cured film formed from the photosensitive resin composition has high liquid repellency. When the cured film is partially irradiated with ultraviolet rays, the liquid repellency of the portion irradiated with the ultraviolet rays decreases (improves lyophilicity), and as a result, the surface has a liquid-repellent region and a lyophilic region. A pattern can be formed. When a liquid material for forming another layer (for example, an electrode) is applied to the surface, it selectively adheres to the lyophilic region. By utilizing this, another layer can be selectively formed on the surface.

As the liquid repellent compound (D), a known material can be used as a material for forming the pattern of the liquid repellent region and the lyophilic region as described above.
Preferable examples of the liquid repellent compound (D) include a polymer (D1) having the following structural unit (d1).
Structural unit (d1): a structural unit derived from the compound (M) containing in the molecule a fluoroalkyl group and a site (UV decomposing site) that decomposes upon irradiation with ultraviolet rays.
The polymer (D1) has liquid repellency because the structural unit (d1) contains a fluoroalkyl group. Further, since the structural unit (d1) contains an ultraviolet decomposition site, decomposition occurs in the molecule when irradiated with ultraviolet rays, and the decomposition residue containing the fluoroalkyl group is detached from the polymer (D1), It has the property of reducing liquid repellency (improving lyophilicity).

  Examples of the compound (M) include compounds (m1) to (m7) represented by the following formulas (m1) to (m7), respectively. Among these, the compound (m1) and the compound (m2) are preferable because they can be decomposed by irradiation with ultraviolet rays having a wavelength of 300 nm or more.

［式中、Ｒ^１は、水素原子、炭素数１〜６のアルキル基またはフェニル基であり；Ｒ^２は、単結合またはフッ素原子を有しない２価の有機基であり；Ｃｆは、炭素数１〜２０のフルオロアルキル基、または炭素原子間にエーテル性酸素原子を有する炭素数２〜２０のフルオロアルキル基であり；Ｘは、酸素原子、硫黄原子、窒素原子またはＮＨであり；ｍは、Ｘが酸素原子、硫黄原子またはＮＨである場合には１であり、Ｘが窒素原子である場合には２であり；ｎは、０〜４の整数であり；ｋは、０または１であり；Ｚは、Ｒ^４Ｒ^５Ｃ＝ＣＲ^３−ＣＯ−であり、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立に水素原子またはメチル基である。］

[Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; R ² is a single bond or a divalent organic group having no fluorine atom; A fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon atoms; X is an oxygen atom, sulfur atom, nitrogen atom or NH; 1 when X is an oxygen atom, sulfur atom or NH; 2 when X is a nitrogen atom; n is an integer from 0 to 4; k is 0 or 1 ; Z ^is R ⁴ R ^{5 C} = a ^{CR 3 -CO-, R 3, R} 4 and ^{R 5} are each independently a hydrogen atom or a methyl group. ]

［式中、Ｃｆ、Ｘ、Ｚ、およびｎはそれぞれ前記と同義であり；Ｒ^６およびＲ^７は、それぞれ独立に水素原子、炭素数１〜６のアルキル基またはフェニル基であり；ｌは、Ｘが酸素原子、硫黄原子またはＮＨである場合には１であり、Ｘが窒素原子である場合には２である。］

[Wherein, Cf, X, Z, and n are as defined above; R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; It is 1 when X is an oxygen atom, a sulfur atom or NH, and 2 when X is a nitrogen atom. ]

V ¹ -R ⁸ -Cf ¹ (m3)
^{V 2 -Ph-Y 3 -R 8} -Cf 1 ··· (m4)
_{^{V 1 - (CH 2) g}} -Ph-Y 3 -R 8 -Cf 1 ··· (m5)
^{V 2 -Ph-Y 2 -Ph-} Y 3 -R 8 -Cf 1 ··· (m6)
_{^{V 1 - (CH 2) g}} -Ph-Y 4 -Ph-Y 3 -R 8 -Cf 1 ··· (m7)
[Wherein Cf ¹ is a C 2-15 perfluoroalkyl group; V ¹ is a (meth) acryloyloxy group; V ² is a vinyl group or a (meth) acryloyloxy group; R ⁸ Is a C 1-10 alkylene group or a single bond; Ph is a phenylene group; Y ³ is —CH ₂ O— or —COO—; Y ⁴ is —OCH ₂ — or —CH ₂ O—. G is 1 or 2. ]

R ¹ is preferably an alkyl group having 1 to 6 carbon atoms from the viewpoint of excellent solubility of the compound (m1).
Examples of the divalent organic group for R ² include —C ₆ H ₄ —, —C ₆ H ₄ O (CH ₂ ) _w1 — (wherein w1 is an integer of 0 to 10), —C ₆ H _{4. COO (CH 2) w2 -,} ( provided that, w2 is an integer of _{0~10.) - CH 2 -,} - (CH 2) w3 COO (CH 2) w4 - ( However, w3 is an integer of from 1 to 10 And w4 is an integer of 0 to 10.), —CH ₂ O (CH ₂ ) _w5 — (where w5 is an integer of 0 to 10), —CH (CH ₃ ) O (CH ₂ ) _W6- (where w6 is an integer of 0 to 10). From the viewpoint of easily absorb more UV wavelength 300nm _{is, -C 6 H 4 -, -} C 6 H 4 O (CH 2) w1 -, - C 6 H 4 COO (CH 2) w2 - are preferred. Further, from the viewpoint that the decomposition residue is easily removed, including a Cf group, a single _{bond, -CH 2 -, - (CH} 2) w3 COO (CH 2) w4 -, - CH 2 O (CH 2) w5 -, _{-CH (CH 3) O (CH} 2) w6 - it is preferred. Each of w1, w2, and w4 to w6 is preferably an integer of 0 to 4, and an integer of 0 to 2 is particularly preferable from the viewpoint of easy production. w3 is preferably an integer of 0 to 6, and an integer of 1 to 3 is particularly preferable from the viewpoint of easy production.

The carbon number of Cf is preferably 2 to 20, more preferably 2 to 15, and particularly preferably 4 to 8 from the viewpoint of excellent liquid repellency and excellent compatibility with other monomers. Further, the number of carbon atoms in the Cf group is preferably 6 or less, more preferably 2 to 6 and particularly preferably 4 to 6 from the viewpoint of low environmental load.
Cf is preferably such that the number of fluorine atoms is 80% or more with respect to the total number of fluorine atoms and hydrogen atoms, from the point that the liquid repellency of the surface of the cured film becomes better, That is, a C 1-20 perfluoroalkyl group or a C 2-20 perfluoroalkyl group having an etheric oxygen atom between carbon atoms is particularly preferred.
Cf may be linear or branched.

As Cf, specifically, —CF ₃ , —CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CH (CF ₃ ) ₂ , —CF ₂ CHF ₂ , — (CF ₂ ) ₂ CF ₃ , _{- (CF 2) 3 CF 3} , - (CF 2) 4 CF 3, - (CF 2) 5 CF 3, - (CF 2) 6 CF 3, - (CF 2) 7 CF 3, - (CF 2) ₈ CF ₃ , — (CF ₂ ) ₉ CF ₃ , — (CF ₂ ) ₁₁ CF ₃ , — (CF ₂ ) ₁₅ CF ₃ , —CF (CF ₃ ) O (CF ₂ ) ₅ CF ₃ , —CF ₂ O (CF ₂ CF ₂ O) _p CF ₃ (where p is an integer of 1 to 8), —CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _q C ₆ F ₁₃ (where q is an integer from 1 to _{4), -. CF (CF 3} ) O (CF 2 CF (CF 3) O) r C F ₇ (where, r is an integer of 0-5.) Are exemplified.

  X is preferably an oxygen atom, a sulfur atom or NH from the viewpoint of easy production of the polymer (D1) (the polymer (D1) is difficult to gel), and from the point of easy availability of raw materials, A sulfur atom is particularly preferable from the viewpoint of easy production of the compound (m1).

m is preferably 1 from the viewpoint of easy production of the polymer (D1) (the polymer (D1) is difficult to gel).
n is preferably an integer of 0 to 2, particularly preferably 0 or 1, from the viewpoint of availability of raw materials and ease of synthesis.
k is particularly preferably 1 from the viewpoint of availability of raw materials and ease of synthesis. In this case, the positional relationship between X and O in —O-benzene ring —X— in formula (m1) is preferably a para positional relationship from the viewpoint of availability of raw materials.

  Z is preferably an acryloyl group or a methacryloyl group from the viewpoint of high reactivity.

Since the carbon-carbon unsaturated double bond in the Z group, the V ¹ group and the V ² group (the same kind as the crosslinkable functional group) of the compounds (m1) to (m7) is lost by polymerization, the unit (d1) Does not have a crosslinkable functional group.

  The proportion of the structural unit (d1) in the polymer (D1) is preferably 10 to 90 mass%, more preferably 15 to 90 mass%, particularly preferably 20 to 85 mass%, based on the total mass of the polymer (D1). preferable. When the proportion of the structural unit (d1) is not less than the lower limit of the above range, the liquid repellency on the surface of the cured film becomes better. When the amount is not more than the upper limit of the above range, the polymer (D1) is easily dissolved in the non-fluorinated solvent.

The polymer (D1) has a crosslinkable functional group and a Cf group (a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon atoms). It is preferable to further have a structural unit (d2) not having. The crosslinkable functional group of the structural unit (d2) reacts with the crosslinkable functional group of the fluororesin (A) or the compound (B) and forms a cured film excellent in hardness, solvent resistance, etc. together with these. Form.
The polymer (D1) may have a structural unit (d3) other than the structural unit (d1) and the structural unit (d2).
Specific examples of the structural units (d2) and (d3) are the same as the “unit having a crosslinkable functional group (c2)” and “other units (c3)” described in International Publication No. 2011/162001, respectively. Can be mentioned. However, it is not limited to these.
In addition, the structural unit (d1), the structural unit (d2), and the structural unit (d3) in the polymer (D1) may be bonded in a random manner or a block shape.

  The proportion of the structural unit (d2) in the polymer (D1) is preferably 10 to 90% by mass, more preferably 10 to 85% by mass, further preferably 10 to 80% by mass, and particularly preferably 10 to 50% by mass. When the proportion of the structural unit (d2) is not less than the lower limit of the above range, the reaction with the fluororesin (A) and the compound (B) becomes good. When the amount is not more than the upper limit of the above range, the liquid repellency on the surface of the cured film becomes better.

  The proportion of the structural unit (d3) in the polymer (D1) is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 20% by mass or less. The lower limit is preferably 0% by mass. When the proportion of the structural unit (d3) is not more than the upper limit of the above range, a sufficient proportion of the structural unit (d1) and the structural unit (d2) can be secured, and the liquid repellency and photosensitive resin composition on the surface of the cured film can be secured. Does not impair the curability of the product.

  5-60 mass% is preferable and, as for the fluorine atom content rate of a polymer (D1), 8-40 mass% is especially preferable. When the fluorine content is not less than the lower limit of the above range, the liquid repellency on the surface of the cured film becomes better. Adhesiveness of a cured film and the layer adjacent to this becomes favorable as it is below the upper limit of the said range.

  The number average molecular weight (Mn) of the polymer (D1) is preferably from 1,000 to 50,000, particularly preferably from 3,000 to 20,000. When the number average molecular weight (Mn) is not less than the lower limit of the above range, the polymer (D1) is sufficiently transferred to the surface of the cured film, so that better liquid repellency can be expressed. When the amount is not more than the upper limit of the above range, the compatibility with the fluororesin (A) in the photosensitive resin composition becomes good, and a cured film having no defects can be formed.

  When the photosensitive resin composition contains the liquid repellent compound (D), the content is 0.1 to 20 with respect to the total (100 parts by mass) of the fluororesin (A) and the compound (B). Part by mass is preferable, and 0.2 to 15 parts by mass is particularly preferable. When the content of the liquid repellent compound (D) is not less than the lower limit of the above range, the effect of improving the liquid repellent property is easily obtained. A film physical property becomes it favorable that it is below the upper limit of the said range.

(Additive (E))
An additive (E) can be mix | blended with the photosensitive resin composition in the range which does not impair the effect of this invention as needed other than the component of said (A)-(D).
Additives (E) include stabilizers such as antioxidants and thermal polymerization inhibitors; adhesion promoters such as coupling agents; surfactants such as leveling agents, antifoaming agents, suspending agents, and dispersing agents. A plasticizer; a thickener and the like, which can be appropriately selected from various additives well known in the coating field.
Among the above, when an adhesion promoter is contained in the photosensitive resin composition, the adhesion between the cured film of the photosensitive resin composition and the layer adjacent thereto (such as the first insulating film 7) is improved. be able to. The adhesion can also be improved by applying an adhesion promoter to the adjacent layer in advance. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.
When the additive (E) is contained in the photosensitive resin composition, the content is 0.0001 to 30 parts by mass with respect to the total (100 parts by mass) of the fluororesin (A) and the compound (B). Is preferable, 0.0001-20 mass parts is more preferable, and 0.0001-10 mass parts is especially preferable.

(solvent)
It is preferable that the photosensitive resin composition further includes a solvent in terms of easy wet application.
The solvent is removed by volatilization after applying the photosensitive resin composition. Therefore, the solvent needs to have a lower boiling point than components other than the solvent in the photosensitive resin composition. Since the compound having the lowest boiling point among the components (A) to (E) is usually the compound (B), when the photosensitive resin composition contains the compound (B), it has a lower boiling point. A solvent is used. On the other hand, as the compound (B), it is preferable to use a compound having a boiling point sufficiently higher than the solvent used.

The fluororesin (A) having a fluorine atom content in the solid content of the photosensitive resin composition of 45% by mass or less is usually dissolved in a non-fluorinated solvent, but not in a fluorinated solvent.
Therefore, when the photosensitive resin composition contains a solvent, a non-fluorinated solvent is used as the solvent.
The non-fluorinated solvent is an organic solvent that does not contain a fluorine atom. Examples of non-fluorinated solvents include ketone solvents, ester solvents, ether solvents, amide solvents, aromatic hydrocarbon solvents, and the like.
Examples of the ketone solvent include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methyl amyl ketone.
Examples of ester solvents include ethyl lactate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Examples include ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), propylene glycol monoethyl ether acetate, and the like.
Examples of ether solvents include tetrahydrofuran, pyran, dioxane, dimethoxyethane, diethoxyethane, diphenyl ether, anisole, phenetole, diglyme, and triglyme.
Examples of the amide solvent include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, and methylnaphthalene.

The solvent contained in the photosensitive resin composition may be one type or two or more types.
The content of the solvent in the photosensitive resin composition is preferably such that the total content of the fluororesin (A) and the compound (B) with respect to the total mass of the photosensitive resin composition is 1 to 60% by mass, An amount of 1 to 50% by mass is particularly preferred.

(Preferred composition)
As the photosensitive resin composition, the solid content is preferably composed of the following fluororesin (A), compound (B), and photopolymerization initiator (C1). The solid content and the non-fluorinated solvent More preferably, the non-fluorinated solvent is at least one selected from the group consisting of PGMEA and cyclohexanone.
Fluororesin (A): Prepolymer (A1-1) (particularly a prepolymer obtained by condensation reaction of perfluorobiphenyl, 1,3,5-trihydroxybenzene and acetoxystyrene in the presence of a deHF agent) . Of the total (100 parts by mass) of the fluororesin (A) and the compound (B), the fluororesin (A) is 40 to 90 parts by mass.
Compound (B): ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,9- At least one selected from the group consisting of nonanediol dimethacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, and tricyclodecane dimethanol diacrylate. Of the total (100 parts by mass) of the fluororesin (A) and the compound (B), the compound (B) is 10 to 60 parts by mass.
Photopolymerization initiator (C1): IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), IRGACURE 369 (manufactured by BASF), IRGACURE 907 (manufactured by BASF), DAROCUR TPO (manufactured by BASF) At least one selected from 3-20 mass parts of photoinitiators (C1) with respect to the sum total (100 mass parts) of a fluororesin (A) and a compound (B).

(Fluorine atom content in solids)
In this invention, the fluorine atom content rate in solid content of the said photosensitive resin composition is 10-45 mass%, 20-45 mass% is preferable and 30-45 mass% is especially preferable.
The surface of the first insulating film 7 having a high liquid repellency (low surface energy) having a water contact angle of 105 ° or more when the fluorine atom content in the solid content of the photosensitive resin composition is 10% by mass or more. In addition, a photosensitive resin film can be formed by a wet coating method directly without surface treatment such as plasma treatment, ozone treatment, or ashing. Moreover, the adhesiveness to the 1st insulating film 7 of the photosensitive resin film formed and the 2nd insulating film 8 obtained by exposing and developing this is also excellent.
When the fluorine atom content is 45% by mass or less, the solid content of the photosensitive resin composition (fluorine resin (A), etc.) tends to be soluble in non-fluorinated solvents and insoluble in fluorine-containing solvents. There is. Therefore, a fluorine-containing solvent is not used as a solvent for the photosensitive resin composition, and a non-fluorine-containing solvent is used.
The high liquid repellency (low surface energy) as described above of the first insulating film 7 is mainly caused by the fluororesin (F), and the fluororesin (F) capable of forming such a high liquid repellency insulating film is They tend to be soluble in fluorine-containing solvents and insoluble in non-fluorinated solvents. Since the photosensitive resin composition does not contain a fluorine-containing solvent as a solvent, it is possible to prevent the first insulating film 7 from being dissolved by the solvent of the photosensitive resin composition when the photosensitive resin composition is applied. It is possible to prevent the organic semiconductor layer 6 from being damaged.

The “solid content of the photosensitive resin composition” in the present invention indicates the total of components other than the solvent in the photosensitive resin composition (amount obtained by removing the mass of the solvent from the total mass of the photosensitive resin composition).
The fluorine atom content in the solid content of the photosensitive resin composition can be determined from the fluorine atom content of each component constituting the solid content of the photosensitive resin composition and the ratio (mass%) in the solid content. . For example, when the solid content of the photosensitive resin composition is composed of the fluororesin (A), the compound (B) and the radical polymerization initiator (C), (fluorine resin (A) fluorine atom content (mass%) × solid content Content (mass%) / 100) + (fluorine atom content of compound (B) (mass%) × solid content (mass%) / 100) + (radical polymerization initiator (C) The value of fluorine atom content (mass%) × content in solid (mass%) / 100) is the fluorine atom content in the solid.

The fluorine atom content in the solid content of the photosensitive resin composition can also be determined by analyzing the cured film (second insulating film 8) of the photosensitive resin composition.
The analysis of the cured film can be performed, for example, by combustion-ion chromatography. In the combustion-ion chromatography method, a sample is burned and decomposed by an automatic combustion device, the generated gas is collected in an absorbing solution, and the absorbing solution is analyzed by ion chromatography, so that the fluorine atoms collected in the absorbing solution are collected. Can be quantified.

[Coating composition]
The coating composition used for forming the first insulating film 7 is a resin composition containing a fluororesin (F) and a fluorinated solvent.

(Fluororesin (F))
<Fluoropolymer (F1)>
The fluoropolymer (F1) is a fluoropolymer having an aliphatic ring structure in the main chain.
The number of atoms constituting the ring skeleton of the aliphatic ring is preferably 4 to 7, and particularly preferably 5 to 6. That is, the aliphatic ring is preferably a 4- to 7-membered ring, particularly preferably a 5- to 6-membered ring.
Examples of the aliphatic ring include a saturated or unsaturated aliphatic hydrocarbon ring, an aliphatic heterocyclic ring in which a part of carbon atoms in the aliphatic hydrocarbon ring is substituted with a hetero atom such as an oxygen atom or a nitrogen atom, A fluorine-containing aliphatic ring in which a hydrogen atom in an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring is substituted with a fluorine atom is preferred.
In particular, the fluorinated polymer (F1) preferably has a fluorinated aliphatic ring or an aliphatic hydrocarbon ring in the main chain.

“The main chain has an aliphatic ring structure” means that at least one of carbon atoms constituting the ring skeleton of the aliphatic ring is a carbon atom constituting the main chain of the fluoropolymer (F1). Means.
In the fluoropolymer (F1), the fluorine atom may be bonded to the carbon atom constituting the main chain, or may be bonded to the side chain. From the viewpoint of obtaining a polymer having a low water absorption and a low dielectric constant, a high dielectric breakdown voltage, and a high volume resistivity, it is preferable to have at least fluorine atoms bonded to carbon atoms constituting the main chain. That is, the fluorine-containing polymer preferably has a fluorine-containing aliphatic ring structure in the main chain.
In particular, since the fluorinated aliphatic ring is a fluorinated aliphatic ring having a heterocyclic structure having 1 to 2 etheric oxygen atoms in the skeleton, it is easy to produce a polymer from a monomer. Is preferable from the viewpoint of easy availability.

The fluoropolymer (F1) may have a reactive functional group.
The “reactive functional group” is bonded by reacting with other components blended between the molecules of the fluoropolymer (F1) or together with the fluoropolymer (F1) when heating or the like is performed. Means a reactive group capable of forming.
For example, when the coating composition contains a silane coupling agent or a polyvalent polar compound together with the fluorine-containing polymer (F1), the fluorine-containing polymer (F1) is a functional group or a polyvalent polarity possessed by the silane coupling agent. You may have the reactive functional group which can react with the polar functional group which a compound has.
Considering the strength of the interaction with the silane coupling agent or the polyvalent polar compound and the ease of introduction into the polymer, the reactive functional group possessed by the fluoropolymer (F1) is a carboxy group, an acid At least one selected from the group consisting of a halide group, an alkoxycarbonyl group, a carbonyloxy group, a carbonate group, a sulfo group, a phosphono group, a hydroxy group, a thiol group, a silanol group and an alkoxysilyl group is preferred, and a carboxy group or an alkoxycarbonyl group Is more preferable.

Preferred fluorine-containing polymers (F1) include the following fluorine-containing cyclic polymers (I) and fluorine-containing cyclic polymers (II).
Fluorine-containing cyclic polymer (I): a polymer having a structural unit based on a cyclic fluorine-containing monomer.
Fluorine-containing cyclic polymer (II): a polymer having a structural unit formed by cyclopolymerization of a diene-based fluorine-containing monomer.
“Cyclic polymer” means a polymer having a cyclic structure.
Hereinafter, the structural unit is also simply referred to as “unit”.

The fluorinated cyclic polymer (I) has units based on “cyclic fluorinated monomer”.
“Cyclic fluorine-containing monomer” means a monomer having a polymerizable double bond between carbon atoms constituting a fluorine-containing aliphatic ring, or a carbon atom constituting a fluorine-containing aliphatic ring and a fluorine-containing fat. It is a monomer having a polymerizable double bond with a carbon atom outside the group ring.
As the cyclic fluorine-containing monomer, the compound (1) represented by the following formula (1) or the compound (2) represented by the following formula (2) is preferable.

［式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｙ^１およびＹ^２は、それぞれ独立に、フッ素原子、酸素原子が介在してもよいペルフルオロアルキル基、または酸素原子が介在してもよいペルフルオロアルコキシ基である。Ｘ^３およびＸ^４は相互に結合して環を形成してもよい。］

[Wherein, X ¹ , X ² , X ³ , X ⁴ , Y ¹ and Y ² are each independently a fluorine atom, a perfluoroalkyl group that may be intervened by an oxygen atom, or an oxygen atom. A good perfluoroalkoxy group. X ³ and X ⁴ may be bonded to each other to form a ring. ]

The perfluoroalkyl group in X ¹ , X ² , X ³ , X ⁴ , Y ¹ and Y ² preferably has 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The perfluoroalkyl group is preferably linear or branched, and particularly preferably linear. Specific examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like, and a trifluoromethyl group is particularly preferable.
Examples of the perfluoroalkoxy group in X ¹ , X ² , X ³ , X ⁴ , Y ¹ and Y ² include those in which an etheric oxygen atom (—O—) is bonded to the perfluoroalkyl group, and a trifluoromethoxy group Is particularly preferred.
When the perfluoroalkyl group or perfluoroalkoxy group has 2 or more carbon atoms, an etheric oxygen atom may be interposed between carbon atoms of the perfluoroalkyl group or perfluoroalkoxy group.

In formula (1), X ¹ is preferably a fluorine atom.
X ² is preferably a fluorine atom, a trifluoromethyl group, or a C 1-4 perfluoroalkoxy group, and particularly preferably a fluorine atom or a trifluoromethoxy group.
X ³ and X ⁴ are each independently preferably a fluorine atom or a C 1-4 perfluoroalkyl group, particularly preferably a fluorine atom or a trifluoromethyl group.
X ³ and X ⁴ may be bonded to each other to form a ring. The number of atoms constituting the ring skeleton of the ring is preferably 4 to 7, and particularly preferably 5 to 6.
Specific examples of compound (1) include compounds (1-1) to (1-5).

In Formula (2), Y ¹ and Y ² are each independently preferably a fluorine atom, a C 1-4 perfluoroalkyl group or a C 1-4 perfluoroalkoxy group, and a fluorine atom or a trifluoromethyl group is preferred. Particularly preferred.
Specific examples of compound (2) include compounds (2-1) to (2-2).

The fluorinated cyclic polymer (I) may be composed only of units formed by the cyclic fluorinated monomer, or may be a copolymer having the units and other units. Good.
However, the proportion of units based on the cyclic fluorinated monomer in the fluorinated cyclic polymer (I) is 20 mol% or more based on the total of all repeating units constituting the fluorinated cyclic polymer (I). Is preferable, 40 mol% or more is more preferable, and 100 mol% may be sufficient.
The other monomer is not particularly limited as long as it is copolymerizable with the cyclic fluorine-containing monomer. Specific examples include diene fluorine-containing monomers, monomers having a reactive functional group in the side chain, tetrafluoroethylene, chlorotrifluoroethylene, perfluoro (methyl vinyl ether), and the like. Examples of the diene-based fluorine-containing monomer include the same as those mentioned in the description of the fluorine-containing cyclic polymer (II) described later. Examples of the monomer having a reactive functional group in the side chain include monomers having a polymerizable double bond and a reactive functional group. The polymerizable double _{bond, CF 2 = CF-, CF 2} = CH-, CH 2 = CF-, CFH = CF-, CFH = CH-, CF 2 = C-, include CF = CF-, etc. . Examples of the reactive functional group include the same functional groups as those described in the explanation of the fluorine-containing cyclic polymer (II) described later.
A polymer obtained by copolymerization of a cyclic fluorine-containing monomer and a diene-based fluorine-containing monomer is considered as a fluorine-containing cyclic polymer (I).

The fluorinated cyclic polymer (II) has units formed by cyclopolymerization of a diene fluorinated monomer.
The “diene fluorine-containing monomer” is a monomer having two polymerizable double bonds and fluorine atoms. Although it does not specifically limit as this polymerizable double bond, A vinyl group, an allyl group, and a (meth) acryloyl group are preferable.
As the diene fluorine-containing monomer, the following compound (3) is preferable.
_{CF 2 = CF-Q-CF} = CF 2 ··· (3).
In formula (3), Q may have an etheric oxygen atom, and a part of fluorine atoms may be substituted with a halogen atom other than fluorine atoms, preferably 1 to 5 carbon atoms, preferably 1 to 1 carbon atoms. 3 is a perfluoroalkylene group which may have a branch. Examples of halogen atoms other than fluorine include chlorine atom and bromine atom.
Q is preferably a perfluoroalkylene group having an etheric oxygen atom. In that case, the etheric oxygen atom in the perfluoroalkylene group may be present at one end of the group, may be present at both ends of the group, and is present between the carbon atoms of the group. It may be. From the viewpoint of cyclopolymerizability, it is preferably present at one end of the group.

Specific examples of the compound (3) include the following compounds.
_{CF 2 = CFOCF 2 CF = CF} 2, CF 2 = CFOCF (CF 3) CF = CF 2, CF 2 = CFOCF 2 CF 2 CF = CF 2, CF 2 = CFOCF 2 CF (CF 3) CF = CF 2, _{CF 2 = CFOCF (CF 3)} CF 2 CF = CF 2, CF 2 = CFOCFClCF 2 CF = CF 2, CF 2 = CFOCCl 2 CF 2 CF = CF 2, CF 2 = CFOCF 2 OCF = CF 2, CF 2 = _{CFOC (CF 3) 2 OCF =} CF 2, CF 2 = CFOCF 2 CF (OCF 3) CF = CF 2, CF 2 = CFCF 2 CF = CF 2, CF 2 = CFCF 2 CF 2 CF = CF 2, CF 2 _{= CFCF 2 OCF 2 CF = CF} 2.

  Examples of the units formed by the cyclopolymerization of the compound (3) include the following units (3-1) to (3-4).

  A commercially available product may be used as the fluoropolymer (F1), and examples thereof include CYTOP (registered trademark, manufactured by Asahi Glass Co., Ltd.).

<Fluoropolymer (F2)>
The fluoropolymer (F2) is a fluororesin having no ring structure in the main chain and having a perfluoroalkyl group in the side chain.
“The main chain does not have a ring structure” means that the carbon atom constituting the main chain of the fluoropolymer (F2) is not the carbon atom constituting the ring skeleton.
Examples of the polymer having no ring structure in the main chain include a polymer formed by polymerization of a compound having one polymerizable double bond. In this case, the main chain of the polymer is a linear hydrocarbon chain formed by a reaction (polymerization) of a polymerizable double bond.

As a perfluoroalkyl group which a fluoropolymer (F2) has in a side chain, a C2-C8 linear or branched perfluoroalkyl group is preferable, and a C4-C6 perfluoroalkyl group is especially preferable. When the carbon number of the perfluoroalkyl group is 2 or more, the liquid repellency is high and the water contact angle of the first insulating film tends to be 105 ° or more. When the number of carbon atoms is 8 or less, when a decomposition product is generated, an adverse effect due to the decomposition product is hardly generated.
The perfluoroalkyl _{group, - (CF 2) 3 CF} 3, -CF 2 CF (CF 3) 2, -C (CF 3) 3, - (CF 2) 4 CF 3, - (CF 2) 2 CF ( _{CF 3) 2, -CF 2 C} (CF 3) 3, -CF (CF 3) CF 2 CF 2 CF 3, - (CF 2) 5 CF 3, - (CF 2) 3 CF (CF 3) 2 , etc. It can be _{mentioned, - (CF 2) 3 CF} 3, - (CF 2) 5 CF 3 is particularly preferred.

Examples of the fluoropolymer (F2) include the following fluoropolymer (III).
Fluoropolymer (III): A polymer having units (f21) derived from the monomer (α1) represented by the following formula (α1).
CH ₂ = CR ¹¹ —C (═O) O—R— ¹² (α1)
[Wherein, R ¹¹ represents a hydrogen atom, a methyl group or a halogen atom, Y represents a divalent aliphatic group having 1 to 4 carbon atoms, and R ¹² represents a linear or branched group having 2 to 8 carbon atoms. Is a perfluoroalkyl group of

As the halogen atom for R ¹¹ , a chlorine atom and a fluorine atom are preferable.
R ¹¹ is preferably a hydrogen atom or a methyl group from the viewpoint of water and oil repellency.
Y is preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably an ethylene group, from the viewpoint of water and oil repellency.
Examples of R ¹² include the same groups as those described as the perfluoroalkyl group that the fluoropolymer (F2) has in the side chain.

Specific examples of the monomer (α1) include, for example, 2-perfluorohexylethyl acrylate (hereinafter referred to as “C6FA”), 2-perfluorohexylethyl methacrylate (hereinafter referred to as “C6FMA”), and 2-perfluorobutyl. Ethyl acrylate, 3,3,4,4,5,5,6,7,7,7-decafluoro-6- (trifluoromethyl) heptyl acrylate, 2-perfluorohexylethyl α-chloroacrylate) (hereinafter “ α-ClC6FA ”) and the like. Of these, C6FA, C6FMA, 3,3,4,4,5,5,6,7,7,7-decafluoro-6- (trifluoromethyl) heptyl acrylate and α are preferred because of their excellent water and oil repellency. -ClC6FA is preferred, C6FA, C6FMA and α-ClC6FA are particularly preferred.
The structural unit (f21) possessed by the fluoropolymer (III) may be one type or two or more types.
The content of the unit (f21) in the fluoropolymer (III) is preferably 70 to 100 mol%, particularly 80 to 100 mol%, based on the total of all units constituting the fluoropolymer (III). preferable.

The fluoropolymer (III) may further have other units (f22) other than the unit (f21).
The unit (f22) is not particularly limited as long as it is derived from the monomer (α2) that can be copolymerized with the monomer (α1) and does not introduce a ring structure into the main chain.
As the monomer (α2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, behenyl (meth) acrylate, phenyl (Meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate monomers such as benzyl methacrylate; aromatic hydrocarbon vinyl such as styrene and 4-hydroxystyrene Monomers; vinyl ether monomers such as t-butyl vinyl ether and cyclohexyl vinyl ether; vinylidene monomers such as 1,1-dichloroethylene and 1,1-difluoroethylene.

From the viewpoint of the heat resistance of the first insulating film 7 to be formed, the unit (f22) preferably has a unit having a ring structure in the side chain. The ring structure may be an aromatic ring or an aliphatic ring.
Examples of the unit (f22) having a ring structure in the side chain include units derived from cyclohexyl (meth) acrylate, styrene, cyclohexyl vinyl ether, and the like.

  As the fluoropolymer (F2), a polymer synthesized by polymerizing the above-described monomers may be used, or a commercially available product may be used.

The mass average molecular weight of the fluororesin (F) is preferably 10,000 or more, and more preferably 30,000 or more. When the mass average molecular weight is 10,000 or more, the first insulating film 7 can be formed satisfactorily. When the mass average molecular weight is 30,000 or more, the heat resistance of the first insulating film 7 is improved.
On the other hand, when the mass average molecular weight is too large, it is difficult to dissolve in a solvent, and there is a possibility that problems such as difficulty in preparing a coating composition and wet coating of the coating composition may occur. Therefore, the mass average molecular weight of the fluororesin (F) is preferably 1 million or less, more preferably 800,000 or less, and further preferably 500,000 or less.
Especially, 100,000-300,000 are especially preferable as a mass mean molecular weight in case a fluororesin (F) is a fluoropolymer (F1). The mass average molecular weight when the fluororesin (F) is a fluoropolymer (F2) is particularly preferably from 50,000 to 200,000.

When the fluororesin (F) is used as a resin for an interlayer insulating film, the relative dielectric constant is preferably 1.8 to 8.0, more preferably 1.8 to 5.0. 8 to 3.0 is particularly preferable. The relative dielectric constant is a value measured at a frequency of 1 MHz in accordance with ASTM D150.
The fluororesin (F) preferably has a high volume resistivity and a high dielectric breakdown voltage. The volume resistivity of the fluororesin (F) is preferably 10 ¹⁰ to 10 ²⁰ Ωcm, particularly preferably 10 ¹⁶ to 10 ¹⁹ Ωcm. The volume resistivity is measured according to ASTM D257. The dielectric breakdown voltage of the fluororesin (F) is preferably 1 to 10 kV / mm, and particularly preferably 3 to 10 kV / mm. The breakdown voltage is measured by a mercury flow bar (product name: SSM-495, manufactured by SSM).
As the fluororesin (F), those having high hydrophobicity are preferable in order to eliminate water that adversely affects the insulating properties and maintain high insulating properties.

(Optional component)
The coating composition may further contain other components other than the fluororesin (F).
Examples of the other components include a silane coupling agent and a polyvalent polar compound. By containing a silane coupling agent or a polyvalent polar compound, it is possible to improve the heat resistance of the first insulating film 7 to be formed, the adhesion to other layers, and the like.

<Silane coupling agent>
As the silane coupling agent, a silane coupling agent having an amino group is preferable. For example, when the fluororesin (F) has a carboxy group, when the silane coupling agent is blended, the carboxy group and the amino group react and the carboxy group disappears. For example, when the silane coupling agent is a compound represented by H ₂ N—L—Si (OR) _n (where L is a linking group), the reaction causes the carboxy group to be —CONH—L—Si (OR). ) _N. Therefore, the fluororesin (F) in the first insulating film does not have a carboxy group.
From the viewpoint of easy availability, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl)- γ-Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) -γ-aminopropyltriethoxysilane are preferred.

  The content of the silane coupling agent is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass with respect to the total amount of the fluororesin (F) and the silane coupling agent. 5-5 mass% is especially preferable. When it is in the above range, it can be uniformly mixed with the fluororesin (F), and when each component is dissolved in a solvent to form a coating composition, phase separation hardly occurs.

<Polyvalent polar compound>
The polyvalent polar compound is a compound having two or more polar functional groups and a molecular weight of 50 to 2,000 (excluding the silane coupling agent).
The “polar functional group” is a functional group having one or both of the following properties (1a) and (1b).
(1a) Two or more types of atoms having different electronegativity are included, and the functional group has polarity due to polarization.
(1b) Polarization is caused by the difference in electronegativity with carbon bonded to the functional group.

Specific examples of the polar functional group having only the above characteristic (1a) include a hydroxyphenyl group.
Specific examples of the polar functional group having only the characteristic (1b) include a primary amino group (—NH ₂ ), a secondary amino group (—NH—), a hydroxy group, and a thiol group.
Specific examples of the polar functional group having both the above characteristics (1a) and (1b) include sulfo group, phosphono group, carboxy group, alkoxycarbonyl group, acid halide group, formyl group, isocyanate group, cyano group, carbonyl group. Examples thereof include an oxy group and a carbonate group.

  Examples of the polyvalent polar compound include pentane-1,5-diamine, hexane-1,6-diamine, cyclohexane-1,2-diamine, cyclohexane-1,3-diamine, cyclohexane-1,4-diamine, and 1,2. -Diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, cyclohexane-1,3,5-triamine , Cyclohexane-1,2,4-triamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 2,4,6-triaminotoluene, 1,3,5-tris (2 -Aminoethyl) benzene, 1,2,4-tris (2-aminoethyl) benzene, 2,4,6-tris (2-aminoethyl) to Ene, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine are more preferred, and tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, cyclohexane-1,3-diamine, hexane-1,6 Particularly preferred are diamines, diethylenetriamine and polyethyleneimine.

  0.01-30 mass% is preferable with respect to content of a fluororesin (F), and, as for content of the polyvalent polar compound in a coating composition, 0.05-10 mass% is especially preferable. When the content is not less than the lower limit of the above range, the effect of blending the polyvalent polar compound is sufficiently obtained, and when it is not more than the upper limit, the compatibility with the fluororesin (F) is excellent.

(solvent)
The coating composition contains a fluorine-containing solvent as a solvent for dissolving the fluororesin (F). The fluorine-containing solvent is an organic solvent containing a fluorine atom.
As the fluorine-containing solvent for dissolving the fluororesin (F), an aprotic fluorine-containing solvent is preferable. The “aprotic fluorinated solvent” is a fluorinated solvent having no proton donating property.
Examples of the aprotic fluorine-containing solvent include polyfluoroaromatic compounds such as 1,4-bis (trifluoromethyl) benzene, polyfluorotrialkylamine compounds such as perfluorotributylamine, and polyfluorocycloalkanes such as perfluorodecalin. A compound, polyfluoro cyclic ether compound such as perfluoro (2-butyltetrahydrofuran), perfluoropolyether, polyfluoroalkane compound, hydrofluoroether (HFE), hydrofluorocarbon (HFC) and the like can be used.

When a silane coupling agent or a polyvalent polar compound is contained, a protic fluorine-containing solvent may be used as a solvent for dissolving them. The “protic fluorine-containing solvent” is a fluorine-containing solvent having proton donating properties.
As the protic fluorine-containing solvent, for example, fluorine-containing alcohol such as 2- (perfluorooctyl) ethanol, fluorine-containing carboxylic acid, amide of fluorine-containing carboxylic acid, fluorine-containing sulfonic acid and the like can be used.

The fluorine-containing solvent of the coating composition is preferably a fluorine-containing solvent having a fluorine atom content of 45% or more because the solubility of the fluororesin (F) is large and a good solvent, and the fluorine atom content is 45%. The above aprotic fluorine-containing solvents are particularly preferable.
The boiling point of the fluorinated solvent is preferably 100 to 200 ° C. If the boiling point of the fluorine-containing solvent is at least the lower limit of the above range, a film having a uniform thickness can be easily formed by wet coating.
The fluorine-containing solvent used for preparing the coating composition preferably has a low water content from the viewpoint of damage to the organic semiconductor layer 6. The water content is preferably 100 ppm by mass or less, particularly preferably 10 ppm by mass or less.

The content of the fluorine-containing solvent in the coating composition can be appropriately set in consideration of the concentration of the fluororesin (F) in the coating composition, the solid content concentration, the fluorine atom content in the solid content, and the like.
The concentration of the fluororesin (F) in the coating composition is preferably 0.1 to 30% by mass, and particularly preferably 0.5 to 20% by mass.
The solid content concentration of the coating composition is usually 0.1 to 30% by mass, and preferably 0.5 to 20% by mass.
The solid content of the coating composition indicates the total of components other than the solvent in the coating composition (amount obtained by removing the mass of the solvent from the total mass of the coating composition). Desired.
Solid content concentration (% by mass) = total mass of components other than solvent / total mass of coating composition × 100

The fluorine atom content in the solid content of the coating composition is preferably 40 to 70 mass%, more preferably 50 to 70 mass%, and particularly preferably 60 to 70 mass%. When the fluorine atom content in the solid content of the coating composition is not less than the lower limit of the above range, the solubility in a fluorine-containing solvent is excellent, and the dielectric constant and water absorption can be reduced. It is excellent in adhesiveness with the photosensitive resin layer as it is below the upper limit of the said range.
The fluorine atom content in the solid content of the coating composition can be determined in the same procedure as the fluorine atom content in the solid content of the photosensitive resin composition.

The coating composition may be obtained by preparing in advance a composition containing each component (fluororesin (F), optional component, solvent) to be contained in the coating composition, and dissolving this in a solvent. May be obtained by dissolving each in a solvent and mixing each solution. As a method for producing the composition in the case of preparing a composition containing each component in advance, the solid and the solid, or the solid and the liquid may be mixed by kneading, eutectic extrusion, etc. Each solution dissolved in may be mixed.
Especially, it is more preferable to mix each solution. For example, when the fluoropolymer (F1) and a silane coupling agent are used in combination, the coating composition is a fluoropolymer (F1) solution in which the fluoropolymer (F1) is dissolved in an aprotic fluorinated solvent. And a silane coupling agent solution in which a silane coupling agent is dissolved in a protic fluorine-containing solvent, and the fluorine-containing polymer (F1) solution and the silane coupling agent solution are mixed. preferable.

[Second Embodiment]
FIG. 2 is a cross-sectional view showing a schematic configuration of the organic transistor element 20 manufactured by the manufacturing method of the second embodiment of the present invention.
The organic transistor element 20 includes a substrate 1, a gate electrode 2, a gate insulating film 23 formed on the gate electrode 2, a source electrode 4 and a drain electrode 5 formed on the gate insulating film 23, and a gate insulating film. An organic semiconductor layer 6 formed between the source electrode 4 and the drain electrode 5, a first insulating film 7 covering the organic semiconductor layer 6, and a second insulating film 8. .
The organic transistor element 20 is the same as the organic transistor element 10 of the first embodiment, except that it has a gate insulating film 23 instead of the gate insulating film 3 in the first embodiment.
In the embodiments described below, the same reference numerals are given to the components corresponding to the first embodiment, and detailed description thereof will be omitted.

The gate insulating film 23 contains a fluororesin (F).
The gate insulating film 23 has a higher fluorine atom content and a lower relative dielectric constant than the gate insulating film 3 in the first embodiment. Therefore, carrier delocalization is unlikely to occur at the interface with the organic semiconductor layer 6, and the carrier mobility tends to increase.

The organic transistor element 20 can be manufactured by the same procedure as that of the organic transistor element 10 of the first embodiment except that the gate insulating film 23 is formed instead of the gate insulating film 3.
The gate insulating film 23 can be formed by a method similar to that for the first insulating film 7.
In the organic transistor element 20, not only the surface of the first insulating film 7 but also the surface of the gate insulating film 23 has a water contact angle of 105 ° or more.
In this case, since it is difficult to form the source electrode 4 and the drain electrode 5 thereon by a wet coating method, the source electrode 4 and the drain electrode 5 can be formed by a dry process such as a sputtering method or a vacuum deposition method. preferable. Similarly, the organic semiconductor layer 6 is preferably formed by a dry process such as a vacuum evaporation method. However, the present invention is not limited to this, and these may be formed by a wet coating method. When the gate insulating film 23 is formed by a wet coating method, surface treatment such as plasma treatment, ozone treatment, or ashing may be performed.

[Third embodiment]
FIG. 3 is a sectional view showing a schematic configuration of the organic transistor element 30 manufactured by the manufacturing method of the third embodiment of the present invention.
The organic transistor element 30 includes a substrate 1, a gate electrode 2, a gate insulating film 31 formed on the gate electrode 2, a source electrode 4 and a drain electrode 5 formed on the gate insulating film 31, and a gate insulating film. 31, the organic semiconductor layer 6 formed between the source electrode 4 and the drain electrode 5, the first insulating film 7 covering the organic semiconductor layer 6, and the first insulating film 7. And a second insulating film 8.
The organic transistor element 30 is the same as the organic transistor element 10 of the first embodiment, except that it has a gate insulating film 31 instead of the gate insulating film 3 in the first embodiment.

The gate insulating film 31 includes a lower layer 32 in contact with the gate electrode 2 and an upper layer 33 provided on the lower layer 32.
The lower layer 32 consists of a cured film obtained by curing a curable composition containing a fluororesin (A) having a crosslinkable group and a radical polymerization initiator (C).
The upper layer 33 contains a fluororesin (F).
The upper layer 33 has a higher fluorine atom content and a lower dielectric constant than the lower layer 32. Since the portion in contact with the source electrode 4, the drain electrode 5, and the organic semiconductor layer 6 is the upper layer 33, similarly to the second embodiment, carrier delocalization hardly occurs at the interface with the organic semiconductor layer 6. There is a tendency for mobility to increase. In addition, the lower layer 32 is advantageous in that the withstand voltage can be increased.

  The organic transistor element 30 can be manufactured in the same procedure as the manufacture of the organic transistor element 20 of the second embodiment, except that the lower layer 32 is formed before the gate insulating film 31 (upper layer 33) is formed. The lower layer 32 can be formed in the same procedure as the formation of the gate insulating film 3 of the first embodiment.

[Fourth embodiment]
FIG. 4 is a cross-sectional view showing a schematic configuration of an organic transistor element 40 manufactured by the manufacturing method of the fourth embodiment of the present invention.
The organic transistor element 40 includes a substrate 1, a gate electrode 2, a gate insulating film 3 formed on the gate electrode 2, a source electrode 4 and a drain electrode 5 formed on the gate insulating film 3, and a gate insulating film. 3, the organic semiconductor layer 6 formed between the source electrode 4 and the drain electrode 5, the first insulating film 47 covering the organic semiconductor layer 6, and the first insulating film 47. And a second insulating film 48.
The organic transistor element 40 is the first embodiment except that the organic transistor element 40 includes a first insulating film 47 and a second insulating film 48 instead of the first insulating film 7 and the second insulating film 8 in the first embodiment. This is the same as the organic transistor element 10.

The first insulating film 47 contains a fluororesin (F) and is formed on the substrate 1 so as to cover the gate electrode 2, the gate insulating film 3, the source electrode 4, the drain electrode 5, and the organic semiconductor layer 6. Yes.
The second insulating film 48 is composed of a cured film obtained by curing a curable composition containing a fluororesin (A) having a crosslinkable group and a radical polymerization initiator (C). The first insulating film It is provided on the upper surface of 47 and is in contact with only the first insulating film 47.
The hole 9 penetrates not only the second insulating film 48 but also the first insulating film 47.

The organic transistor element 40 extends to the second insulating film 8 (second insulating film 48) in the same manner as in the manufacture of the organic transistor element 10 of the first embodiment except that the range in which the first insulating film 7 is provided is changed. After the formation, the first insulating film 7 can be etched using the second insulating film 8 as a mask to form holes 9 in the first insulating film 7 (the first insulating film 47 is formed). .
The first insulating film 7 can be etched by a method such as dry etching using oxygen plasma or wet etching using a fluorine-containing solvent.

Although the present invention has been described with reference to the first to fourth embodiments, the present invention is not limited to these embodiments. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, in the first to fourth embodiments, an example of manufacturing a so-called bottom gate / top contact type organic transistor element has been shown. However, the manufacturing method of the present invention includes a bottom gate / bottom contact type and a top gate / bottom contact. The present invention can also be applied to the manufacture of a type or top gate / top contact type organic transistor element.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Examples 1 to 7 and 11 are examples, and examples 8 to 10 are comparative examples.
The materials and measurement / evaluation methods used in each example are shown below.

[Materials used]
(Material for forming first insulating film)
Coating composition (1-1): Cytop CTL-809M (product name, manufactured by Asahi Glass Co., Ltd., formed by cyclopolymerization of perfluorobutenyl vinyl ether (CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ ), main chain A solution in which a fluorine-containing cyclic polymer having -CONH-L-Si (OR) _n at the terminal is dissolved in perfluorotributylamine at a concentration of 9% by mass).
Composition for coating (1-2): Cytop CTL-809A (product name, manufactured by Asahi Glass Co., Ltd. Concentration of fluorine-containing cyclic polymer formed by cyclopolymerization of perfluorobutenyl vinyl ether and having —COOH at the end of the main chain) 9% by weight solution in perfluorotributylamine).
Coating composition (1-3): Cytop CTL-810S (product name, manufactured by Asahi Glass Co., Ltd.) Fluorocyclic cyclic polymer formed by cyclopolymerization of perfluorobutenyl vinyl ether and having —CF ₃ at the main chain terminal A solution dissolved in perfluorotributylamine at a concentration of 10% by mass).
Coating composition (1-4): obtained by dissolving a powdery compound (F2-1) produced by the following procedure in 9% by mass in perfluorotributylamine and filtering with a 0.2 μm pore PTFE filter. Compound (F2-1) solution.

<Production of Compound (F2-1)>
Fluoroacrylate (CH ₂ = CHCOOCH ₂ CH ₂ C _n F _{2n + 1} , n is 6 on average) (5 g), 1,1,2-trifluorotrichloroethane (68 g) and azoisobutyronitrile (0.52 g) withstand pressure Placed in a glass ampoule. After the inside of the system was replaced with nitrogen three times, polymerization was carried out at 60 ° C. for 15 hours. The reaction solution was poured into methanol for reprecipitation purification and dried under reduced pressure to obtain 2.2 g of a powdery compound (F2-1) (polymer having a polyfluoroalkyl group). The number average molecular weight (Mn) of the compound (F2-1) was 10,000.

(Material for forming second insulating film)
<Compound (A)>
Compound (A1-1): A fluorine-containing polyarylene ether prepolymer produced by the following procedure.
Perfluorobiphenyl (PFB) (650 g) and 1,3,5-trihydroxybenzene (120 g) in the presence of potassium carbonate (570 g) in N, N-dimethylacetamide (DMAc) (6.2 kg) solvent. After reacting at 40 ° C. for 6 hours, 4-acetoxystyrene (200 g) was subsequently reacted in the presence of a 48 mass% potassium hydroxide aqueous solution (530 g) to obtain compound (A1-1). The DMAc solution of the compound (A1-1) was poured into a hydrochloric acid aqueous solution (3.5% by mass aqueous solution) for purification by reprecipitation, followed by vacuum drying to obtain 800 g of a powdery compound (A1-1). The number average molecular weight (Mn) of the compound (A1-1) was 10,000.

<Compound (B)>
ADCP: product name, manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate (number average molecular weight (Mn): 304).
ATMPT: Product name, manufactured by Shin-Nakamura Chemical Co., Ltd., trimethylolpropane triacrylate (number average molecular weight (Mn): 296).

<Radical polymerization initiator (C)>
OXE01: product name, manufactured by BASF, 1,2-octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime)].

<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate.

[Measurement and evaluation method]
(Number average molecular weight)
The number average molecular weight (Mn) was measured by gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample with a known molecular weight (polystyrene conversion).

(Water contact angle)
Using a contact angle meter CAA (product name) manufactured by Kyowa Interface Science Co., Ltd., about 1 μL of water was dropped on a horizontally disposed cured film under the condition of 25 ° C., and the contact angle of water was measured.

(Relative permittivity)
The relative dielectric constant of 1 MHz was determined by performing CV (capacitance-voltage) measurement using a mercury flow bar (product name: SSM-495, manufactured by SSM).

(Withstand voltage)
Using a mercury flow bar (manufactured by SSM, product name: SSM-495), IV (current-voltage) measurement was performed to determine the voltage at which dielectric breakdown occurred.

(Film thickness measurement)
A value obtained by using a stylus type surface shape measuring apparatus (product name: DEKTAK3ST, manufactured by Veeco) was used.

[Example 1]
(Production and evaluation of first insulating film)
The coating composition shown in Table 1 was spin coated on a Si substrate having a diameter of about 15.24 cm (6 inches) at 3,000 rpm for 30 seconds and heated on a hot plate at 100 ° C. for 120 seconds. Subsequently, heating was performed at 160 ° C. for 1 hour in an oven under a nitrogen atmosphere to obtain a cured film having a thickness of 1 μm. The water contact angle, relative dielectric constant, and withstand voltage of the cured film (first insulating film) were measured and shown in Table 1.

(Manufacture of second insulating film and evaluation of relative dielectric constant and withstand voltage)
Next, compound (A1-1) (3.8 g), PGMEA (10.6 g), and OXE01 (0.3 g) were placed in a sample bottle to obtain a solution-like photosensitive resin composition.
The photosensitive resin composition is spin-coated on the first insulating film (on the side opposite to the substrate) at 1,000 rpm for 30 seconds, and heated on a hot plate at 60 ° C. for 90 seconds to photosensitive resin. A film was formed. Next, the entire surface of the photosensitive resin film was exposed so that the exposure energy was 600 mJ / cm ² to obtain a cured film having a thickness of 1 μm. The relative dielectric constant and withstand voltage of the cured film (second insulating film) were measured and shown in Table 1.

(Manufacture of second insulating film and evaluation of adhesion to first insulating film)
Separately, the photosensitive resin composition is spin-coated on the surface of the first insulating film opposite to the base material at 1,000 rpm for 30 seconds, and heated on a hot plate at 60 ° C. for 90 seconds to be photosensitive. A functional resin film was formed. Next, the photosensitive resin film is exposed through a mask (a cylindrical isolated hole pattern having a diameter of 30 μm, a mask in which a line and space pattern having a space width of 30 μm is cut) using a high-pressure mercury lamp as a light source. It exposed so that energy might be 600 mJ / cm < ² >, and hardened a part (exposed part) of the photosensitive resin film.
Next, the photosensitive resin film was subjected to paddle development for 20 seconds and PGMEA rinse for 30 seconds using PGMEA as a developer to obtain a second insulating film. Thereafter, in order to remove the developer and the rinsing solution, spin drying was performed at 2,000 rpm for 30 seconds, and heating was performed on a hot plate at 100 ° C. for 90 seconds. The thickness of the second insulating film in the portion that was not removed by development was 1 μm.
The second insulating film was observed with a microscope (manufactured by KEYENCE, product name: VHX DIGITAL MICROSCOPE), and the adhesion of the second insulating film to the first insulating film was evaluated according to the following criteria. Table 1 It was shown to.
○ (good): The second insulating film was not peeled off during development, and a fine pattern (the cylindrical isolated hole pattern and line and space pattern) was confirmed on the second insulating film.
X (defect): The second insulating film was peeled off during development, and a fine pattern could not be confirmed.

[Examples 2 to 4 and Examples 8 to 10]
In the same manner as in Example 1 except that the compounds shown in the compound (A) column and the compound (B) column of Table 1 were used instead of the compound (A) (3.8 g), a solution-like photosensitive resin composition was used. Got. The compounding amount shown in Table 1 is the ratio (mass%) of each compound when the total of the compound (A) and the compound (B) is 100 mass%. The total of compound (A) and compound (B) was 3.8 g.
(Production of second insulating film and evaluation of relative dielectric constant and withstand voltage), and (first evaluation), except that the obtained photosensitive resin composition was used for forming the second insulating film. 2) and evaluation of adhesion to the first insulating film). The results are shown in Table 1. Since the contact angle of water, the relative dielectric constant, and the withstand voltage of the first insulating film are the same as those in Example 1, the measurement was omitted.

[Examples 5 and 7]
The coating composition described in Table 1 was spin-coated on a Si substrate having a diameter of about 15.24 cm for 30 seconds at 1,000 revolutions per minute, heated on a hot plate at 100 ° C. for 120 seconds, and then nitrogen. Heating was performed at 160 ° C. for 1 hour in an oven under an atmosphere to obtain a cured film having a thickness of 1 μm. The water contact angle, relative dielectric constant, and withstand voltage of the cured film (first insulating film) were measured and shown in Table 1.
A second insulating film was formed on the obtained cured film in the same manner as in Example 2, and the adhesion to the first insulating film was evaluated. The results are shown in Table 1. Note that the relative dielectric constant and the withstand voltage of the second insulating film were the same as in Example 2, and thus the measurement was omitted.

[Example 6]
The surface of the Si base material having a diameter of about 15.24 cm was treated with an adhesion promoter (KBE903 (product name, 3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.), and this treatment was performed on the Si substrate. This was carried out by spin-coating an agent in a mixed solvent of ethanol and pure water (solution diluted to 0.05% by mass with 95: 5 (mass ratio)) at 5,000 rpm for 20 seconds.
Next, a cured film having a thickness of 1 μm was obtained in the same manner as in Example 1 except that the coating composition shown in Table 1 was used on the surface of the Si substrate treated with the adhesion promoter. The water contact angle, relative dielectric constant, and withstand voltage of the cured film (first insulating film) were measured and shown in Table 1.
A second insulating film was formed on the obtained cured film in the same manner as in Example 2, and the adhesion to the first insulating film was evaluated. The results are shown in Table 1. Note that the relative dielectric constant and the withstand voltage of the second insulating film were the same as in Example 2, and thus the measurement was omitted.

As shown in the above results, in Examples 1 to 7 where a photosensitive resin composition having a fluorine-containing atom content of 10 to 45% by mass in the solid content was used as the material for forming the second insulating film, the surface water A photosensitive resin film could be formed on the first insulating film having a contact angle of 105 ° or more by a wet coating method. In addition, the cured film obtained by curing the photosensitive resin film by exposure is excellent in adhesion to the first insulating film, and does not peel off from the first insulating film during development, and the second insulating film having a fine pattern is a problem. It was possible to form without.
On the other hand, in Examples 8 to 10 where a photosensitive resin composition having a fluorine-containing atomic ratio of 8.2% or 0% as a material for forming the second insulating film was used, the photosensitivity by the wet coating method was used. Although a resin film could be formed, a cured film obtained by curing the photosensitive resin film by exposure was peeled off from the first insulating film during development.

[Example 11]
An organic thin film transistor element having the same configuration as that of the organic transistor element 20 shown in FIG. 2 was manufactured by the following procedure.
On the glass substrate, 30 nm of Al (aluminum) was deposited to form a gate electrode. Next, the coating composition (1-1) was spin-coated at 1,000 rpm for 30 seconds, heated on a hot plate at 90 ° C. for 10 minutes and 150 ° C. for 30 minutes, and a gate insulating film having a thickness of 200 nm Formed. Next, on the gate insulating film, pentacene as an organic semiconductor was formed to a thickness of 30 nm by a vacuum deposition method to form an organic semiconductor layer. Furthermore, Au (gold) was deposited to a thickness of 50 nm by a vacuum vapor deposition method through a metal mask to form a source electrode and a drain electrode. The gate width was 1 mm and the gate length was 50 μm. Next, the coating composition (1-1) is spin-coated on the organic semiconductor layer at 1,000 rpm for 30 seconds, and heated on a hot plate at 90 ° C. for 10 minutes and 150 ° C. for 30 minutes. A first insulating film (an organic semiconductor sealing layer) was formed. On the 1st insulating film, the 2nd insulating film was formed like Example 2, and the organic thin-film transistor element was manufactured.

About the obtained organic thin-film transistor element, the voltage-current characteristic was measured at room temperature (20-25 degreeC) in nitrogen. At this time, the mobility (μ) was 0.10 cm ² / Vs and the dark value voltage (V _TH ) was −11 V, which showed sufficiently excellent characteristics as a transistor.
The mobility (μ) is a value calculated by the following method.

The drain current (I _D ) is expressed by the following formula (1), and the following formula (2) is obtained by modifying the formula (1). From this equation, the mobility (μ) of the organic semiconductor can be obtained from the slope of the graph when the square root of the absolute value of the drain current (I _D ) is plotted on the vertical axis and the gate voltage (V _G ) is plotted on the horizontal axis. it can.
_{I D = W × C × μ} × (V G -V TH) 2 / (2 × L) ... (1)
μ = ((2 × L) / (W × C)) × (I D / ((V G -V TH) 2) = ((2 × L) / (W × C)) × α 2 ... (2 )
Where W is the channel width of the transistor, C is the capacitance of the gate insulating film, L is the gate length of the transistor, V _G is the gate voltage, V _TH is the dark voltage, α is the drain current ( _ID absolute value and the vertical axis the square root of) shows the slope of the graph when plotted on the horizontal axis of the gate voltage (V _G).)

The organic transistor element manufactured by the manufacturing method of the present invention has advantages such as a simple manufacturing process and less damage to the organic semiconductor layer in the manufacturing process.
The organic transistor element manufactured by the manufacturing method of the present invention is used as an organic thin film transistor (TFT) element, a field effect transistor (FET) element, and the like for electronic devices such as liquid crystal televisions, organic EL televisions, electronic paper, and RF-IDs. be able to.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Gate electrode 3 Gate insulating film 4 Source electrode 5 Drain electrode 6 Organic semiconductor layer 7 First insulating film 8 Second insulating film 9 Hole 10 Organic transistor element 20 Organic transistor element 30 Organic transistor element 40 Organic transistor element

Claims (7)

A method for producing an organic transistor element having a gate electrode, a source electrode, a drain electrode, and an organic semiconductor layer on a substrate,
On the first insulating film covering the organic semiconductor layer,
Applying a photosensitive resin composition to form a photosensitive resin film at least partially in contact with the first insulating film;
A step of partially exposing and developing the photosensitive resin film to form a second insulating film,
The first insulating film contains a fluororesin (F), and the water contact angle of the surface of the first insulating film is 105 ° or more;
The said photosensitive resin composition contains the fluororesin (A) which has a crosslinkable group, and a radical polymerization initiator (C), and the fluorine atom content rate in solid content of this photosensitive resin composition is 10-45. The manufacturing method of the organic transistor element characterized by the above-mentioned.   The method for producing an organic transistor element according to claim 1, wherein the photosensitive resin composition further contains a non-fluorinated solvent.   The manufacturing method of the organic transistor element of Claim 1 or 2 with which the said photosensitive resin composition further contains the compound (B) which has a 2 or more crosslinkable functional group, and does not have a fluorine atom.   The manufacturing method of the organic transistor element as described in any one of Claims 1-3 whose said fluororesin (A) is a fluorine-containing polyarylene prepolymer.   The fluororesin (F) is a fluoropolymer (F1) having an aliphatic ring structure in the main chain, and a fluoropolymer (F2) having no ring structure in the main chain and having a perfluoroalkyl group in the side chain. The method for producing an organic transistor element according to any one of claims 1 to 4, comprising any one or both of   The organic transistor element according to claim 1, wherein the first insulating film is a film formed from a resin composition containing the fluororesin (F) and a fluorine-containing solvent. Manufacturing method.   The electronic device which has an organic transistor element obtained with the manufacturing method as described in any one of Claims 1-6.

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