JP2013077521A - Substrate for electromagnetic wave detachable flexible device and method of manufacturing electronic element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for an electromagnetic wave detachable flexible device that allows an electronic element part to be stably formed.SOLUTION: A substrate for an electromagnetic wave detachable flexible device includes: a metal base having flexibility; an insulating layer formed on at least one surface of the metal base; and an electromagnetic wave detachable adhesive layer that is formed on the other surface of the metal base and contains an electromagnetic wave detachable adhesive resin having electromagnetic wave detachability.

Description

  The present invention relates to an electromagnetic wave releasable flexible device substrate capable of stably forming an electronic element portion.

Electronic element portions such as organic electroluminescence elements (hereinafter, electroluminescence may be referred to as EL) and thin film transistors (hereinafter, thin film transistors may be referred to as TFTs) have low resistance to moisture, and element characteristics depend on moisture. Decreases.
As a technique for suppressing deterioration in element characteristics due to moisture, a technique for preventing moisture from entering the element from the outside, such as sealing the element with a sealing member or a sealing structure, is the mainstream. At this time, a base material having gas barrier properties is used.

As the substrate having gas barrier properties, a glass substrate, a plastic film provided with gas barrier properties, a metal substrate, or the like is used.
A glass substrate is excellent in smoothness and heat resistance, but lacks flexibility, is unsuitable for thinning and weight reduction, and has a disadvantage that it is inferior in impact resistance.
Since a plastic film is generally inferior to a glass or metal in gas barrier properties, it is necessary to impart gas barrier properties in order to prevent moisture from entering. A plastic film with gas barrier properties has the advantages of flexibility, light weight, and impact resistance, but it is not sufficient in heat resistance and has a large coefficient of linear thermal expansion. There is a disadvantage that it is inferior and has high hygroscopicity.
On the other hand, as for the metal base material, various types of metal types and thicknesses are available and can be appropriately selected, and can satisfy heat resistance, light weight, and flexibility. However, since the metal substrate tends to be inferior in surface flatness to the glass substrate and has conductivity, it is insulated to produce an electronic element part such as an organic EL element or TFT on the metal substrate. It is necessary to provide a layer. For example, Patent Document 1 proposes a metal substrate having an insulating layer formed on the surface.

By the way, the electronic element part formed on such a base material is produced by forming the several member which comprises an organic electroluminescent element and a thin-film transistor in pattern shape.
However, when a base material having flexibility is used when forming such a member, the electronic element portion cannot be stably formed due to deformation of the base material during the formation of the electronic element portion. There was a problem that there was.

JP 2000-324368 A

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide an electromagnetic wave releasable flexible device substrate capable of stably forming an electronic element portion.

  In order to solve the above problems, the present invention provides a flexible metal substrate, an insulating layer formed on at least one surface of the metal substrate, and the other surface of the metal substrate. An electromagnetic wave releasable pressure-sensitive adhesive layer comprising an electromagnetic wave releasable pressure-sensitive adhesive resin formed and having an electromagnetic wave releasability is provided.

According to the present invention, since the electromagnetic wave peelable pressure-sensitive adhesive layer (hereinafter sometimes referred to simply as an adhesive layer) has adhesiveness and electromagnetic wave peelability, for example, by bonding the pressure-sensitive adhesive layer to a support substrate, Even when the metal substrate has flexibility, an electronic element portion such as an organic EL or a TFT can be stably formed on the insulating layer.
In addition, by using an electromagnetic wave peeling adhesive layer for the above adhesive layer, it is possible to reduce the adhesive strength by electromagnetic wave irradiation at the time of peeling, so it takes up the flexible device part at the time of peeling compared to a normal pressure sensitive adhesive. Stress can be reduced, damage to the element can be reduced, and handling properties can be improved.
Furthermore, when using a heat-peelable adhesive layer, it is difficult to apply a process at a temperature higher than the peeling temperature, and it is necessary to heat at the time of peeling. Can be small.

  In the present invention, the electromagnetic wave peelable adhesive resin includes any one of an acrylic pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyimide pressure-sensitive adhesive, an electromagnetic wave polymerizable monomer or an electromagnetic wave polymerizable oligomer, and an electromagnetic wave polymerization initiator. It is preferable. This is because the adhesiveness to the metal base material and the support substrate and the peelability from the adherend (metal base material and support substrate) after exposure are excellent, so that the handling property can be further improved.

  In the present invention, it is preferable that the 1% weight loss temperature of the electromagnetic wave peelable adhesive resin is 200 ° C. or higher. Decrease in adhesiveness to the metal substrate and support substrate and peelability from the adherend after exposure, even when heated when forming an electronic element such as an organic EL or TFT on the insulating layer It is because it can suppress.

  In the present invention, the insulating layer preferably contains a polyimide resin. It is because it can be excellent in heat resistance and insulation.

  In the present invention, the polyimide resin preferably has a repeating unit represented by the following general formula (1). It is because it can be made more excellent in heat resistance and insulation.

(In Formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, and R ¹ and R ² that are repeated may be the same or different. n is a natural number of 1 or more.)

  In this invention, it is preferable that the peeling film is formed on the surface of the said electromagnetic wave peelable adhesion layer. It is because it can be excellent in handling property.

  In the present invention, a support substrate is preferably bonded to the electromagnetic wave releasable adhesive layer. This is because even when the metal substrate has flexibility, an electronic element portion such as an organic EL or a TFT can be stably formed on the insulating layer.

  The present invention is a method of manufacturing an electronic device having a flexible metal substrate, an insulating layer formed on the metal substrate, and an electronic device portion formed on the insulating layer, A preparation process for preparing an electromagnetic wave releasable flexible device substrate having a support substrate on the electromagnetic wave releasable adhesive layer, and an electronic element part forming process for forming an electronic element part on the insulating layer of the electromagnetic wave releasable flexible device substrate And an electromagnetic wave irradiation step of irradiating the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate having the electronic element part, and the support substrate from the electromagnetic wave peelable flexible device substrate after the electromagnetic wave irradiation step. There is provided a method for manufacturing an electronic device, comprising: a peeling step for peeling.

According to the present invention, by using the above-mentioned substrate for electromagnetic wave peelable flexible device as the substrate for forming the above electronic element portion, the above-mentioned electronic element portion forming step can be performed in a stable state of the above electromagnetic wave peelable flexible device substrate. It can be carried out. For this reason, the said electronic element part can be formed stably.
Moreover, since an electronic element can be taken out easily by performing an electromagnetic wave irradiation process, it can be excellent in handling property.

  In this invention, the said preparatory process is what bonds a support substrate on the electromagnetic wave peelable adhesive layer of the said substrate for electromagnetic wave peelable flexible devices, or on the said metal base material and the said metal base material An insulating laminate having an insulating layer formed and an electromagnetic wave peelable support substrate having an electromagnetic wave peelable adhesive layer formed on the support substrate and the support substrate, and a metal contained in the insulating laminate It is preferable that a base material and the electromagnetic wave peelable adhesive layer contained in the said electromagnetic wave peelable support substrate are bonded together. This is because an electromagnetic wave releasable flexible device substrate having a support substrate can be stably formed on the electromagnetic wave releasable pressure-sensitive adhesive layer.

In the present invention, the electronic element portion is formed on the back electrode layer formed on the insulating layer, the EL layer formed on the back electrode layer and including at least the organic light emitting layer, and the EL layer. It is preferable that the organic EL device has a transparent electrode layer.
Since the electromagnetic wave peelable adhesive layer can be easily peeled by performing an electromagnetic wave irradiation process, for example, compared with a case where a heat peelable adhesive layer containing a heat peelable resin that is cured by heating is used. Since the electronic element portion can be exposed to a high temperature without any problems such as thermal deterioration, the EL element can be prevented from being exposed to a high temperature. As a result, it is possible to prevent the EL layer from being deteriorated by heat, causing unevenness in luminance and shortening of the element lifetime.
Moreover, since the heat | fever at the time of light emission of an organic EL element can be discharge | released through a metal base material, it is because the said EL element can make a thing with little deterioration by a heat | fever.

In the present invention, the electronic element part is preferably a thin film transistor formed on the insulating layer.
Since the electromagnetic wave peelable adhesive layer can be easily peeled by performing an electromagnetic wave irradiation process, for example, compared with a case where a heat peelable adhesive layer containing a heat peelable resin that is cured by heating is used. This is because the electronic element portion can be exposed to a high temperature and can be free from defects such as thermal degradation, so that it is possible to prevent the TFT from thermal degradation and deterioration of transistor characteristics.

  The present invention has an effect of providing an electromagnetic wave peelable flexible device substrate capable of stably forming an electronic element portion.

It is a schematic sectional drawing which shows an example of the board | substrate for electromagnetic wave peelable flexible devices of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for electromagnetic wave peelable flexible devices of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for electromagnetic wave peelable flexible devices of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for electromagnetic wave peelable flexible devices of this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for electromagnetic wave peelable flexible devices of this invention. It is process drawing which shows an example of the manufacturing method of the electronic device of this invention. It is a schematic sectional drawing which shows an example of the electronic element part used for this invention. It is a schematic sectional drawing which shows the other example of the electronic element part used for this invention. It is a schematic sectional drawing which shows the other example of the electronic element part used for this invention. It is a schematic sectional drawing which shows the other example of the electronic element part used for this invention.

The present invention relates to an electromagnetic wave releasable flexible device substrate and a method for producing an electronic element using the same.
Hereinafter, the manufacturing method of the board | substrate for electromagnetic wave peelable flexible devices and electronic element of this invention is demonstrated in detail.

A. Electromagnetic wave peelable flexible device substrate The electromagnetic wave peelable flexible device substrate of the present invention comprises a flexible metal base, an insulating layer formed on at least one surface of the metal base, and the metal base. And an electromagnetic wave releasable pressure-sensitive adhesive layer formed on the other surface of the material and having electromagnetic wave releasability.

  Such an electromagnetic wave peelable flexible device substrate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a substrate for an electromagnetic wave peelable flexible device of the present invention. As illustrated in FIG. 1, an electromagnetic wave releasable flexible device substrate 10 of the present invention includes a metal substrate 1, an insulating layer 2 formed on one surface of the metal substrate 1, and the metal substrate. And the electromagnetic wave releasable pressure-sensitive adhesive layer 3 formed on the other surface of 1 and having electromagnetic wave releasability.

According to the present invention, since the adhesive layer has adhesiveness and electromagnetic wave releasability, for example, by bonding the adhesive layer to a support substrate, a metal base material used for the electromagnetic wave releasable flexible device substrate is acceptable. Even when it has flexibility, when the said electronic element part is formed, it can prevent that the said metal base material and an insulating layer deform | transform.
Therefore, electronic element parts such as organic EL and TFT can be stably formed on the insulating layer.
In addition, since it loses its adhesiveness only by electromagnetic wave irradiation and can be easily peeled off, it does not require the use of a solution for dissolving the above adhesive layer or a large force for peeling off, and at the time of peeling It is possible to reduce the stress applied to the flexible device portion, and it is possible to reduce damage to the element and to have excellent handling properties.
Furthermore, when using a heat-peelable adhesive layer, it is difficult to apply a process having a temperature higher than the peeling temperature, but the application process can be widened and a heating step at the time of peeling is not required. It is possible to reduce the damage to the device.
Furthermore, since the use of a solution or the like that dissolves the adhesive layer can be made unnecessary, problems such as deterioration of the electronic element portion due to the solution can be prevented.
In addition, since the metal substrate generally has an electromagnetic wave shielding property, for example, after the electronic element portion is formed on the insulating layer, the electronic element is irradiated with electromagnetic waves from the electromagnetic wave peelable adhesive layer side of the metal substrate. The influence of electromagnetic waves on the part can be prevented. In addition, a process involving electromagnetic wave irradiation, such as patterning by photolithography, can be applied to the surface opposite to the surface on which the electromagnetic wave releasable adhesive layer of the metal substrate is formed.
For this reason, a high-quality electronic element portion can be formed stably and with good handling properties.

The board | substrate for electromagnetic wave peelable flexible devices of this invention has a metal base material, an insulating layer, and an electromagnetic wave peelable adhesion layer at least.
Hereinafter, each structure of the board | substrate for electromagnetic wave peelable flexible devices of this invention is demonstrated in detail.

1. Electromagnetic wave peelable adhesive layer The electromagnetic wave peelable adhesive layer used in the present invention is formed on the other surface of the metal substrate and contains an electromagnetic wave peelable adhesive resin having electromagnetic wave peelability.
Here, the electromagnetic wave peeling adhesiveness indicates a property that has adhesiveness before electromagnetic wave irradiation and is cured and easily peelable after electromagnetic wave irradiation.

(1) Electromagnetic wave peelable adhesive layer The adhesiveness to the metal base material and the support substrate before the electromagnetic wave irradiation of the electromagnetic wave peelable adhesive layer used in the present invention is stably bonded to the metal base material and the support substrate. Although it will not specifically limit if it can fix, Specifically, it is preferable that the adhesive force with respect to the said metal base material and a support substrate is 0.5 N / 25mm or more, especially 1.0 N / More preferably, it is 25 mm or more. It is because the said support substrate and a metal base material can be stably fixed because the said adhesive force is the said range.
In addition, the said adhesive force can be calculated | required by measuring to 180 degree peeling adhesive force, sticking to the sample of 25 mm width by the method based on JISZ0237.
Moreover, about the upper limit of the said adhesive force, since it is so preferable that it is high, it is not specifically limited.

  The adhesiveness of the electromagnetic wave releasable pressure-sensitive adhesive layer used in the present invention to the metal substrate after irradiation with electromagnetic waves is not particularly limited as long as it can be easily peeled off from the metal substrate by electromagnetic wave irradiation. Specifically, the adhesive force to the metal base material or the support substrate is preferably 0.4 N / 25 mm or less, and more preferably 0.2 N / 25 mm or less. Moreover, it is preferable that especially the adhesive force with respect to the said metal base material and a support substrate is 0.4 N / 25mm or less, and it is preferable that it is 0.2 N / 25mm or less especially. It is because it can peel easily from the said adherend and can make it excellent in handling property because the said adhesive force exists in the above-mentioned range. Moreover, it is because the electromagnetic wave peelable adhesive layer can be prevented from remaining on the adherend.

  The thickness of the electromagnetic wave releasable adhesive layer used in the present invention is not particularly limited as long as it can be stably bonded and fixed to the metal substrate and the supporting substrate and can be easily peeled off by electromagnetic wave irradiation. However, it is different depending on the material constituting the electromagnetic wave releasable pressure-sensitive adhesive layer, for example, preferably within a range of 3 μm to 50 μm, and more preferably within a range of 5 μm to 30 μm. . This is because when the film thickness is within the above range, the metal base material can be smoothly bonded and fixed to the support substrate.

The location where the electromagnetic wave releasable adhesive layer used in the present invention is formed is particularly limited as long as it can be stably bonded and fixed to the support substrate and can be easily peeled off by electromagnetic wave irradiation. For example, it can be the entire surface of the metal substrate or a part of the surface of the metal substrate.
In the present invention, the formation location of the electromagnetic wave peelable adhesive layer is preferably 50% or more of the surface of the metal substrate, more preferably 80% or more, and 90% or more. Is particularly preferred. This is because the metal base material can be bonded and fixed smoothly and stably to the support substrate.

The method for forming the electromagnetic wave releasable pressure-sensitive adhesive layer used in the present invention is not particularly limited as long as it is a method capable of obtaining an electromagnetic wave releasable pressure-sensitive adhesive layer having good smoothness. A method of applying the coating solution for forming an electromagnetic wave-releasable pressure-sensitive adhesive layer containing a release resin and a solvent, and a method of thermocompression bonding a metal substrate and a film made of the electromagnetic wave-releasable pressure-sensitive adhesive resin can be used.
In the present invention, the method of applying the coating solution for forming an electromagnetic wave releasable pressure-sensitive adhesive layer is particularly preferable. This is because an electromagnetic wave releasable pressure-sensitive adhesive layer having excellent smoothness can be obtained.
In addition, in this invention, although the method of forming an electromagnetic wave peelable adhesive layer on a metal base material may be sufficient, an electromagnetic wave peelable adhesive layer may be formed on a support substrate. In this case, an electromagnetic wave peelable flexible device substrate (with a support substrate) can be obtained by laminating a metal substrate or the like on the electromagnetic wave peelable adhesive layer formed on the support substrate.

In the present invention, when the pressure-sensitive adhesive that is a component of the electromagnetic wave-releasable pressure-sensitive adhesive resin contained in the coating liquid for forming an electromagnetic wave-releasable pressure-sensitive adhesive layer contains a crosslinking agent, usually, after applying the coating liquid, Crosslinking treatment is performed. For the crosslinking treatment, general conditions such as heating can be used. The temperature and heating time of the crosslinking treatment using heating are appropriately set according to the type of pressure-sensitive adhesive to be used, and general conditions can be used.
Moreover, when the coating liquid for electromagnetic wave peelable adhesion layer formation contains a solvent, normally, after apply | coating the said coating liquid, the drying process which removes a solvent is performed. As such a drying method, a general method such as a method using hot air can be used. Moreover, such a drying process may be performed simultaneously with the said crosslinking process.

(2) Electromagnetic wave peelable adhesive resin The electromagnetic wave peelable adhesive resin used in the present invention is not particularly limited as long as the electromagnetic wave peelable adhesive layer can have electromagnetic wave peelable adhesive properties. .

As such an electromagnetic wave peeling adhesive resin, the thing of Unexamined-Japanese-Patent No. 2009-256442 can be used, for example.
More specifically, examples include an adhesive, an electromagnetic wave polymerizable monomer or an electromagnetic wave polymerizable oligomer, and an electromagnetic wave polymerization initiator. It is because it can be made excellent in electromagnetic wave peeling adhesiveness by using the said resin.

(A) Adhesive The adhesive used in the present invention is not particularly limited as long as it can be bonded to a metal substrate and a support substrate with sufficient strength as an electromagnetic wave releasable adhesive layer. For example, acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyimide-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like can be used. From the viewpoint of compatibility, acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polyimide-based pressure-sensitive adhesives are used. preferable. Moreover, having such an adhesive, that is, the electromagnetic wave peelable adhesive resin, either an acrylic adhesive, a polyester adhesive and a polyimide adhesive, an electromagnetic polymerizable monomer or an electromagnetic polymerizable oligomer, By including an electromagnetic wave polymerization initiator, it is excellent in adhesiveness to the metal base material and the support substrate and peelability from the adherend (metal base material and support substrate) after exposure. It is because it can be made excellent.
Moreover, it is preferable to use a polyester-type adhesive and a polyimide-type adhesive from a heat resistant viewpoint.
Each pressure-sensitive adhesive usually contains a pressure-sensitive adhesive main agent and a crosslinking agent.

(I) Acrylic pressure-sensitive adhesive The acrylic pressure-sensitive adhesive in the present invention is not particularly limited as long as it exhibits a desired pressure-sensitive adhesive property. For example, transparency, heat resistance, moist heat resistance, durability Examples thereof include an acrylic polymer which is excellent in coating suitability and the like and is low in cost as an adhesive main agent.

  The acrylic polymer in the present invention is not particularly limited as long as the desired adhesiveness can be exhibited. For example, an acrylic ester copolymer obtained by copolymerizing an acrylic ester and another monomer. Coalescence is mentioned.

  Examples of the acrylate ester include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, hydroxylethyl acrylate, propylene glycol acrylate, acrylamide, and glycidyl acrylate. It is done. These can be used alone or in combination of two or more. In the present invention, among the above acrylate esters, in particular, n-butyl acrylate and 2-ethylhexyl acrylate are excellent in transparency, heat resistance, moist heat resistance, durability, suitability for coating, etc. This is preferable in terms of cost.

  Other monomers include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide Methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and n-ethylhexyl methacrylate. These can be used alone or in combination of two or more. In the present invention, methacrylic acid-n-ethylhexyl is preferable among the other monomers.

  Moreover, as an acrylic polymer in the present invention, an acrylic ester as a main component, a polymer obtained by copolymerization of the acrylic ester with a copolymerizable hydroxyl group-containing monomer or an acrylic ester as a main component, Those obtained by copolymerization of an acrylic ester with a copolymerizable hydroxyl group-containing monomer and carboxyl group-containing monomer can also be used.

  The copolymerizable hydroxyl group-containing monomer is not particularly limited as long as it has a copolymerizable polymerizable group and a hydroxyl group in its structure. For example, 2-hydroxyethyl acrylate, 2-hydroxyacrylate Examples thereof include hydroxypropyl, 2-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, polyethylene glycol acrylate, and the like.

  The copolymerizable carboxyl group-containing monomer is not particularly limited as long as it has a copolymerizable polymerizable group and a carboxyl group in its structure. For example, acrylic acid, methacrylic acid, carboxyethyl ( Examples include meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

  In the present invention, when the acrylic polymer is obtained by copolymerization of the acrylic ester with a copolymerizable hydroxyl group-containing monomer and a carboxyl group-containing monomer, the hydroxyl group-containing monomer and the carboxyl group-containing monomer Is preferably in the range of 51:49 to 100: 0, and more preferably in the range of 75:25 to 100: 0. By setting the mass ratio of the hydroxyl group-containing monomer to the carboxyl group-containing monomer in the acrylic polymer within the above range, an adhesive that does not cause adhesive residue even on the adherend (metal substrate and support substrate). It can be a composition.

  The copolymerization ratio (mass ratio) between the acrylic ester and the copolymerizable hydroxyl group-containing monomer is not particularly limited as long as the acrylic ester is a main component, and is appropriately selected so as to exhibit a desired adhesive strength. Can be set.

  The main component means that the copolymerization ratio is 51% by mass or more, preferably 65% by mass or more.

  When the acrylic polymer is an acrylate copolymer, the mass average molecular weight (Mw) of the acrylate copolymer is not particularly limited as long as it exhibits a desired adhesive force, but is 100,000 to 110. It is preferably in the range of 10,000, more preferably in the range of 200,000 to 900,000. If it is the said range, sufficient initial adhesive force can be exhibited, and it can be set as the adhesive layer of sufficient intensity | strength. The weight average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

The cross-linking agent contained in the acrylic pressure-sensitive adhesive in the present invention is not particularly limited as long as desired tackiness is obtained, and examples thereof include an isocyanate cross-linking agent and an epoxy cross-linking agent. .
As an isocyanate type crosslinking agent, for example, a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having a terminal isocyanate group obtained by reacting a polyisocyanate compound and a polyol compound, 3 of the urethane prepolymer Examples include a polymer. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.
In addition, as a commercial item of the said isocyanate type crosslinking agent, L45 (made by Soken Chemical Co., Ltd.), TD75 (made by Soken Chemical Co., Ltd.), BXX5627 (made by Toyo Ink Manufacturing Co., Ltd.), X-301-422SK (Siden), for example. (Made by Kagaku Co., Ltd.) etc. can be used suitably.

Examples of the epoxy-based crosslinking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diester. Examples include polyfunctional epoxy compounds such as glycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.
In addition, as a commercial item of the said epoxy-type crosslinking agent, E-5XM (made by Soken Chemical Co., Ltd.), E-5C (made by Soken Chemical Co., Ltd.) etc. can be used suitably, for example.

  The crosslinking agent can be used alone or in combination of two or more, and may be appropriately selected according to the type of the acrylic polymer.

The content of the cross-linking agent contained in the acrylic pressure-sensitive adhesive in the present invention varies depending on the type of the cross-linking agent. It is preferably within a range of 0.01 to 20 parts by mass, and more preferably within a range of 0.01 to 10 parts by mass with respect to parts by mass. If the said content is the said range, the adhesiveness of an adhesion layer and a to-be-adhered body (a metal base material and a support substrate) can be improved. If it is less than 0.01 parts by mass, the adhesion between the adhesive layer and the adherend (metal substrate and support substrate) will be insufficient, or it will be difficult for the adhesive layer to have sufficient strength, When peeling from the adherend, the adhesive layer may cause cohesive failure, resulting in adhesive residue. It is because it will bridge | crosslink more than necessary and the intensity | strength of an adhesion layer will fall when it exceeds 20 mass parts.
The solid content refers to a solid portion excluding volatile substances such as water and solvent, and the solid content is obtained by measuring the mass of residual components after removing volatile components such as water and solvent by heating. Can be sought.

  Moreover, in the case of an epoxy-type crosslinking agent, it is preferable that it exists in the range of 0.01 mass part-20 mass parts with respect to 100 mass parts of solid content of the acrylic polymer which is an adhesive main ingredient, 0.01 More preferably, it is within the range of 10 to 10 parts by mass. If it is the said range, the adhesive force and cohesion force before energy ray irradiation can be controlled to desired intensity | strength. If it is less than 0.01 part by mass, it is difficult for the adhesive layer to have sufficient strength, and the adhesive layer may cause cohesive failure when peeled from the adherend, resulting in adhesive residue. This is because if the amount exceeds 20 parts by mass, the adhesive strength before energy beam irradiation is reduced, and thus the element may be peeled off from the support substrate during the element formation process.

(Ii) Polyester-based pressure-sensitive adhesive The polyester-based pressure-sensitive adhesive used in the present invention is not particularly limited as long as the desired pressure-sensitive adhesiveness can be exhibited. Specific examples include those containing a polyester-based resin as the main component of the pressure-sensitive adhesive and an isocyanate-based crosslinking agent and / or a bismaleimide-based compound as the crosslinking agent.

  Here, the polyester resin can react with the crosslinking agent by having a functional group highly reactive with the isocyanate group, and can crosslink between the polyester resins. And the hardness of a polyester-type adhesive can be improved by bridge | crosslinking between polyester-type resins. In addition, since at least one polyester-based resin has a hydroxyl group at the terminal (polymerization reaction termination terminal) of the resin, it can react with an isocyanate group.

  The polyester resin can be produced by various production methods such as a commonly known transesterification method and direct polymerization method. Even when any of the above production methods is used, the polyester-based resin has a hydroxyl group at its terminal (polymerization reaction termination terminal). Examples of the method for producing the polyester resin include a transesterification reaction in which an aliphatic or aromatic carboxylic acid is reacted with a polyhydric alcohol in the presence of a catalyst.

  In the said manufacturing method, although it does not restrict | limit especially as aliphatic carboxylic acid which can be used, Adipic acid, sebacic acid, dodecanedicarboxylic acid etc. can be illustrated. Examples of the aromatic carboxylic acid include dicarboxylic acids such as terephthalic acid and isophthalic acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, 1,4-butanediol, polytetramethylene ether glycol, polytetramethylene glycol, and the like.

  Moreover, as a manufacturing method of the said polyester-type resin, ester decomposition reaction which reacts aromatic ester and a polyhydric alcohol in presence of a catalyst can be illustrated. Examples of the aromatic ester that can be used in the above production method include dibutyl phthalate, dimethyl terephthalate, and dimethyl phthalate. The polyhydric alcohol is the same polyhydric alcohol as described above. Can do.

  Furthermore, as a manufacturing method of the said polyester-type resin, the manufacturing method with which a polybasic acid, branched diol, and hydrogenated polybutadiene polyol are made to react in presence of a catalyst can be illustrated. Examples of the polybasic acid that can be used in the above production method include dodecanedicarboxylic acid, isophthalic acid, hydrogenated dimer acid, and the like. As the branched diol, 2,2′-butylethylpropanediol, Examples thereof include ethylene glycol and neopentyl glycol.

  The molecular weight of the polyester-based resin is not particularly limited as long as the desired adhesiveness can be exhibited. For example, the molecular weight is within the range of 50,000 to 50,000. preferable. When the molecular weight of the polyester-based resin is 50,000 or more, the crystallinity of the polyester-based resin is improved, and the pressure-sensitive adhesive can have heat resistance even at a high temperature of 200 ° C. or higher. It is preferable from the viewpoint of polyester resin production.

  Moreover, it is preferable that the glass transition temperature (Tg) of the said polyester-type resin exists in the range of -60-25 degreeC. When the glass transition temperature (Tg) is −60 ° C. or higher, the cohesive strength can be maintained even when the polyester-based pressure-sensitive adhesive is thermoset, and the pressure-sensitive adhesive strength does not decrease. When the temperature is 25 ° C. or less, the tackiness of the polyester resin itself is not deteriorated, which is preferable.

  The isocyanate-based crosslinking agent contained as a crosslinking agent in the polyester-based pressure-sensitive adhesive in the present invention is not particularly limited as long as the polyester-based resin can be crosslinked. It is preferable that it can be bridge | crosslinked by. The isocyanate-based crosslinking agent preferably contains an isocyanate compound having two or more isocyanate groups per molecule. If the isocyanate compound has two or more isocyanate groups, the polyester resin can be effectively polymerized by a crosslinking reaction.

  Examples of the isocyanate compound having two or more isocyanate groups per molecule include isocyanate compounds represented by the following general formula.

(In the above general formula, R ¹¹ is a divalent organic group having 1 to 18 carbon atoms, and an aliphatic group, an alicyclic group, and other substituents may be included in part of the structure.)

  Specific examples of the isocyanate compound include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diene. Examples thereof include aromatic isocyanates such as isocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate.

  Further, an isocyanurate adduct can also be used. Examples of the isocyanurate adduct include trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct ( Examples thereof include a product name “Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd., an isocyanurate of hexamethylene diisocyanate (trade name “Coronate HX” manufactured by Japan Polyurethane Industry Co., Ltd.), and the like. In addition, these isocyanate compounds may be used independently and may mix and use 2 or more types.

  The isocyanate-based crosslinking agent is contained in the polyester-based pressure-sensitive adhesive as a crosslinking agent, but the content is not particularly limited as long as the desired adhesiveness can be exhibited. However, it is preferable that it is in the range of 1 mass part-40 mass parts with respect to solid content of 100 mass parts of polyester-type resin, for example, More preferably, it contains in the range of 5 mass parts-30 mass parts. . When the amount is 1 part by mass or more, the degree of crosslinking of the polyester-based resin can be increased, and the heat resistance of the pressure-sensitive adhesive is excellent, and when the amount is 40 parts by weight or less, the pressure-sensitive adhesive is excellent in adhesiveness. This is preferable.

The bismaleimide compound contained as a crosslinking agent in the polyester-based pressure-sensitive adhesive in the present invention is not particularly limited as long as it can be cured by heating and can improve durability. For example, the following general formula Can be mentioned.
A bismaleimide compound represented by the following general formula is obtained by crosslinking two molecules of a maleimide compound produced by a reaction between maleic anhydride, which is an acid anhydride, and an amine. In addition, the imide compound represented by the following general formula has two five-membered rings containing nitrogen atoms, and each five-membered ring is cross-linked with an organic group. By containing a bismaleimide compound having such a chemical structure in a polyester adhesive, the heat resistance of the adhesive can be improved.

(In the above general formula, Z is a divalent organic group.)

  Specific examples of the bismaleimide compound that can be used in the polyester-based pressure-sensitive adhesive include N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N ′-(4,4′-diphenyloxy). ) Bismaleimide, N, N ′-(4,4′-diphenylsulfone) bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-phenylenebismaleimide, N, N′-2, 4-tolylene bismaleimide, N, N′-2,6-tolylene bismaleimide, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-{4,4 ′ -[2,2′-bis (4 ″, 4 ′ ″-phenoxyphenyl) isopropylidene]} bismaleimide, N, N ′-{4,4 ′-[2,2′-bis (4 ″) , 4 '' '− Enoxyphenyl) hexafluoroisopropylidene]} bismaleimide, N, N ′-[4,4′-bis (3,5-dimethylphenyl) methane] bismaleimide, N, N ′-[4,4′-bis (3 , 5-diethylphenyl) methane] bismaleimide, N, N ′-[4,4 ′-(3-methyl-5-ethylphenyl) methane] bismaleimide, N, N ′-[4,4′-bis ( 3,5-diisopropylphenyl) methane] bismaleimide, N, N ′-(4,4′-dicyclohexylmethane) bismaleimide, N, N′-p-xylylene bismaleimide, N, N′-m-xylylene Bismaleimide, N, N ′-(1,3-dimethylenecyclohexane) bismaleimide, N, N ′-(1,4-dimethylenecyclohexane) bismaleimide, polypheny It can be exemplified methane maleimide.

  Among these bismaleimide-based compounds, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N ′-[4,4 ′-(3- Methyl-5-ethylphenyl) methane] bismaleimide and polyphenylmethanemaleimide are preferred.

  The content of the bismaleimide compound as a crosslinking agent in the polyester-based pressure-sensitive adhesive is in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the solid content of the polyester-based resin that is the pressure-sensitive adhesive main agent. Preferably, it is contained within the range of 1 to 20 parts by mass. Since it is possible to increase the degree of crosslinking of the polyester-based resin when it is 0.5 parts by mass or more and the heat resistance of the adhesive is excellent, it is preferable that it is 30 parts by mass or less. It is preferable because it can be used.

(Iii) Polyimide-based pressure-sensitive adhesive The polyimide-based pressure-sensitive adhesive used in the present invention is not particularly limited as long as the desired pressure-sensitive adhesiveness can be exhibited. The thermosetting polyimide adhesive which contains the bismaleimide compound which is a crosslinking agent can be mentioned.

  Examples of such a thermosetting polyimide-based pressure-sensitive adhesive (composition (K)) include those produced by sequentially performing the first to third steps shown below.

  That is, the step of reacting compound (Q) with an aliphatic diamine (imidation reaction) to synthesize polyimide (A) (first step), the polyimide (A) and aromatic diamine are heated and reacted. A composition by performing a step of synthesizing polyimide (B) (second step), a step of mixing polyimide (B) and a bismaleimide compound and mixing them at a predetermined temperature (third step). (K) is manufactured.

(About the first step)
In the first step, the aliphatic diamine and the compound (Q) as described above are heated in the absence of a solvent to carry out an imidation reaction between the aliphatic diamine and the compound (Q), and polyimide is obtained as a reaction product of the imidization reaction. (A) is synthesized.

  In the imidization reaction, an acid anhydride group or a functional group of a dicarboxylic acid derivative that can be imidized is arranged at both ends of the polyimide (A), and a compound having a functional group capable of imidization ( From the viewpoint of suppressing the residual amount of Q), the compound (Q) is preferably blended and carried out so that the number of moles of the compound (Q) is larger than the number of moles of the aliphatic diamine. The compound (Q) is preferably blended at a ratio of 1 mol or more and 2 mol or less with respect to mol.

  In addition, a 1st process may be implemented by making imidation reaction of aliphatic diamine and a compound (Q) in various organic solvents. The organic solvent that can be used is not particularly limited. For example, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, m -Cresol, phenol, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, etc. can be used, but N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -It is preferable to use dimethylformamide and γ-butyrolactone alone or in combination.

  In the first step, the imidization reaction is preferably carried out under conditions of a reaction time of 1 to 12 hours and a reaction temperature of 150 to 200 ° C.

(Compound (Q))
Compound (Q) is one or more compounds selected from the group consisting of tetracarboxylic dianhydrides represented by the following formula (11) and tetracarboxylic acids represented by the following formula (12) and derivatives thereof.

（Ｒ^１２は４価の有機基である）

(R ¹² is a tetravalent organic group)

(R ¹³ is a tetravalent organic group, and Y ^{1 to} Y ⁴ are independently hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.)

  Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides. Moreover, in order to express desired heat resistance, the aromatic tetracarboxylic dianhydride illustrated as needed can also be used.

  Examples of the aliphatic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic Examples thereof include acid dianhydride and dicyclohexyltetracarboxylic dianhydride. Although it does not specifically limit as what is used, Preferably, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 2,3,4-cyclobutanetetracarboxylic dianhydride, more preferably 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

  As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) Ether dianhydride 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 4,4 ′-(p-phenylenedioxy) diphthal Acid dianhydride, 4,4 ′-(m-phenylenedioxy) diphthalic dianhydride, ethylenetetracarboxylic dianhydride, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, etc. I can list them.

  Examples of tetracarboxylic acid and derivatives thereof include aliphatic tetracarboxylic acid and derivatives thereof, and aromatic tetracarboxylic acid and derivatives thereof.

  Examples of the aliphatic tetracarboxylic acid include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2 3,4-cyclopentanetetracarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyltetracarboxylic acid and the like. Examples of the derivative of the aliphatic tetracarboxylic acid include esters of the above-described aliphatic tetracarboxylic acid and alcohol (having 1 to 8 carbon atoms).

  As aromatic tetracarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2-bis (3, 4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,4-dicarboxyphenyl) sulfone, bis ( 3,4-dicarboxyphenyl) ether, bis (2,3-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone Lacarboxylic acid, 4,4 ′-(p-phenylenedioxy) diphthalic acid, 4,4 ′-(m-phenylenedioxy) diphthalic acid, ethylenetetracarboxylic acid, 3-carboxymethyl-1,2,4-cyclo Examples include pentanetricarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, and bis (3,4-dicarboxyphenyl) methane. Examples of the aromatic tetracarboxylic acid derivative include esters of the above aromatic tetracarboxylic acid and an alcohol (having 1 to 8 carbon atoms).

(Aliphatic diamine)
The aliphatic diamine is represented by the following formula (13).

(R ¹⁴ is a C1-221 divalent organic group in which an aliphatic group or alicyclic group is directly bonded to an amino group, and an aromatic group, an ether group, (It may contain a substituent.)

  Therefore, the aliphatic diamine is a diamine having a molecular structure in which an aliphatic group or an alicyclic group is directly bonded to an amino group. The aliphatic diamine may contain an aromatic group, an ether group, or other substituents in a part of the molecular structure. Examples of the aliphatic diamine include polyoxyalkylene diamine, 4,4′-diaminodicyclohexyl methane, isophorone diamine, ethylene diamine, tetramethylene diamine, norbornane diamine, paraxylylenediamine, 1,3-bis (amino Examples include methyl) cyclohexane, 1,3-diaminocyclohexane, hexamethylenediamine, metaxylylenediamine, 4,4′-methylenebis (cyclohexylamine), bicyclohexyldiamine, and siloxane diamines. The aliphatic diamine is preferably a polyoxyalkylene diamine in order to make the cured product of the pressure-sensitive adhesive composition excellent in flexibility and tackiness.

(About the second step)
In the second step, polyimide (B) is synthesized by blending aromatic diamine with polyimide (A) and heating in the absence of a solvent to carry out an imidization reaction.

  In the second step, the imidization reaction of polyimide (A) and aromatic diamine may be carried out in various organic solvents. As the organic solvent, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, tetrahydrofuran, acetone and the like can be used. Further, m-cresol, phenol, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, etc. can be used, but N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and γ-butyrolactone are preferably used alone or in combination.

  In the second step, as in the first step, the imidation reaction is preferably carried out under conditions of a reaction time of 1 to 12 hours and a reaction temperature of 150 to 200 ° C.

(Aromatic diamine)
The aromatic diamine is represented by the following formula (14).

(R ¹⁵ is a divalent organic group having 6 to 27 carbon atoms in which an aromatic ring is directly bonded to an amino group, and an aliphatic group, an alicyclic group, and other substituents are added to a part of the structure. May be included.)

  An aromatic diamine is a diamine in which an aromatic ring is directly bonded to an amino group. As aromatic diamines, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 2 , 4-toluenediamine, diaminobenzophenone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1 , 3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, α, α′-bis (3-aminophenyl) -1,4-diisopropylbenzene, bis [4- (4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminopheno) Xyl) phenyl] sulfone, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 2,2-bis (4-aminophenoxyphenyl) propane and the like. Among these, from the viewpoint of heat resistance and adhesiveness, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis (4-amino) Phenoxyphenyl) propane is preferred.

(About the third step)
In a 3rd process, the bismaleimide compound which is a polyimide (B) which is the adhesive main ingredient synthesize | combined by the 2nd process, and a crosslinking agent is mixed. What is obtained by this is a polyimide-based adhesive (thermosetting polyimide-based adhesive (composition (K)).

  The bismaleimide compound used as the crosslinking agent in the present invention may be the same as that described in the above section “(ii) Polyester adhesive”.

  The content of the bismaleimide compound in the present invention is not particularly limited as long as the bismaleimide compound exhibits a function as a crosslinking agent. The aliphatic diamine 1 used for producing the polyimide (A) In order to make the hardened | cured material of an adhesive excellent in flexibility, it is preferable to mix | blend with 0.25 mol or more and 4 mol or less with respect to mol.

  In the polyimide-based pressure-sensitive adhesive used in the present invention, a latent basic substance such as a basic substance or an energy-sensitive base generator that acts as a catalyst when the crosslinking reaction proceeds may be used. In particular, in the present invention, it is preferable to use a latent basic substance from the viewpoint of storage stability.

  In the present invention, the energy sensitive base generator used as the latent basic substance is one that generates a base by heat or energy rays.

  The energy ray is a concept including light rays and ionizing radiation, the light ray is a concept including at least one of ultraviolet rays, visible rays, and infrared rays, and the ionizing radiation includes X-rays, γ rays, and the like. The concept includes radiation having energy for ionizing a substance and particle beams such as an electron beam.

  The energy-sensitive base generator is preferably one that generates at least one base selected from primary amines, secondary amines, tertiary amines, and amidine compounds by heat or energy rays. The primary amine, secondary amine, and tertiary amine are not particularly limited, but N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl)- Examples include 2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, and 1,3-bis (4-aminophenoxy) benzene. The amidine-based compound comprises a compound having an amidine structure as shown in the following formula (21) and a heterocyclic compound having a partial structure of amidine. Specifically, the amidine-based compound includes diazabicycloundecene, diazabicyclononene, imidazole, pyrimidine, and purine, which are heterocyclic compounds having a partial structure of amidine.

(R ²¹ to R ²⁴ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Also, R ²¹ to R ²⁴ are They may be connected to each other to form a ring structure.)

  In the present invention, since peeling is performed using electromagnetic waves, it is preferable to use an energy sensitive base generator that generates a base without using electromagnetic waves such as a thermal base generator. However, it is also possible to use an energy sensitive base generator that generates a base by electromagnetic waves, such as by using electromagnetic waves having different wavelengths during crosslinking and peeling. In this case, known energy-sensitive base generators that generate bases by electromagnetic waves can be used.

  As an energy sensitive base generator that generates a base by heat, a known thermal base generator can be used, and examples of a thermal base generator that can be used for the pressure-sensitive adhesive composition include U-CAT 5002 manufactured by San Apro Co., Ltd. The U-CAT series can be specifically mentioned.

  Among energy sensitive base generators, those that generate bases by heat (thermal base generators) are those that generate bases at temperatures below 200 ° C, but bases that are at temperatures above room temperature (25 ° C) and below 200 ° C. It is preferable that it is generated, and it is more preferable that the base is generated at a temperature of 80 ° C. or higher and lower than 180 ° C. If such an energy-sensitive base generator generates a base at a temperature that is too low, the energy-sensitive base generator becomes too sensitive to the base-generating reaction, and the coating composition is obtained by dissolving the adhesive composition in a solvent. There is a risk that the stability of the product will deteriorate. If the energy sensitive base generator does not generate a base unless the temperature is too high such that the temperature exceeds 200 ° C., it serves as a catalyst for the crosslinking polymerization reaction of the thermosetting polyimide resin composition There is a risk that it will disappear.

  The compounding amount of the energy sensitive base generator is 0.1 to 35 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the adhesive main component contained in the adhesive. is there. If the blending amount of the energy sensitive base generator is less than 0.1 parts by mass in the adhesive composition, the blending amount is too small and the effect of blending the energy sensitive base generator may be insufficient. When the compounding amount of the energy sensitive base generator exceeds 35 parts by mass in the agent composition, the compounding amount is too large, and low molecular components such as the energy sensitive base generator may bleed from the cured product.

(B) Electromagnetic wave polymerizable monomer or electromagnetic wave polymerizable oligomer As the electromagnetic wave polymerizable monomer or electromagnetic wave polymerizable oligomer in the present invention, when electromagnetic wave irradiation is applied, the electromagnetic wave releasable adhesive resin is cured by three-dimensional cross-linking. Any material may be used as long as it has a function of reducing the force and increasing the cohesive force of the pressure-sensitive adhesive so as not to transfer to the adherend surface.
Such an electromagnetic wave polymerizable monomer or electromagnetic wave polymerizable oligomer is preferably an unsaturated compound containing three or more acryloyl groups in one molecule.

  Specifically, trimethylol methane triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol hexaacrylate, ethylene oxide or propylene oxide adducts thereof may be used. it can.

  The amount of the electromagnetic wave polymerizable monomer or the electromagnetic wave polymerizable oligomer used is not particularly limited as long as it can exhibit the desired peelability. For example, the solid content of the adhesive main component contained in the adhesive It is preferably within the range of 10 to 200 parts by mass, more preferably within the range of 20 to 200 parts by mass with respect to 100 parts by mass. This is because if the amount of the electromagnetic wave polymerizable monomer or electromagnetic wave polymerizable oligomer used is too small, the crosslinking density after irradiation with electromagnetic waves such as ultraviolet rays is not sufficient, and proper peelability cannot be realized. If the amount of the electromagnetic wave polymerizable monomer or electromagnetic wave polymerizable oligomer used is too large, the amount of heat generated during the electromagnetic wave irradiation is too large, and the adherend may be deformed. This is because the protrusion of the agent occurs.

(C) Electromagnetic wave polymerization initiator As the electromagnetic wave polymerization initiator in the present invention, a general electromagnetic wave polymerization initiator can be used, for example, as benzoin and its alkyl etherified product, benzyl ketals, acetophenones, acetophenones. For example, hydroxyacetophenone, aminoacetophenone, dialkoxyacetophenone, halogenated acetophenone and the like can be used.

  Although the usage-amount of the electromagnetic wave polymerization initiator in this invention will not be specifically limited if the desired peelability can be exhibited, For example, 100 mass of solid content of the adhesive main ingredient contained in an adhesive It is preferable that it exists in the range of 0.1 mass part-30 mass parts with respect to a part. If the amount of the electromagnetic wave polymerization initiator used is too small, it is not preferable because a decrease in the adhesive strength after curing is not sufficient. If the amount of the electromagnetic wave polymerization initiator used is too large, the reaction rate becomes too fast and the reaction heat generated increases, which causes deformation of the metal base material or the support substrate, which is not preferable.

(D) Other component In addition to the said component, components, such as antioxidant, binder resin, an organic solvent, and a filler, can be contained in the electromagnetic wave peelable adhesive resin used for this invention as needed. For example, it can be diluted with an organic solvent in conjunction with the coating method. Examples of the organic solvent used for the dilution include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and acetic acid. Examples thereof include ester solvents such as ethyl and cellosolve.

(Antioxidant)
The antioxidant used in the present invention is not particularly limited as long as it can improve the heat resistance of the electromagnetic wave peelable adhesive resin. Specific examples of the antioxidant include hindered amine derivatives, hindered phenol derivatives, phosphorus compounds, sulfur compounds, hydroxyl compounds, triazole derivatives, benzotriazole derivatives, and triazine derivatives. Among the antioxidants, hindered phenol derivatives or benzotriazole derivatives are preferable. By including such an antioxidant in the electromagnetic wave peelable pressure-sensitive adhesive resin, it is possible to effectively suppress deterioration of the polyester-based pressure-sensitive adhesive even when a high-temperature heat history exceeding 200 ° C. is applied. This is preferable.

  The content of the antioxidant is not particularly limited as long as the desired heat resistance can be exhibited. However, the content of the antioxidant is 0 with respect to 100 parts by mass of the solid content of the adhesive main component contained in the adhesive. It is preferable to be within the range of 1 part by mass to 10.0 parts by mass. When the content of the antioxidant is 0.1 parts by mass or more, the ability to suppress the oxidative deterioration of the pressure-sensitive adhesive is improved, and when the content of the antioxidant is 10.0 parts by mass or less, the antioxidant is prevented. This is preferable because there is no risk of adhesive residue due to the bleeding of the agent.

(Fluorine resin)
The fluororesin in the present invention is contained for imparting or improving removability to the electromagnetic wave releasable adhesive resin.

  Examples of the fluorine resin include a polymer obtained by copolymerizing a monomer having a reactive group with an olefin resin such as vinylidene difluoride, hexafluoropropylene, tetrafluoroethylene, and perfluoromethyl vinyl ether, or two or more kinds thereof. Examples of such a copolymer can be exemplified. Furthermore, a fluororesin copolymer obtained by adding ethylene, propylene, alkyl vinyl ether, or the like to be polymerized may be used. Among these fluorine resins, a fluorine-containing olefin resin having a reactive group is particularly preferable because it contains a large amount of fluorine and is excellent in heat resistance.

  Further, a preferred fluororesin is a copolymer obtained by polymerizing a monomer raw material specifically containing (1) a fluoroolefin and (2) a hydrocarbon monomer such as vinyl ether or vinyl ester, and a hydroxyl group. , Fluororesins having functional groups such as carboxy group and epoxy group. Here, the above “(1) fluoroolefin” is a concept including one in which part or all of the hydrogen atoms of the olefin are substituted with fluorine atoms. For example, a compound in which some or all of the hydrogen atoms of the olefin are substituted with fluorine atoms and, as exemplified below, the hydrogen atoms of the olefin are substituted with fluorine atoms, and some of the remaining hydrogen atoms or All of them are substituted with other atoms such as chlorine atoms.

  The fluororesin having the functional group is obtained, for example, by adding the monomer raw materials (1) and (2) above to the raw material monomer, further blending the monomer raw material having a reactive group, and copolymerizing them. Can do. Moreover, after manufacturing fluororesin which has unsaturated bonds, such as a vinyl group, of the said fluororesin, it can obtain by introduce | transducing reactive groups, such as an epoxy group, into this unsaturated bond, such as a vinyl group. Examples of the monomer having a reactive group include monomers having a vinyl bond and a reactive group such as acrylic acid and methacrylic acid.

  Among these fluororesins, it is possible to provide an electromagnetic wave releasable pressure-sensitive adhesive resin that can be peeled off when there is no adhesive residue when bonded to an adherend, so that a monomer raw material containing fluoroolefin and vinyl ether is polymerized. And a copolymer obtained by polymerizing a monomer raw material containing a fluoroolefin and a vinyl ester. In particular, the copolymer is preferably a fluororesin having a functional group such as a hydroxyl group, a carboxy group, or an epoxy group.

  Examples of commercially available fluorine-based resins include a fluoroethylene vinyl ether copolymer having a hydroxyl group and a carboxyl group (trade name: “Lumiflon” manufactured by Asahi Glass Co., Ltd.).

  The content of the fluororesin is not particularly limited as long as it can exhibit a desired peelability, but is preferably with respect to 100 parts by mass of the solid content of the adhesive main component contained in the adhesive. Is in the range of 1 to 40 parts by weight, more preferably in the range of 10 to 30 parts by weight. When the content is 1 part by mass or more, the peelability of the electromagnetic wave peelable pressure-sensitive adhesive resin is improved and adhesive residue can be prevented, which is preferable. On the other hand, when the amount is 40 parts by mass or less, compatibility with other resin components such as a pressure-sensitive adhesive is improved, which is advantageous in production. In addition, the said fluorine-type resin can be used 1 type or in mixture of 2 or more types.

  When it is necessary to further improve the peel strength of the electromagnetic wave peelable adhesive resin, a fluorine-based additive can be further contained. Examples of the fluorine-based additive include a fluorine-containing graft polymer, a fluorine-containing block copolymer, a fluorine-containing aliphatic polymer ester (these may be oligomers) and the like.

  Specific examples of the fluorine-containing graft polymer include fluorine-containing acrylic graft polymers. Examples of commercially available products include trade name: Chemitry LF-700 manufactured by Soken Chemical Co., Ltd. The fluorine-containing acrylic graft polymer is composed of a trunk polymer and a plurality of branch polymers extending from the trunk polymer, the trunk polymer is composed of an acrylic polymer, and the branch polymer is composed of a polymer containing fluorine. .

  Examples of the fluorine-containing block copolymer include a block copolymer comprising a fluorinated alkyl group-containing polymer segment and an acrylic polymer segment. For example, as a commercial product, a product name manufactured by Nippon Oil & Fats Co., Ltd .: Modiper F series (Modiper F200, Modiper F220, Modiper F2020, Modiper F3035, Modiper F600) can be exemplified. Moreover, as a fluorine-containing aliphatic polymer ester, what has the characteristic as a nonionic surfactant is preferable. For example, as a commercial item, the brand name made by 3M: Novec FC-4430 etc. can be mentioned. Among these fluorine-containing block copolymers, a fluorine-containing graft polymer or a fluorine-containing block copolymer is preferable from the viewpoint of eliminating the adhesive residue of the electromagnetic wave peelable adhesive resin.

(solvent)
The electromagnetic wave releasable pressure-sensitive adhesive resin in the present invention may contain a solvent component in order to obtain good coatability to a metal substrate or the like and handling suitability. Examples of such a solvent component include ketones such as methyl ethyl ketone (MEK) and acetone, carboxylic acid esters such as ethyl acetate, methyl acetate and methyl propionate, amides such as N, N-dimethylacetylamide and N-methylpyrrolidone, Examples include 1,3-dioxolane, but are not limited thereto.
The electromagnetic wave releasable adhesive resin contains an adhesive (adhesive main agent and crosslinking agent), an electromagnetic wave polymerizable monomer or an electromagnetic wave polymerizable oligomer, an electromagnetic wave polymerization initiator, and other additives as required. Used in adhesives, solvent components used in electromagnetic polymerizable monomers or electromagnetic polymerizable oligomers, solvent components used in electromagnetic polymerization initiators, and other additives. Further, the solvent used for each component constituting the pressure-sensitive adhesive is independently selected and may be the same or different.

(E) Electromagnetic wave peelable pressure-sensitive adhesive resin The 1% weight reduction temperature of the electromagnetic wave peelable pressure sensitive adhesive resin used in the present invention is not particularly limited as long as it exhibits desired heat resistance, but at 200 ° C. or higher. Preferably there is.
Even when heated when forming an electronic element such as an organic EL or TFT on the insulating layer, the adhesion to the metal substrate and the support substrate and the peelability of the adherend after exposure are reduced. This is because it can be suppressed. The upper limit of the 1% weight reduction temperature is not particularly limited because it is preferably as high as possible, and is appropriately set according to the type of each component contained in the electromagnetic wave-releasable adhesive resin, coating properties, and the like. Is.

Here, the 1% weight loss temperature is 200 ° C. or more means that when measuring weight loss using a thermogravimetric analyzer, the temperature is increased to 100 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. Then, after heating at 100 ° C. for 60 minutes, the mixture was allowed to cool in a nitrogen atmosphere for 15 minutes or more, and then 1% weight loss measured on the basis of the weight after cooling when measured at a heating rate of 10 ° C./min. A temperature of 200 ° C. or higher.
The 1% weight reduction temperature is the time when the weight of the sample is reduced by 1% from the initial weight when the weight reduction is measured using a thermogravimetric analyzer (that is, the sample weight becomes 99% of the initial weight). Temperature). In addition, since the measured weight reduction excludes the influence of the weight reduction due to moisture or solvent, the sample after drying is used as the measurement sample.

  The method for adjusting the electromagnetic wave peeling adhesive resin in the present invention can be obtained by sufficiently kneading each of the above components. The method of blending each component of the electromagnetic wave releasable adhesive resin is not particularly limited, but by a method of dissolving and mixing each component in a solvent as described above, or by a mechanical method such as a kneader roll. Can also be kneaded.

2. Insulating layer The insulating layer used in the present invention is formed on at least one surface of the metal substrate and has an insulating property.

The insulating property of such an insulating layer varies depending on the type of the electronic element portion formed on the insulating layer, and is specifically 1.0 × 10 ⁹ Ω · m or more. Preferably, it is 1.0 × 10 ¹⁰ Ω · m or more, and more preferably 1.0 × 10 ¹¹ Ω · m or more.
The volume resistance can be measured by a method based on standards such as JIS K6911, JIS C2318, and ASTM D257.

The hygroscopic expansion coefficient of the insulating layer used in the present invention is not particularly limited as long as the electronic element portion can be stably formed. Specifically, the hygroscopic expansion coefficient is 0 ppm. /% RH to 15 ppm /% RH, preferably 0 ppm /% RH to 12 ppm /% RH, and more preferably 0 ppm /% RH to 10 ppm /% RH.
When the hygroscopic expansion coefficient is within the above-described range, it is possible to suppress changes in dimensions due to moisture absorption. As a result, it is possible to suppress the occurrence of cracks and peeling in the electronic element portion such as TFT.

The hygroscopic expansion coefficient is measured as follows. First, a film having only an insulating layer is produced. The insulating layer film is produced by a method of peeling off the insulating layer film after insulating layer film is formed on a heat-resistant film (Upilex S 50S (manufactured by Ube Industries)) or a glass substrate and then insulating on a metal substrate. There is a method of obtaining an insulating layer film by removing a metal by etching after producing a layer film. Next, the obtained insulating layer film is cut into a width of 5 mm and a length of 20 mm to obtain an evaluation sample. The hygroscopic expansion coefficient is measured by a humidity variable mechanical analyzer (Thermo Plus TMA8310 (manufactured by Rigaku Corporation)). For example, the temperature is kept constant at 25 ° C., the humidity is first set to a stable state in an environment of 15% RH, the state is maintained for about 30 minutes to 2 hours, and the humidity of the measurement site is set to 20%. RH and hold for 30 minutes to 2 hours until the sample is stable. Thereafter, the humidity is changed to 50% RH, and the difference between the sample length when the humidity becomes stable and the sample length when the humidity becomes stable at 20% RH is expressed as a change in humidity (in this case, 50-20). 30) and the value divided by the sample length is the hygroscopic expansion coefficient (CHE). At the time of measurement, the tensile weight is set to 1 g / 25000 μm ² so that the weight per cross-sectional area of the evaluation sample becomes the same.

The linear thermal expansion coefficient of the insulating layer used in the present invention is not particularly limited as long as it can stably form the electronic element portion. From the viewpoint of dimensional stability, a metal substrate is used. The difference from the linear thermal expansion coefficient of the material is preferably 15 ppm / ° C. or less, more preferably 10 ppm / ° C. or less, and further preferably 5 ppm / ° C. or less. The closer the linear thermal expansion coefficient between the insulating layer and the metal substrate, the more the warpage is suppressed and the stress at the interface between the insulating layer and the metal substrate becomes smaller when the thermal environment of the electronic element changes. Improve. In addition, the electromagnetic wave releasable flexible device substrate of the present invention is preferably not warped in the temperature environment in the range of 0 ° C. to 100 ° C. for handling, but because the linear thermal expansion coefficient of the insulating layer is large. If the linear thermal expansion coefficients of the insulating layer and the metal substrate are greatly different, they are warped by changes in the thermal environment.
It should be noted that the warp does not occur in the electronic element part means that the electromagnetic wave releasable flexible device substrate is cut into a strip shape having a width of 10 mm and a length of 50 mm, and one short side of the obtained sample is horizontal and smooth. When fixed on a table, the flying distance from the table surface on the other short side of the sample is 1.0 mm or less.

  Furthermore, it is preferable that the linear thermal expansion coefficient of the insulating layer is appropriately selected according to the type of the electronic element portion formed on the insulating layer. For example, when the electronic element portion is a TFT, it is preferable that the linear thermal expansion coefficient of the insulating layer is relatively small from the linear thermal expansion coefficient of the semiconductor layer constituting the TFT. For example, when the electronic element portion is an organic EL element, it is preferable that the linear thermal expansion coefficient of the insulating layer is relatively small from the linear thermal expansion coefficient of the electrodes constituting the organic EL element.

  Specifically, the linear thermal expansion coefficient of the insulating layer is preferably in the range of 0 ppm / ° C. to 30 ppm / ° C., more preferably in the range of 0 ppm / ° C. to 25 ppm / ° C., from the viewpoint of dimensional stability. More preferably, it is in the range of 0 ppm / ° C. to 18 ppm / ° C., particularly preferably in the range of 0 ppm / ° C. to 12 ppm / ° C. Especially, when an electronic element part is TFT, it is most preferable to be in the range of 0 ppm / ° C. to 7 ppm / ° C. Moreover, when an electronic element part is an organic EL element, it is most preferable that it is about 0 ppm / degrees C-10 ppm / degrees C.

The linear thermal expansion coefficient is measured as follows. First, a film having only an insulating layer is produced. The method for producing the insulating layer film is as described above. Next, the obtained insulating layer is cut into a width of 5 mm and a length of 20 mm to obtain an evaluation sample. The linear thermal expansion coefficient is measured by a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation)). The measurement conditions were a heating rate of 10 ° C./min, a tensile load of 1 g / 25,000 μm ² so that the weight per cross-sectional area of the evaluation sample was the same, and an average linear thermal expansion within the range of 100 ° C. to 200 ° C. The coefficient is the linear thermal expansion coefficient (CTE).

  The surface roughness Ra of the insulating layer used in the present invention is not particularly limited as long as the electronic element portion can be accurately formed, but is smaller than the surface roughness Ra of the metal substrate. preferable. Specifically, the surface roughness Ra of the insulating layer is preferably 25 nm or less, and more preferably 10 nm or less. This is because if the surface roughness Ra of the insulating layer is too large, when the electronic element portion is a TFT, the electrical performance of the TFT may be deteriorated by unevenness. In addition, if the surface roughness Ra of the insulating layer is too large, when the electronic element portion is an organic EL element, there is a risk that a short circuit may occur between the electrodes due to the unevenness or luminance unevenness may occur.

  The surface roughness Ra is a value measured using an atomic force microscope (AFM) or a scanning white interferometer. For example, when measuring using AFM, using Nanoscope V multimode (Veeco), in tapping mode, cantilever: MPP11100, scanning range: 50 μm × 50 μm, scanning speed: 0.5 Hz, surface shape Ra can be obtained by taking an image and calculating an average deviation from the center line of the roughness curve calculated from the obtained image. Further, when measuring using a scanning white interferometer, using New View 5000 (manufactured by Zygo), objective lens: 100 times, zoom lens: 2 times, Scan Length: 15 μm, 50 μm × 50 μm Ra can be obtained by imaging the surface shape of the range and calculating the average deviation from the center line of the roughness curve calculated from the obtained image.

The insulating layer forming material constituting such an insulating layer is not particularly limited as long as it satisfies the above-described characteristics and has flexibility. For example, an organic material, an inorganic material, and Examples thereof include those in which an inorganic material is dispersed in an organic material.
In the present invention, it is preferable that the organic material is the main component. It is because it can be made excellent in flexibility.
Note that the main component means that the insulating layer forming material contains an organic material to the extent that the above characteristics are satisfied. Specifically, the content of the organic material is 75% by mass or more in the insulating layer forming material, preferably 90% by mass or more, and it is particularly preferable that the insulating layer forming material is composed only of the organic material. . This is because it can be particularly excellent in flexibility.

The organic material used in the present invention is not particularly limited as long as it satisfies the above-mentioned characteristics. For example, polyimide resin, phenol resin, PPS (polyphenylene sulfide), PPE (polyphenylene ether), PEK (polyethylene). Examples include ether ketone), PEEK (polyether ether ketone), polyphthalamide, PTFE (polyethylene terephthalate), acrylic resin, polycarbonate, polystyrene, polypropylene, polycyclooxide, and epoxy resin. Among these, polyimide resin, PPS (polyphenylene sulfide), PPE (polyphenylene ether), and epoxy resin are preferably used from the viewpoints of heat resistance and insulation.
In the present invention, it is particularly preferable that a polyimide resin is included. This is because, when the organic material is a polyimide resin, an insulating layer that is more excellent in insulation, heat resistance, and dimensional stability can be obtained. Further, by using polyimide resin, the insulating layer can be thinned, the thermal conductivity of the insulating layer can be improved, and the heat dissipation can be improved.

  The polyimide resin used in the present invention is a polyimide resin containing an aromatic skeleton from the viewpoint of making the linear thermal expansion coefficient and hygroscopic expansion coefficient of the insulating layer suitable for the electromagnetic wave-releaseable flexible device substrate of the present invention. Preferably there is. Among polyimide resins, a polyimide resin containing an aromatic skeleton is derived from its rigid and highly planar skeleton, has excellent heat resistance and insulation in a thin film, and has a low linear thermal expansion coefficient. It is preferably used for the insulating layer of the substrate for electromagnetic wave peelable flexible devices.

  Since the polyimide resin is required to have low hygroscopic expansion and low linear thermal expansion, the polyimide resin preferably has a repeating unit represented by the following formula (1). Such a polyimide resin exhibits high heat resistance and insulation derived from its rigid skeleton, and exhibits linear thermal expansion equivalent to that of metal. Furthermore, the hygroscopic expansion coefficient can be reduced.

(In Formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, and R ¹ and R ² that are repeated may be the same or different. n is a natural number of 1 or more.)

In the formula (1), R ¹ is generally a structure derived from tetracarboxylic dianhydride, and R ² is a structure derived from diamine.

Examples of the tetracarboxylic dianhydride applicable to the polyimide resin include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxypheny ) Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4- Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) Phenoxy] phenyl} propane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarbox Cis) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) Phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafulpropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6,7 -Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,4,9,1 - Bae Li Ren dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, and the like.
These may be used alone or in combination of two or more.

The tetracarboxylic dianhydride preferably used from the viewpoint of the heat resistance of the polyimide resin, the linear thermal expansion coefficient, etc. is an aromatic tetracarboxylic dianhydride. Particularly preferably used tetracarboxylic dianhydrides include pyromellitic dianhydride, merophanic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4. , 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, 2, 2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1, Examples include 1,3,3,3-hexafluoropropane dianhydride and bis (3,4-dicarboxyphenyl) ether dianhydride.
Among these, from the viewpoint of reducing the hygroscopic expansion coefficient, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3 2,2 ′, 3′-biphenyltetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) ether dianhydride are particularly preferred.

When tetracarboxylic dianhydride into which fluorine is introduced is used as the tetracarboxylic dianhydride used in combination, the hygroscopic expansion coefficient of the polyimide resin is lowered. However, a polyimide precursor having a skeleton containing fluorine is difficult to dissolve in a basic aqueous solution and needs to be developed with a mixed solution of an organic solvent such as alcohol and a basic aqueous solution.
In addition, pyromellitic dianhydride, merophanic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride , 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and other rigid tetracarboxylic dianhydrides, polyimide resin Is preferable because the coefficient of linear thermal expansion is small. Among these, from the viewpoint of the balance between the linear thermal expansion coefficient and the hygroscopic expansion coefficient, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid The anhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride is particularly preferred.

  When it has an alicyclic skeleton as tetracarboxylic dianhydride, since the transparency of a polyimide precursor improves, it becomes a highly sensitive photosensitive polyimide precursor. On the other hand, the heat resistance and insulation of the polyimide resin tend to be inferior compared to the aromatic polyimide resin.

When an aromatic tetracarboxylic dianhydride is used, there is a merit that it becomes a polyimide resin having excellent heat resistance and a low linear thermal expansion coefficient. Therefore, in the polyimide resin, it is preferable that 33 mol% or more of R ¹ in the above formula (1) has any structure represented by the following formula.

When the polyimide resin contains any structure of the above formula, it is derived from these rigid skeletons and exhibits low linear thermal expansion and low hygroscopic expansion. Furthermore, there is also an advantage that it is easily available on the market and is low cost.
The polyimide resin having the structure as described above is a polyimide resin exhibiting high heat resistance and a low linear thermal expansion coefficient. Therefore, the content of the structure represented by the above formula is preferably closer to 100 mol% of R ^{1 in} the above formula (1), but at least 33% of R ^{1 in} the above formula (1) is contained. do it. Among them, the content of the structure represented by the above formula is preferably 50 mol% or more, and more preferably 70 mol% or more of R ^{1 in} the above formula (1).

On the other hand, the diamine component applicable to the polyimide resin can also be used alone or in combination of two or more diamines. The diamine component used is not particularly limited, and examples thereof include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′. -Diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4, , 4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3, 4'-diaminodiphenyl meta 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2- Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoro Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1- Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3 -Aminophenoxy) benzene, 1,3-bis (4 Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis ( 4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) Benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-) α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoro) Methylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6 -Bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) Biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4 -Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Cis) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) Benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [ -(4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)- α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy Diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3 '-Diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis ( 4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4- Aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (amino) Methyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2 -(3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] Ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ) Ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12- Diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (amino) Methyl) bicyclo [2.2.1] heptane. In addition, a diamine obtained by substituting some or all of the hydrogen atoms on the aromatic ring of the diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group may be used. it can.
Furthermore, depending on the purpose, any one or two or more of ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a cross-linking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the polyimide resin has a low expansion coefficient. Examples of rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.
In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, There exists what is represented by following formula (2). Specific examples include benzidine and the like.

(In the formula (2), a is 0 or a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

Furthermore, in the above formula (2), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which is not involved in the bond with another benzene ring can also be used. These substituents are monovalent organic groups, but they may be bonded to each other. Specific examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl and the like can be mentioned.
In addition, when fluorine is introduced as a substituent of the aromatic ring, the hygroscopic expansion coefficient can be reduced. However, polyimide precursors containing fluorine, particularly polyamic acid, are difficult to dissolve in a basic aqueous solution. When an insulating layer is partially formed on a metal substrate, alcohol or the like may be used during processing of the insulating layer. It may be necessary to develop with a mixed solution with an organic solvent.

  On the other hand, when a diamine having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine, the adhesion with the metal substrate is improved or the elastic modulus of the polyimide resin is lowered. In addition, the glass transition temperature can be lowered.

  Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, depending on the desired physical properties, the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%. Non-aromatic diamines such as diamines may be used.

Moreover, in polyimide resin, it is preferable that 33 mol% or more among R < ² > in said Formula (1) is either structure represented by a following formula.

(R ³ is a divalent organic group, oxygen atom, sulfur atom, or sulfone group, and R ⁴ and R ⁵ are a monovalent organic group or a halogen atom.)

When the polyimide resin contains any structure of the above formula, it is derived from these rigid skeletons and exhibits low linear thermal expansion and low hygroscopic expansion. Furthermore, there is also an advantage that it is easily available on the market and is low cost.
When it has the above structure, the heat resistance of a polyimide resin improves and a linear thermal expansion coefficient becomes small. Therefore, the content of the structure represented by the above formula is preferably closer to 100 mol% of R ^{2 in} the above formula (1), but at least 33% or more of R ^{2 in} the above formula (1). It may be contained. Among them, the content of the structure represented by the above formula is preferably 50 mol% or more, and more preferably 70 mol% or more, of R ^{2 in} the above formula (1).

Generally, the linear thermal expansion coefficient of a metal base material, that is, the linear thermal expansion coefficient of a metal is determined to some extent. Therefore, the linear thermal expansion coefficient of the insulating layer is determined according to the linear thermal expansion coefficient of the metal base material to be used. It is preferable to select the structure as appropriate.
Moreover, when producing a TFT substrate using the electromagnetic wave peelable flexible device substrate of the present invention, the linear thermal expansion coefficient of the metal substrate is determined according to the linear thermal expansion coefficient of the TFT, and the metal substrate It is preferable to determine the linear thermal expansion coefficient of the insulating layer in accordance with the linear thermal expansion coefficient and select the structure of the polyimide resin as appropriate.
Furthermore, when producing an organic EL display device or electronic paper using the electromagnetic wave peelable flexible device substrate of the present invention, the linear heat of the metal substrate is determined according to the linear thermal expansion coefficient of the organic EL display device or electronic paper. It is preferable to determine the expansion coefficient, determine the linear thermal expansion coefficient of the insulating layer according to the linear thermal expansion coefficient of the metal base material, and appropriately select the structure of the polyimide resin.

  In the present invention, the insulating layer is appropriately used as an insulating layer by laminating or combining the polyimide resin having the repeating unit represented by the above formula (1) and another polyimide resin as necessary. Also good.

  Moreover, the polyimide resin which has a repeating unit represented by the said Formula (1) may be obtained using a photosensitive polyimide or a photosensitive polyimide precursor. The photosensitive polyimide can be obtained using a known method. For example, an ethylenic double bond may be introduced into the carboxyl group of polyamic acid by an ester bond or an ionic bond, and a photoradical initiator may be mixed into the resulting polyimide precursor to form a solvent-developed negative photosensitive polyimide precursor. it can. In addition, for example, a naphthoquinone diazide compound is added to polyamic acid or a partially esterified product thereof to obtain an alkali development positive photosensitive polyimide precursor, or an nifedipine compound is added to polyamic acid to form an alkali development negative photosensitive polyimide precursor. For example, a photobase generator can be added to the polyamic acid to obtain an alkali development negative photosensitive polyimide precursor.

  In these photosensitive polyimide precursors, 15% to 35% of a photosensitizing component is added to the weight of the polyimide component. Therefore, even if it heats at 300 to 400 degreeC after pattern formation, the residue derived from a photosensitivity provision component remains in a polyimide resin. Because these residual materials cause the linear thermal expansion coefficient and hygroscopic expansion coefficient to increase, the reliability of the device is greater when using a photosensitive polyimide precursor than when using a non-photosensitive polyimide precursor. Tend to decrease. However, since a photosensitive polyimide precursor obtained by adding a photobase generator to polyamic acid can form a pattern even if the amount of the photobase generator added as an additive is 15% or less, after forming a polyimide resin Is the most preferable as a photosensitive polyimide precursor applicable to the present invention because there are few decomposition residues derived from additives, there is little deterioration in properties such as linear thermal expansion coefficient and hygroscopic expansion coefficient, and there is also little outgassing.

  The polyimide precursor used in the polyimide resin can be developed with a basic aqueous solution. When partially forming an insulating layer on a metal substrate, it is necessary to ensure the safety of the work environment and reduce process costs. To preferred. Since the basic aqueous solution can be obtained at a low cost and the waste liquid treatment cost and the facility cost for ensuring work safety are low, production at a lower cost is possible.

  The inorganic material used in the present invention is not particularly limited as long as it has insulating properties. Specifically, silicon oxide, silicon nitride, aluminum oxide, tantalum oxide, barium strontium titanate (BST) ), Lead zirconate titanate (PZT), and the like.

  The insulating layer may contain additives such as a leveling agent, a plasticizer, a surfactant, and an antifoaming agent as necessary.

  The insulating layer used in the present invention may be formed at least on one surface of the metal substrate, and the other surface of the metal substrate, that is, the metal substrate and the metal substrate. It may be arranged between the electromagnetic wave releasable pressure-sensitive adhesive layer.

  The insulating layer may be formed on the entire surface of the metal substrate, or may be partially formed on the metal substrate. That is, the metal substrate exposed region where the insulating layer is not present and the metal substrate is exposed may be provided on the surface of the metal substrate where the insulating layer is formed. When having such a metal substrate exposed region, the sealing member and the metal substrate are brought into direct contact with each other when the organic EL display device is produced using the electromagnetic wave peelable flexible device substrate of the present invention. This makes it possible to more firmly prevent moisture from entering the organic EL display device. In addition, by selectively forming the sealing portion in the exposed area of the metal base material, it becomes possible to divide the organic EL display device in a plane or to seal it in a multi-faceted state, resulting in high productivity. It has the advantage that an element can be manufactured. In addition, the metal substrate exposed region can also be a through-hole for penetrating the insulating layer and electrically connecting to the metal substrate.

  When the insulating layer is partially formed on the metal substrate, the insulating layer 2 is formed excluding at least the outer edge portion of the metal substrate 1 as illustrated in FIGS. 2 (a) and 2 (b). It may be. FIG. 2A is a cross-sectional view taken along line AA in FIG. When an organic EL display device or electronic paper is produced using the electromagnetic wave releasable flexible device substrate of the present invention, an insulating layer is formed on the entire surface of the metal base and the end of the insulating layer is exposed. In the case where an organic material such as polyimide resin is included as the insulating layer forming material, the organic material generally exhibits hygroscopicity, so that moisture may enter the element from the end face of the insulating layer during manufacturing or driving. This moisture deteriorates the device performance or changes the dimensions of the insulating layer. Therefore, an insulating layer is not formed on the outer edge portion of the metal substrate, and it is preferable to reduce as much as possible the portion where the insulating layer containing the polyimide resin is directly exposed to the outside air.

In the present invention, that the insulating layer is partially formed on the metal base means that the insulating layer is not formed on the entire surface of the metal base.
The insulating layer may be formed on the entire surface of the metal substrate except for the outer edge portion of the metal substrate, or may be further formed in a pattern on the metal substrate except for the outer edge portion of the metal substrate. Good.

  The thickness of the insulating layer is not particularly limited as long as it can satisfy the above-mentioned characteristics. Specifically, when the insulating layer forming material contains an organic material as a main component, specifically, a range of 1 μm to 1000 μm. It is preferably within the range, more preferably within the range of 1 μm to 200 μm, and even more preferably within the range of 1 μm to 100 μm. This is because if the thickness of the insulating layer is too thin, the insulation cannot be maintained, or it is difficult to flatten the irregularities on the surface of the metal substrate. In addition, if the insulating layer is too thick, flexibility is reduced, it becomes excessively heavy, drying during film formation becomes difficult, and the amount of material used increases, resulting in an increase in cost. . Furthermore, in the case of imparting a heat dissipation function to the electromagnetic wave peelable flexible device substrate of the present invention, when the insulating layer is thick, when the organic material is included, the organic material is more thermally conductive than the metal. Is low, the thermal conductivity decreases.

  In addition, the thickness of the insulating layer when the insulating layer forming material is made of an inorganic material is not particularly limited as long as it does not cause defects such as peeling, but specifically, 0.1 nm It is preferably within the range of ˜50 nm, more preferably within the range of 0.5 nm to 20 nm, and even more preferably within the range of 1 nm to 10 nm. This is because if the thickness is less than the above range, it is difficult to obtain a stable insulating layer, and if it is too thick, peeling or cracking may occur.

The method for forming the insulating layer is not particularly limited as long as an insulating layer having good smoothness can be obtained. When the insulating layer forming material is mainly composed of an organic material, the insulating layer is formed on the metal substrate. In addition, a method of applying an insulating layer forming coating solution containing the insulating layer forming material and a solvent, and a method of thermocompression bonding a metal substrate and a film made of the insulating layer forming material can be used.
In the present invention, the method of applying the insulating layer forming coating solution is particularly preferable. This is because an insulating layer having excellent smoothness can be obtained.
Moreover, when the said insulating layer forming material is a polyimide resin, the method of apply | coating a polyimide solution or a polyimide precursor solution is preferable, and the method of apply | coating a polyimide precursor solution is especially suitable. This is because polyimide generally has poor solubility in a solvent. In addition, polyimide having high solubility in a solvent is inferior in physical properties such as heat resistance, linear thermal expansion coefficient, and hygroscopic expansion coefficient.

The coating method is not particularly limited as long as it can obtain an insulating layer with good smoothness. For example, spin coating method, die coating method, dip coating method, bar coating method, gravure printing method, A screen printing method or the like can be used.
When applying a polyimide resin solution or a polyimide precursor solution, the fluidity of the film can be improved and the smoothness can be improved by heating to a temperature higher than the glass transition temperature of the polyimide or polyimide precursor after application.

  Moreover, when forming an insulating layer partially on a metal base material, the method of processing directly by the printing method, the photolithographic method, a laser etc. can be used as the formation method. As a photolithography method, for example, an insulating layer forming layer is formed on a metal substrate using the insulating layer forming coating solution, and then a photosensitive resin film is formed on the insulating layer forming layer. A method of forming a photosensitive resin film pattern by lithography, and then removing the insulating layer forming layer at the pattern opening using the pattern as a mask, and then removing the photosensitive resin film pattern; the photosensitive resin film pattern A method of developing the insulating layer forming layer simultaneously with the formation of the photosensitive resin film pattern and then removing the photosensitive resin film pattern; one metal group of the laminate in which the metal substrate, the insulating layer forming layer, and the metal substrate are stacked A method of patterning a material, etching the insulating layer using the pattern as a mask, and then removing the metal pattern; using the above-mentioned coating solution for forming an insulating layer, the pattern of the insulating layer directly on the metal substrate A method of forming and the like. Examples of the printing method include methods using known printing techniques such as gravure printing, flexographic printing, screen printing, and ink jet method.

  In addition, the method for forming the insulating layer when the insulating layer forming material is made of an inorganic material is not particularly limited as long as it can be an insulating layer having a desired pattern. ) Sputtering method, RF (radio frequency) magnetron sputtering method, plasma CVD (chemical vapor deposition) method and the like.

3. Metal base material The metal base material used for this invention has flexibility, and the said electromagnetic wave peelable adhesion layer, an insulating layer, an electronic element part, etc. are formed.

The thickness of the metal substrate used in the present invention is not particularly limited as long as it exhibits flexibility, but is preferably in the range of 1 μm to 1000 μm, and in particular, in the range of 1 μm to 200 μm. It is preferably within the range, and particularly preferably within the range of 5 μm to 100 μm. When the film thickness is within the above range, the conventional flexible device substrate not including the electromagnetic wave peelable adhesive layer is deformed when the electronic element portion is formed, and the electronic element portion is formed on the flexible device substrate. It may be difficult to form stably.
On the other hand, in the present invention, the electronic element portion can be stably formed by having the electromagnetic wave peelable pressure-sensitive adhesive layer and simply laminating and fixing to the support substrate. It is. In addition, since the support substrate can be easily peeled off simply by irradiating an electromagnetic wave after forming the electronic element part, the use of a solution or the like for dissolving the adhesive layer, and a great force for peeling off Can be made unnecessary. Therefore, it is because the effect of this invention that it can be excellent in handling property can be exhibited more effectively by the said film thickness being in the above-mentioned range.
Moreover, if the film thickness of the metal substrate is too thick, the flexibility is lowered, the weight is excessive, and the cost is increased.

The linear thermal expansion coefficient of the metal substrate used in the present invention is preferably in the range of 0 ppm / ° C. to 25 ppm / ° C., more preferably 0 ppm / ° C. to 18 ppm / ° C. from the viewpoint of dimensional stability. Within the range, more preferably within the range of 0 ppm / ° C. to 12 ppm / ° C., particularly preferably within the range of 0 ppm / ° C. to 7 ppm / ° C.
In addition, about the measuring method of the said linear thermal expansion coefficient, it is the same as the measuring method of the linear thermal expansion coefficient of the said insulating layer except cut | disconnecting a metal base material to width 5mm * length 20mm and making it an evaluation sample.

  The surface roughness Ra of the metal substrate used in the present invention is not particularly limited as long as the electronic member formed on the insulating layer can be accurately formed, but the surface of the insulating layer is not limited. It is larger than the roughness Ra, for example, about 50 nm to 200 nm. The method for measuring the surface roughness is the same as the method for measuring the surface roughness of the insulating layer.

  In the present invention, the metal substrate preferably has oxidation resistance. This is because, when the electromagnetic wave peelable flexible device substrate of the present invention is used for the production of a TFT substrate, it is usually subjected to a high temperature treatment during the production of the TFT. In particular, when the TFT has an oxide semiconductor layer, the metal substrate preferably has oxidation resistance because annealing is performed at a high temperature in the presence of oxygen.

The metal material constituting the metal substrate used in the present invention is not particularly limited as long as it satisfies the above-mentioned characteristics. For example, aluminum, copper, copper alloy, phosphor bronze, stainless steel (SUS) , Gold, gold alloy, nickel, nickel alloy, silver, silver alloy, tin, tin alloy, titanium, iron, iron alloy, zinc, molybdenum and the like. In the present invention, among them, SUS is preferable when applied to a large element. SUS is excellent in oxidation resistance and heat resistance, and has a smaller coefficient of linear thermal expansion than copper and has excellent dimensional stability. Further, SUS304 has an advantage that it is particularly easy to obtain, and SUS430 has an advantage that it is easy to obtain and the linear thermal expansion coefficient is smaller than SUS304.
On the other hand, when the substrate for electromagnetic wave peelable flexible device of the present invention is used for the production of a TFT substrate, considering the linear thermal expansion coefficient of the metal substrate and TFT, from the viewpoint of the linear thermal expansion coefficient, it is even lower than SUS430. Titanium or invar having a thermal expansion coefficient is preferable. However, it is desirable to select not only the linear thermal expansion coefficient but also taking into consideration the workability of the foil and the cost due to the oxidation resistance, heat resistance, malleability and ductility of the metal substrate.

  The shape of the metal substrate used in the present invention is not particularly limited, and may be, for example, a foil shape or a plate shape. As illustrated in FIG. The shape on the layer side may be a shape having irregularities. In particular, as illustrated in FIG. 3, when the electromagnetic wave releasable flexible device substrate of the present invention is used for manufacturing an organic EL element substrate, the shape of the metal substrate 1 on the side of the electromagnetic wave releasable adhesive layer has irregularities. The shape is preferred. When an organic EL element substrate or the like is manufactured using the electromagnetic wave releasable flexible device substrate, the metal base material can have irregularities on the contact surface with air, thereby improving heat diffusion. This is because the heat dissipation can be improved.

  As a method for forming irregularities, for example, a method of directly embossing, etching, sandblasting, frosting, stamping or the like on the surface of a metal substrate, or a method of forming an irregular pattern using a photoresist or the like. Can be mentioned.

  As a method for producing the metal substrate used in the present invention, a general method can be used, which is appropriately selected according to the type of metal material, the thickness of the metal substrate, and the like. For example, a method of obtaining a single metal substrate or a method of obtaining a laminate of a metal substrate and an insulating layer by vapor-depositing a metal material on an insulating layer made of a polyimide film may be used. Among these, from the viewpoint of gas barrier properties, a method of obtaining a metal base material alone is preferable. In the case of a method of obtaining a metal base material alone, when the metal base material is a metal foil, the metal foil may be a rolled foil or an electrolytic foil, but because of its good gas barrier properties Rolled foil is preferred.

4). Others The substrate for an electromagnetic wave releasable flexible device used in the present invention has at least the electromagnetic wave releasable pressure-sensitive adhesive layer, the insulating layer, and the metal substrate, but may have other configurations as necessary. good. Specifically, as such another configuration, specifically, a release film is formed on the surface of the electromagnetic wave releasable pressure-sensitive adhesive layer, that is, a surface on which the support substrate of the electromagnetic wave releasable pressure-sensitive adhesive layer is bonded. It can have a release film to protect.

As the release film, for example, as illustrated in FIG. 4, the release film is formed on the surface of the electromagnetic wave peelable adhesive layer 3, and before the electromagnetic wave peelable adhesive layer is bonded to the support substrate, There is no particular limitation as long as other members can be adhered to the electromagnetic wave releasable pressure-sensitive adhesive layer or dust can be prevented from adhering and handling properties can be improved.
The material constituting such a release film is not particularly limited as long as it can be attached to the electromagnetic wave-releasable pressure-sensitive adhesive layer before irradiation with an electromagnetic wave and can be easily peeled off. Can be used.
Specifically, a PET film having a silicone resin, fluorine resin, or acrylic resin layer on the adhesive surface can be used. A PET film can be preferably used. This is because it can be particularly excellent in handling properties.

Moreover, in this invention, as said other structure, what has a support substrate bonded together by the said electromagnetic wave peelable adhesive layer, More specifically, as shown in FIG. It is preferable that the support substrate 11 is bonded on the surface opposite to the surface on which the metal substrate 1 is bonded. This is because even when the metal substrate has flexibility, an electronic element portion such as an organic EL or a TFT can be stably formed on the insulating layer.
Note that the reference numerals in FIG. 5 are the same as those in FIG.

  The support substrate used in the present invention can be bonded to the electromagnetic wave releasable pressure-sensitive adhesive layer, and supports the electromagnetic wave releasable flexible device substrate of the present invention so as not to be deformed.

  As a material constituting such a support substrate, it can be bonded to the electromagnetic wave releasable pressure-sensitive adhesive layer, can be supported so as not to deform the electromagnetic wave releasable flexible device substrate, and can transmit electromagnetic waves. If it is a thing, it will not specifically limit, For example, a transparent resin substrate and glass can be mentioned. In the present invention, among these, glass is preferable from the viewpoints of transparency and heat resistance.

  The surface roughness Ra of the support substrate used in the present invention is not particularly limited as long as the surface of the insulating layer can be made smooth. Specifically, although it is different, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less.

  The thickness of the support substrate used in the present invention is not particularly limited as long as it can satisfy the above-described characteristics, and any thickness is acceptable as long as it does not cause trouble in the manufacturing process. Good.

The region of the electromagnetic wave releasable pressure-sensitive adhesive layer to which the support substrate in the present invention is bonded is not particularly limited as long as the insulating layer can be made smooth, for example, the electromagnetic wave releasable pressure-sensitive adhesive layer. The entire surface of the film and a part of the electromagnetic wave releasable pressure-sensitive adhesive layer.
In this step, the entire surface of the electromagnetic wave releasable pressure-sensitive adhesive layer is particularly preferable. This is because the insulating layer can be fixed in a smoother state.

In the present invention, the method for producing an electromagnetic wave releasable flexible device substrate in the case of including the support substrate is not particularly limited as long as it can form each of the above components with high thickness accuracy. Preparing a substrate for an electromagnetic wave releasable flexible device including a metal substrate, an insulating layer and an electromagnetic wave releasable pressure-sensitive adhesive layer; An insulating laminate having an insulating layer formed on the metal substrate and the metal substrate; an electromagnetic wave releasable support substrate having the support substrate and an electromagnetic wave releasable adhesive layer formed on the support substrate; And laminating the metal substrate contained in the insulating laminate and the electromagnetic wave peelable adhesive layer contained in the electromagnetic wave peelable support substrate , The supporting substrate, the electromagnetic wave-peelable pressure-sensitive adhesive layer, the metal substrate and the insulating layer may be a method such as that formed in this order.
In the present invention, among others, a method of bonding a support substrate to the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate, or the metal base and the insulating layer formed on the metal base An insulating laminate having the above-mentioned support substrate and an electromagnetic wave-releasable support substrate having an electromagnetic wave-releasable adhesive layer formed on the support substrate, and a metal substrate included in the insulating laminate, and the electromagnetic wave The method is preferably a method in which the electromagnetic wave releasable adhesive layer contained in the releasable support substrate is bonded. By preparing a laminate using such a metal substrate and a support substrate as a support, and bonding them together, the method has excellent process passability and has an electromagnetic wave releasability having a support substrate on the electromagnetic wave releasable adhesive layer. This is because the flexible device substrate can be stably formed.

As an application of the electromagnetic wave releasable flexible device substrate of the present invention, it can be used for a TFT substrate or an organic EL element substrate, and in particular, there is little deterioration of an electronic element part such as a TFT or an organic EL element, and it is highly accurate. It is preferably used for a TFT substrate or an organic EL element that is required.
In addition, as a TFT substrate, it can be used as a TFT array substrate of a display apparatus, for example, It is preferable that it is used especially for the TFT array substrate by which the outstanding switching characteristic is requested | required.
Examples of such a display device include a liquid crystal display device, an organic EL display device, and electronic paper. In addition to the display device, a circuit such as an RFID and a sensor can be exemplified.
Moreover, when an electronic element part is an organic EL element, as a use, an illuminating device and a passive matrix type organic EL display apparatus are mentioned.

B. Next, a method for manufacturing an electronic device according to the present invention will be described.
An electronic device manufacturing method according to the present invention is an electronic device having a flexible metal base, an insulating layer formed on the metal base, and an electronic element portion formed on the insulating layer. A preparation method for preparing a substrate for an electromagnetic wave releasable flexible device having a support substrate on the electromagnetic wave releasable adhesive layer, and forming an electronic element part on the insulating layer of the electromagnetic wave releasable flexible device substrate An electromagnetic wave irradiation step of irradiating an electromagnetic wave to the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate having the electronic element portion, and the electromagnetic wave peelable flexible device after the electromagnetic wave irradiation step And a peeling step of peeling the support substrate from the substrate.

Such a method for manufacturing an electronic device of the present invention will be described with reference to the drawings. FIG. 6 is a process diagram showing an example of a method for manufacturing an electronic device of the present invention. As illustrated in FIG. 6, the electronic device manufacturing method of the present invention includes a metal substrate 1, an insulating layer 2 formed on one surface of the metal substrate 1, and the other of the metal substrate 1. The electromagnetic wave releasable adhesive layer 3 of the electromagnetic wave releasable flexible device substrate 10 having the electromagnetic wave releasable adhesive layer 3 formed on the surface of the substrate and having the electromagnetic wave releasable property is bonded to the support substrate 11, A preparation step (FIG. 6A) for preparing a substrate for an electromagnetic wave releasable flexible device having a support substrate on the adhesive layer, and an electromagnetic wave releasable flexible device having a support substrate on the electromagnetic wave releasable adhesive layer by the above preparation step An electronic element part forming step (FIG. 6B) for forming a TFT 20 as an electronic element part on the insulating layer 2 of the substrate 10 and an electromagnetic wave peelable flexible device substrate 10 having the TFT 20 An electromagnetic wave irradiation step (FIG. 6 (c)) for irradiating the electromagnetic wave peelable adhesive layer 3 with an electromagnetic wave, a peeling step (FIG. 6 (d)) for peeling the support substrate 11 from the electromagnetic wave peelable flexible device substrate, The TFT substrate 30 having the TFT 20 as the electronic element is obtained.
The TFT 20 includes a source electrode 22S, a drain electrode 22D and a semiconductor layer 21 formed on the insulating layer 3, and a gate insulating film 24 formed on the source electrode 22S, the drain electrode 22D and the semiconductor layer 21. And a gate electrode 23G formed on the gate insulating film 24.

According to the present invention, by using the above-mentioned substrate for electromagnetic wave peelable flexible device as the substrate for forming the above electronic element portion, the above-mentioned electronic element portion forming step can be performed in a stable state of the above electromagnetic wave peelable flexible device substrate. It can be carried out. For this reason, the said electronic element part can be formed stably.
Moreover, by performing an electromagnetic wave irradiation process, since a support substrate can be easily peeled in a peeling process and an electronic element can be taken out, it can be excellent in handling property.

The method for manufacturing an electronic device of the present invention includes the above preparation step, electronic device portion forming step, electromagnetic wave irradiation step, and peeling step.
Hereinafter, each process of the manufacturing method of the electronic device of this invention is demonstrated.

1. Preparatory process The preparatory process in this invention is a process of preparing the board | substrate for electromagnetic wave peelable flexible devices which has a support substrate on the above-mentioned electromagnetic wave peelable flexible device board | substrate, ie, the said electromagnetic wave peelable adhesive layer.
Note that the electromagnetic wave releasable flexible device substrate having a support substrate on the electromagnetic wave releasable pressure-sensitive adhesive layer is the same as the content described in the above section “A. Electromagnetic wave releasable flexible device substrate”. Description of is omitted.

In this step, the method for preparing such a substrate for an electromagnetic wave releasable flexible device is not particularly limited as long as it is a method capable of preparing each layer formed with high thickness accuracy. The method described in the section “4. Others” of “Peelable Flexible Device Substrate” can be used. In particular, in this step, the electromagnetic wave peelable adhesive layer of the substrate for electromagnetic wave peelable flexible devices is used as a support substrate. Or an electromagnetic wave having an insulating laminate having an insulating layer formed on the metal substrate and the metal substrate, and an electromagnetic wave releasable adhesive layer formed on the support substrate and the support substrate. A peelable support substrate, a metal base material contained in the insulating laminate, and an electromagnetic wave peelable adhesive contained in the electromagnetic wave peelable support substrate It is preferable that a method of attaching the door. By preparing a laminate using such a metal substrate and a support substrate as a support, and bonding them together, the method has excellent process passability and has an electromagnetic wave releasability having a support substrate on the electromagnetic wave releasable adhesive layer. This is because the flexible device substrate can be stably formed.
In this step, if a release film is formed on the electromagnetic wave-releasable pressure-sensitive adhesive layer, a release film peeling process for peeling the release film may be performed as necessary.

2. Electronic element part formation process The electronic element part formation process in this invention is a process of forming an electronic element part on the insulating layer of the said substrate for electromagnetic wave peelable flexible devices prepared by the said preparatory process.

  The electronic element portion formed on the insulating layer in this step is not particularly limited as long as high formation accuracy is required, and examples thereof include organic EL elements and TFTs. Hereinafter, the description will be divided into the organic EL element and the TFT.

(1) Organic EL element The organic EL element formed in this step is a back electrode layer formed on the insulating layer, an EL layer formed on the back electrode layer and including at least an organic light emitting layer, and the above And a transparent electrode layer formed on the EL layer.
Such an organic EL element will be described with reference to the drawings. As illustrated in FIG. 7, the organic EL element used in the present invention is a back electrode layer 41 formed on the insulating layer and an EL layer formed on the back electrode layer 41 and including at least an organic light emitting layer. 42 and a transparent electrode layer 43 formed on the EL layer 42. The organic EL element 40 is a top emission type that extracts the light L from the transparent electrode layer 43 side.

This step can be performed in a stable state of the electromagnetic wave peelable flexible device substrate. Therefore, when an organic EL element is formed as the electronic element part, the organic EL element can be stably formed.
Moreover, since the support substrate can be easily peeled in the peeling step by performing an electromagnetic wave irradiation step on the electromagnetic wave peelable pressure-sensitive adhesive layer, for example, a heat peelable pressure-sensitive adhesive layer containing a heat peelable resin that is cured by heating is used. Compared with the case where it is used, the electronic element portion is exposed to a high temperature and can be free from defects such as thermal deterioration. Therefore, the EL element can be prevented from being exposed to a high temperature. As a result, it is possible to suppress the EL layer from being deteriorated by heat, causing uneven brightness and shortening the element life.
Further, when an organic EL element substrate is formed using such an electromagnetic wave releasable flexible device substrate, the organic EL element substrate can have the above metal base material. Since it can be released through the substrate, the EL element can be less deteriorated by heat.
Hereinafter, each structure of such an organic EL element is demonstrated.

(A) Back electrode layer The back electrode layer in this step is formed on the insulating layer. In the organic EL element, since light is extracted from the transparent electrode layer side, the back electrode layer may or may not have transparency.

  The material of the back electrode layer is not particularly limited as long as it is a conductive material. For example, Au, Ta, W, Pt, Ni, Pd, Cr, Cu, Mo, alkali metal, alkaline earth metal Simple metals such as, oxides of these metals, Al alloys such as AlLi, AlCa, and AlMg, Mg alloys such as MgAg, alloys such as Ni alloys, Cr alloys, alkali metal alloys, alkaline earth metal alloys, etc. Can be mentioned. These conductive materials may be used alone, in combination of two or more kinds, or may be laminated using two or more kinds. In addition, conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, zinc oxide, indium oxide, and aluminum zinc oxide (AZO) can also be used.

The back electrode layer may have a metal electrode formed on the insulating layer and a transparent electrode formed on the metal electrode layer. That is, the back electrode layer may be a laminate of a metal electrode and a transparent electrode. For example, an organic EL device in which a metal electrode, a transparent electrode, a hole injecting and transporting layer, an organic light emitting layer, an electron injecting and transporting layer, and a transparent electrode layer are sequentially stacked on the insulating layer can be obtained. In this case, since the back electrode layer is a laminate of a metal electrode and a transparent electrode, a conductive material having a work function of about 5.0 eV such as ITO can be used for the transparent electrode. By forming the hole injecting and transporting layer thereon, it is possible to easily transport charges. Further, the optical path length can be adjusted by controlling the thickness of the transparent electrode.
As the material of the metal electrode, the above-described simple metal, oxides of these metals, alloys, and the like can be used. Moreover, as a material of the transparent electrode, the above-described conductive oxide can be used.

The said back electrode layer may be formed in the whole surface, and may be formed in pattern shape. When the electronic device of the present invention is used in a lighting device, the back electrode layer is formed on one surface. When the electronic element of the present invention is used for a passive matrix organic EL display device, the back electrode layer is formed in a pattern.
The formation method and thickness of the back electrode layer can be the same as those of an electrode in a general organic EL element.

(B) EL layer The EL layer in this step is formed on the back electrode layer, includes an organic light emitting layer, and has one or more organic layers including at least the organic light emitting layer. That is, the EL layer is a layer including at least an organic light-emitting layer, and the layer configuration is a layer having one or more organic layers. Usually, when forming an EL layer by a coating method, it is difficult to stack a large number of layers in relation to the solvent, so the EL layer often has one or two organic layers, It is possible to further increase the number of layers by devising an organic material so that the solubility in a solvent is different or by combining a vacuum deposition method.

Examples of the layer formed in the EL layer other than the organic light emitting layer include a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer. The hole injection layer and the hole transport layer may be integrated. Similarly, the electron injection layer and the electron transport layer may be integrated. In addition, as a layer formed in the EL layer, a hole or an electron penetrating like a carrier block layer is prevented, and further, diffusion of excitons is prevented to confine excitons in the light emitting layer. Examples thereof include a layer for increasing the coupling efficiency.
Thus, the EL layer often has a laminated structure in which various layers are laminated, and there are many types of laminated structures.

  Each layer constituting the EL layer can be the same as that used in a general organic EL display device.

(C) Transparent electrode layer The transparent electrode layer in this step is formed on the EL layer. In the organic EL element, since light is extracted from the transparent electrode layer side, the transparent electrode layer has transparency.

  The material for the transparent electrode layer is not particularly limited as long as it is a conductive material capable of forming a transparent electrode. For example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, zinc oxide, A conductive oxide such as indium oxide or zinc aluminum oxide (AZO) can be used.

The transparent electrode layer may be formed on one surface or may be formed in a pattern. When using the electronic device manufactured by the manufacturing method of this invention for an illuminating device, a transparent electrode layer is formed in one surface. Moreover, when using the electronic element manufactured by the manufacturing method of this invention for a passive matrix type organic electroluminescence display, a transparent electrode layer is formed in pattern shape.
The formation method and thickness of the transparent electrode layer can be the same as those of an electrode in a general organic EL element.

(2) TFT
The TFT formed in this step is formed on the insulating layer.
In this step, the electromagnetic wave peelable flexible device substrate can be bonded and fixed to the support substrate, and deformation of the electromagnetic wave peelable flexible device substrate can be suppressed. For this reason, the TFT can be formed stably.
Moreover, since the said electromagnetic wave peelable adhesive layer can perform a peeling process easily by performing an electromagnetic wave irradiation process, for example, when using the heat peelable adhesive layer containing the heat peelable resin hardened | cured by heating In comparison, the electronic element portion can be exposed to a high temperature and can be free from defects such as thermal degradation, so that the TFT can be prevented from thermal degradation and deterioration of transistor characteristics.

As the structure of the TFT, for example, a top gate structure (forward stagger type) as shown in FIGS. 6 and 8 already described, and a bottom gate structure (reverse stagger type) as shown in FIGS. 9A and 9B are used. And a coplanar structure as shown in FIGS. 10 (a) and 10 (b). In the case of the top gate structure (forward stagger type) and the bottom gate structure (reverse stagger type), a top contact structure and a bottom contact structure can be further exemplified. These structures are appropriately selected according to the type of semiconductor layer constituting the TFT.
8 to 10 are the same as those in FIG. 9 and 10, a protective layer 25 is formed.

  The semiconductor layer constituting the TFT is not particularly limited as long as it can be formed on an insulating layer. For example, silicon, an oxide semiconductor, or an organic semiconductor is used.

As the silicon, polysilicon or amorphous silicon can be used.
Examples of the oxide semiconductor include zinc oxide (ZnO), titanium oxide (TiO), magnesium zinc oxide (Mg _x Zn _1-x O), cadmium zinc oxide (Cd _x Zn _1-x O), and cadmium oxide (CdO). ), Indium oxide (In ₂ O ₃ ), gallium oxide (Ga ₂ O ₃ ), tin oxide (SnO ₂ ), magnesium oxide (MgO), tungsten oxide (WO), InGaZnO-based, InGaSnO-based, InGaZnMgO-based, InAlZnO-based InFeZnO, InGaO, ZnGaO, and InZnO can be used.
Examples of organic semiconductors include π-electron conjugated aromatic compounds, chain compounds, organic pigments, and organosilicon compounds. More specifically, pentacene, tetracene, thiophen oligomer derivatives, phenylene derivatives, phthalocyanine compounds, polyacetylene derivatives, polythiophene derivatives, cyanine dyes and the like can be mentioned.

Especially, it is preferable that a semiconductor layer is an oxide semiconductor layer which consists of the above-mentioned oxide semiconductor. Although the electrical characteristics of an oxide semiconductor change due to the influence of water and oxygen, since the metal base material has a gas barrier property against water vapor, deterioration of the characteristics of the semiconductor can be suppressed.
The method for forming the semiconductor layer and the thickness thereof can be the same as those in general.

The gate electrode, source electrode, and drain electrode that constitute the TFT are not particularly limited as long as they have desired conductivity, and a conductive material that is generally used for TFTs can be used. Examples of such materials include Ta, Ti, Al, Zr, Cr, Nb, Hf, Mo, Au, Ag, Pt, Mo-Ta alloys, W-Mo alloys, ITO, IZO and other inorganic materials, and And organic materials having conductivity such as PEDOT / PSS.
The formation method and thickness of the gate electrode, source electrode, and drain electrode can be the same as those in general.

As the gate insulating film constituting the TFT, the same one as a gate insulating film in a general TFT can be used. For example, silicon oxide, silicon nitride, aluminum oxide, tantalum oxide, barium strontium titanate (BST) Insulating inorganic materials such as lead zirconate titanate (PZT), acrylic resins, phenolic resins, fluorine resins, epoxy resins, cardo resins, vinyl resins, imide resins, novolac resins, etc. Insulating organic materials such as insulating organic materials can be used.
The formation method and thickness of the gate insulating film can be the same as a general one.

A protective film may be formed on the TFT. The protective film is provided to protect the TFT. For example, the semiconductor layer can be prevented from being exposed to moisture or the like contained in the air. By forming the protective film, deterioration of the TFT performance with time can be reduced. For example, silicon oxide or silicon nitride is used as such a protective film.
The method for forming the protective film and the thickness thereof can be the same as those in general.

3. Electromagnetic wave irradiation process The electromagnetic wave irradiation process in this invention is a process of irradiating the said electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate which has the said electronic element part with an electromagnetic wave.

In this step, as the method of irradiating the electromagnetic wave peelable adhesive layer with electromagnetic waves, the electromagnetic wave peelable adhesive resin contained in the electromagnetic wave peelable adhesive layer is cured to reduce the adhesiveness to the adherend, The method is not particularly limited as long as it is a method capable of stably peeling the support substrate, and a method of irradiating all areas of the adhesion region bonded to the support substrate of the electromagnetic wave peelable adhesive layer, A method of irradiating a part of the adhesion region can be used.
In the present invention, it is particularly preferable to irradiate all the areas of the bonding area. This is because the electromagnetic wave releasable pressure-sensitive adhesive layer can be prevented from remaining, and the subsequent processability can be improved.

  Further, the irradiation direction of the electromagnetic wave is not particularly limited as long as the electromagnetic wave releasable pressure-sensitive adhesive resin contained in the electromagnetic wave releasable pressure-sensitive adhesive layer is cured and can reduce the adhesion to the adherend. However, there is a method of irradiating electromagnetic waves from the insulating layer side or from the support substrate side. However, since the metal substrate shields the electromagnetic waves, it is preferable to irradiate from the support substrate side.

  As the light source for irradiating the electromagnetic wave in this step, a general electromagnetic light source can be used, and examples thereof include an ultrahigh pressure mercury lamp, a low pressure mercury lamp, and a metal halide lamp.

4). Peeling process The peeling process in this invention is a process of peeling a support substrate from the said board | substrate for electromagnetic wave peelable flexible devices.

  In this step, the method of peeling off the support substrate is not particularly limited as long as the electronic device can be stably taken out. A general peeling method such as peeling from the end can be used.

5. Manufacturing method of electronic device The manufacturing method of the electronic device of this invention has the said preparatory process, an electronic device part formation process, an electromagnetic wave irradiation process, and a peeling process at least.

  The electronic device manufactured by the present invention has the metal base and the insulating layer. Since such a metal base material and an insulating layer are the same as the content described in the above-mentioned "A. Electromagnetic wave peelable flexible device substrate", description here is abbreviate | omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described using examples and comparative examples.

[Preparation Example 1]
1. Preparation of electromagnetic wave releasable adhesive resin Acrylic adhesive composition (trade name: E-306, acrylic polymer (adhesive main ingredient) + energy ray polymerizable oligomer + energy ray polymerizable monomer + polymerization initiator, acrylic polymer: Copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate and acrylonitrile, mass ratio of constituent monomers: n-butyl acrylate + methyl methacrylate + 2-hydroxyethyl acrylate / acrylonitrile (95/5), acrylic polymer Weight average molecular weight: about 650,000, energy ray polymerizable oligomer: polyurethane acrylate oligomer, energy ray polymerizable monomer: dipentaerythritol triacrylate, polymerization initiator: 1-hydroxy-cyclohexyl-pheny (Lu-ketone) is mixed with 100 parts by mass of a crosslinking agent (trade name: L-45, isocyanate-based crosslinking agent, solid content 45%, manufactured by Nippon Polyurethane Co., Ltd.), and a mixed solvent of toluene and methyl ethyl ketone (trade name). : KT11, mass ratio 1: 1, manufactured by DIC Graphics Co., Ltd.) It was diluted with 87 parts by mass and sufficiently dispersed to prepare a coating solution 1 for forming an electromagnetic wave peelable adhesive layer.

[Evaluation of electromagnetic wave peelable adhesive layer]
Subsequently, on the support substrate (non-alkali glass OA-10GF (0.7 mm thickness manufactured by Nippon Electric Glass Co., Ltd.)), the coating solution 1 for forming an electromagnetic wave releasable pressure-sensitive adhesive layer so that the thickness after drying becomes 10 μm. The whole surface was coated with an applicator to form an adhesive layer. Then, after heating for 15 minutes at 80 ° C., a release sheet (PET separator, trade name: SP-PET-01, film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc.) was laminated. Thus, the electromagnetic wave peelable adhesive layer forming glass substrate 1 having the electromagnetic wave peelable adhesive layer 1 was produced.

  After sampling the electromagnetic wave releasable adhesive layer 1 on the glass substrate (support substrate), using a thermal analyzer (TG 8120 (manufactured by Rigaku Corporation)), a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. And then heated to 100 ° C. for 60 minutes, allowed to cool in a nitrogen atmosphere for 15 minutes or more, and then based on the weight after cooling when measured at a heating rate of 10 ° C./min. When the thermogravimetric / differential heat (TG-DTA) measurement was performed and the temperature at which the weight of the sample decreased by 1% was measured, it was 236 ° C.

[Preparation Example 2]
In preparing the cured product comprising the pressure-sensitive adhesive composition, an electromagnetic wave-releasable pressure-sensitive adhesive layer-forming coating solution 2 containing the following pressure-sensitive adhesive composition 2 was prepared. The coating solution is 1,3-dioxolane at room temperature so that the electromagnetic wave-releasable pressure-sensitive adhesive layer-forming coating solution 2 is diluted so that the solid content concentration (wt%) is 32.9%. It was obtained by stirring the pressure-sensitive adhesive composition for 1 hour and completely dissolving it.

(Adhesive composition 2)
Polyester resin: High molecular weight saturated copolyester resin (“NP-101S50EO” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts by weight (in solid content)
Isocyanate crosslinking agent: Trimethylolpropane / tolylene diisocyanate adduct (trade name “Coronate L”) 7.5 parts by weight Bismaleimide compound: N, N ′-(4,4′-diphenylmethane) bismaleimide (BMI-) 1) 5 parts by weight Antioxidant: hindered antioxidant (trade name “IRGANOX1010”) 3 parts by weight Fluorine resin: fluoroethylene / vinyl ether alternating polymer (trade name “Lumiflon LF200”) 12 parts by weight Energy ray polymerizable Oligomer: Polyurethane acrylate Oligomer: 15 parts by weight Energy ray polymerizable monomer: Dipentaerythritol triacrylate: 15 parts by weight Polymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone: 5 parts by weight

  Subsequently, on the support substrate (non-alkali glass OA-10GF (0.7 mm thickness manufactured by Nippon Electric Glass Co., Ltd.)), the coating solution 2 for forming the electromagnetic wave-releasable pressure-sensitive adhesive layer so that the film thickness after drying becomes 10 μm. The whole surface was coated with an applicator to form an adhesive layer. Then, after heating at 120 ° C. for 5 minutes, drying and peeling sheet (PET separator, trade name: SP-PET-01, film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc.) were laminated. Thus, the electromagnetic wave peelable adhesion layer forming glass substrate 2 having the electromagnetic wave peelable adhesive layer 2 was produced.

  After sampling the electromagnetic wave releasable adhesive layer 2 on the glass substrate (support substrate), using a thermal analyzer (TG 8120 (manufactured by Rigaku Corporation)), a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. And then heated to 100 ° C. for 60 minutes, allowed to cool in a nitrogen atmosphere for 15 minutes or more, and then based on the weight after cooling when measured at a heating rate of 10 ° C./min. When the thermogravimetric / differential heat (TG-DTA) measurement was performed and the temperature at which the weight of the sample decreased by 1% was measured, it was 243 ° C.

[Preparation Example 3]
As thermosetting polyimide, polyimide (A) was synthesized as follows, and polyimide (B) was further synthesized.

<Synthesis of polyimide (A, B)>
1,2,4,5-cyclohexanetetracarboxylic dianhydride 20.35 g (0.090 mol), polyoxypropylenediamine (manufactured by Mitsui Chemicals Fine Co., Ltd., Jeffamine D2000) 118.81 g (0.060 mol) N-methyl-2-pyrrolidone (91.50 g) was added under a nitrogen stream, heated to 200 ° C. and subjected to an imidization reaction for 3 hours, and the produced water was separated using a Dean-Stark apparatus. After the reaction, it was confirmed that there was no distillation of water, and the mixture was allowed to cool to room temperature (23 ° C.) to obtain a reaction product (polyimide (A)). Whether or not polyimide (A) is produced can be determined by confirming the IR spectrum and confirming the characteristic absorption of the imide ring of ν (C═O) 1770 and 1706 cm ⁻¹ . Next, 12.4 g (0.060 mol) of 4,4′-diaminodiphenyl ether and 9.74 g of N-methyl-2-pyrrolidone are added to the polyimide (A), and the mixture is heated to 200 ° C. and imidized for 3 hours. The reaction was carried out and the produced water was separated using a Dean-Stark apparatus. After the imidation reaction, it was confirmed that the distillation of water stopped, the reaction product solution was allowed to cool to room temperature, and a reaction product (polyimide (B)) was obtained in the reaction product solution. Whether or not polyimide (B) was produced was confirmed from the IR spectrum.

  In preparing a cured product composed of the pressure-sensitive adhesive composition, an electromagnetic wave-releasable pressure-sensitive adhesive layer-forming coating solution 3 containing the following pressure-sensitive adhesive composition 3 was prepared. The coating liquid was a mixed liquid of N, N′-dimethylacetamide (DMAc) and 1,3-dioxolane (the mixing ratio of the mixed liquid was DMAc: 1,3-dioxolane = 30%: 70% by volume ratio) ), The adhesive composition is stirred for 1 hour at room temperature so that the electromagnetic wave-releasable adhesive layer-forming coating solution 3 is diluted so that the solid content concentration (% by weight) is 25%. It was obtained by dissolving.

(Adhesive composition 3)
Polyimide (B): 100 parts by weight Crosslinking agent N, N ′-(4,4′-diphenylmethane) bismaleimide: 15 parts by weight Thermal base generator (San Apro Co., Ltd., U-CAT 5002): 1 part by weight Antioxidation Agent (Ciba Japan Co., Ltd., IRGANOX 1098): 3 parts by weight Energy ray polymerizable oligomer: Polyurethane acrylate oligomer: 15 parts by weight Energy ray polymerizable monomer: dipentaerythritol triacrylate: 15 parts by weight Polymerization initiator: 1-hydroxy -Cyclohexyl-phenyl-ketone): 5 parts by weight

  Subsequently, on the support substrate (non-alkali glass OA-10GF (0.7 mm thickness manufactured by Nippon Electric Glass Co., Ltd.)), the coating solution 3 for forming the electromagnetic wave releasable pressure-sensitive adhesive layer so that the film thickness after drying becomes 10 μm. The whole surface was coated with an applicator to form an adhesive layer. Then, after heating for 5 minutes at 180 degreeC, it dried and the peeling sheet (PET separator, brand name: SP-PET-01, film thickness: 38 micrometers, Mitsui Chemicals Tosero Co., Ltd. product) was laminated. Thus, the electromagnetic wave peelable adhesive layer forming glass substrate 3 having the electromagnetic wave peelable adhesive layer 3 was produced.

  After sampling the electromagnetic wave releasable adhesive layer 3 on the glass substrate (support substrate), using a thermal analyzer (TG 8120 (manufactured by Rigaku Corporation)), a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. And then heated to 100 ° C. for 60 minutes, allowed to cool in a nitrogen atmosphere for 15 minutes or more, and then based on the weight after cooling when measured at a heating rate of 10 ° C./min. When the thermogravimetric / differential heat (TG-DTA) measurement was performed and the temperature at which the weight of the sample decreased by 1% was measured, it was 341 ° C.

[Example 1]
4.0 g (20 mmol) of 4,4′-diaminodiphenyl ether (ODA) and 8.65 g (80 mmol) of paraphenylenediamine (PPD) were put into a 500 ml separable flask, and 200 g of dehydrated N-methyl-2 was added. -It dissolved in pyrrolidone (NMP), and it stirred, heating and monitoring with a thermocouple so that liquid temperature might be 50 degreeC with an oil bath under nitrogen stream. After confirming that they were completely dissolved, 29.1 g (99 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added thereto gradually over 30 minutes. After completion of the addition, the mixture was stirred at 50 ° C. for 5 hours. Then, it cooled to room temperature and obtained the polyimide precursor solution.

  After coating the polyimide precursor solution with a die coater on the surface of SUS304 foil (manufactured by Toyo Seiki Co., Ltd.) having a thickness of 20 μm cut into a 15 cm square, and drying in the atmosphere at 80 ° C. for 60 minutes, In a nitrogen atmosphere, heat treatment was performed at 350 ° C. for 1 hour (temperature increase rate: 10 ° C./min, natural cooling) to form a polyimide film (insulating layer) having a thickness of 10 μm. The thin film device substrate 1 did not warp even when the temperature or humidity environment changed.

  Next, the entire surface of the thin film device substrate 1 is coated with the above-mentioned coating solution 1 for forming an electromagnetic wave-releasable adhesive layer with an applicator so that the film thickness after drying becomes 10 μm, thereby forming an electromagnetic wave-releasable adhesive layer. did. Then, after heating for 15 minutes at 80 ° C., a release sheet (PET separator, trade name: SP-PET-01, film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc.) was laminated. Thus, the electromagnetic wave peelable flexible device substrate 1 was produced.

[Example 2]
On the thin film device substrate 1, the electromagnetic wave-releasable pressure-sensitive adhesive layer-forming coating liquid 2 was applied on the entire surface with an applicator so that the film thickness after drying was 10 μm, thereby forming an electromagnetic wave-releasable pressure-sensitive adhesive layer. Then, after heating at 120 ° C. for 5 minutes, a release sheet (PET separator, trade name: SP-PET-01, film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc.) was laminated. Thus, the electromagnetic wave peelable flexible device substrate 2 was produced.

[Example 3]
On the thin film device substrate 1, the electromagnetic wave-releasable pressure-sensitive adhesive layer-forming coating solution 3 was applied over the entire surface with an applicator so that the film thickness after drying was 10 μm, thereby forming an electromagnetic wave-releasable pressure-sensitive adhesive layer. Then, after heating for 5 minutes at 180 degreeC, it dried and the peeling sheet (PET separator, brand name: SP-PET-01, film thickness: 38 micrometers, Mitsui Chemicals Tosero Co., Ltd. product) was laminated. In this way, an electromagnetic wave peelable flexible device substrate 3 was produced.

[Example 4]
After peeling off the release sheet of the electromagnetic wave releasable flexible device substrate 1, the support substrate is placed on the support substrate (non-alkali glass OA-10GF (0.7 mm thickness manufactured by Nippon Electric Glass Co., Ltd.)) with the adhesive layer facing down. Is placed in contact with the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate, laminated using a 2 kg roller, allowed to stand at room temperature and humidity for 20 minutes, and then at 150 ° C. for 60 minutes. Heated.

  The following device elements were laminated on the polyimide film (insulating layer) contained in the electromagnetic wave releasable flexible device substrate. An aluminum film as a first adhesion layer was formed with a thickness of 5 nm by a DC sputtering method (film formation pressure 0.2 Pa (argon), input power 1 kW, film formation time 10 seconds). Next, a silicon oxide film as a second adhesion layer is formed with a thickness of 100 nm by an RF magnetron sputtering method (deposition pressure 0.3 Pa (argon: oxygen = 3: 1), input power 2 kW, deposition time 30 minutes). Thus, a flexible device substrate was obtained.

Next, a TFT having a bottom gate / bottom contact structure was fabricated on the flexible device substrate. First, an aluminum film having a thickness of 100 nm was formed as a gate electrode film, a resist pattern was formed by photolithography, and then wet etching was performed with a phosphoric acid solution, and the aluminum film was patterned into a predetermined pattern to form a gate electrode. Next, silicon oxide having a thickness of 300 nm was formed as a gate insulating film on the entire surface so as to cover the gate electrode. This gate insulating film uses an RF magnetron sputtering apparatus and is applied to a 6-inch SiO ₂ target with a power of 1.0 kW (= 3 W / cm ² ), a pressure of 1.0 Pa, and a gas of argon + O ₂ (50%). It formed on film-forming conditions. Thereafter, a resist pattern was formed by photolithography and then dry etching was performed to form a contact hole. Next, a 100 nm thick titanium film, aluminum film, and IZO film are deposited on the entire surface of the gate insulating film to form a source electrode and a drain electrode, and then a resist pattern is formed by a photolithography method, and then a hydrogen peroxide solution is formed. Then, wet etching was continuously performed with a phosphoric acid solution, and the titanium film was patterned into a predetermined pattern to form a source electrode and a drain electrode. At this time, the source electrode and the drain electrode were formed on the gate insulating film so as to have a pattern apart from a portion other than directly above the central portion of the gate electrode.

Next, an InGaZnO amorphous oxide thin film (InGaZnO ₄ ) with an In: Ga: Zn ratio of 1: 1: 1 was formed on the entire surface so as to cover the source electrode and the drain electrode so as to have a thickness of 25 nm. The amorphous oxide thin film is 4 inches of InGaZnO (In: Ga: Zn = 1: 1: 1) using an RF magnetron sputtering apparatus under conditions of room temperature (25 ° C.) and Ar: O ₂ of 30:50. It was formed using a target. After that, a resist layer is applied onto the amorphous oxide thin film by spin coating, dried by a hot plate, a resist pattern is formed by photolithography, then wet-etched with an oxalic acid solution, and the amorphous oxide thin film is patterned. An amorphous oxide thin film having a predetermined pattern was formed. The amorphous oxide thin film thus obtained was formed on the gate insulating film so as to contact the source electrode and the drain electrode on both sides and straddle the source electrode and the drain electrode. Subsequently, 100 nm thick silicon oxide was formed as a protective film by RF magnetron sputtering so as to cover the whole, and then a resist pattern was formed by photolithography, followed by dry etching.
Next, after annealing at 200 ° C. for 1 hour in the air, an EL partition layer was formed using an acrylic positive resist to fabricate a TFT substrate. After depositing an EL layer on the TFT substrate so as to be white, an IZO film was deposited as an electrode, and EL was sealed using a barrier film.

After irradiating with ultraviolet rays (integrated light amount: 500 mj / cm ² ) using a fusion H / bulb lamp as a light source from the glass substrate side, the produced flexible device was peeled from the glass plate (support substrate). After that, a flexible color filter formed on the PEN film was bonded next, and a flexible diagonal 4.7 inch, resolution 85 dpi, 320 × 240 × RGB (QVGA) active matrix drive full color EL display was produced. About the produced full color EL display, the operation | movement was confirmed with the scanning voltage 15V, the beta voltage 10V, and the power supply voltage 10V.

[Example 5]
An EL element was produced in the same manner as in Example 4 of the element except that the electromagnetic wave peelable flexible device substrate 2 was used instead of the electromagnetic wave peelable flexible device substrate 1.

[Example 6]
An EL element was produced in the same manner as in Example 4 except that the electromagnetic wave peelable flexible device substrate 3 was used instead of the electromagnetic wave peelable flexible device substrate 1.

[Example 7]
After peeling off the release sheet of the electromagnetic wave releasable adhesive layer-formed glass substrate 1, the exposed surface of the SUS304 foil is brought into contact with the electromagnetic wave releasable adhesive layer on the glass substrate on the adhesive layer. And laminated using a 2 kg roller, left at room temperature and humidity for 20 minutes, and then heated at 150 ° C. for 60 minutes. Thus, an electromagnetic wave peelable flexible device substrate 4 (an electromagnetic wave peelable flexible device substrate with a supporting substrate) was obtained.
Thereafter, an EL element was produced in the same manner as in Example 4 of the element.

[Example 8]
After peeling off the release sheet of the electromagnetic wave peelable adhesive layer-formed glass substrate 2, the exposed surface of the SUS304 foil is in contact with the electromagnetic wave peelable adhesive layer on the glass substrate on the adhesive layer. And laminated using a 2 kg roller, left at room temperature and humidity for 20 minutes, and then heated at 150 ° C. for 60 minutes. Thereby, the substrate 5 for electromagnetic wave peelable flexible devices (the substrate for electromagnetic wave peelable flexible devices with a support substrate) was obtained.
Thereafter, an EL element was produced in the same manner as in Example 4 of the element.

[Example 9]
After peeling off the release sheet of the electromagnetic wave peelable adhesive layer-formed glass substrate 3, the exposed surface of the SUS304 foil is in contact with the electromagnetic wave peelable adhesive layer on the glass substrate on the adhesive layer. And laminated using a 2 kg roller, left at room temperature and humidity for 20 minutes, and then heated at 150 ° C. for 60 minutes. Thereby, the substrate 6 for electromagnetic wave peelable flexible devices (substrate for electromagnetic wave peelable flexible devices with a support substrate) was obtained.
Thereafter, an EL element was produced in the same manner as in Example 4 of the element.

[Comparative example]
The following device elements were laminated on the polyimide film (insulating layer) contained in the thin film device substrate 1. An aluminum film as a first adhesion layer was formed with a thickness of 5 nm by a DC sputtering method (film formation pressure 0.2 Pa (argon), input power 1 kW, film formation time 10 seconds). Next, a silicon oxide film as a second adhesion layer is formed with a thickness of 100 nm by an RF magnetron sputtering method (deposition pressure 0.3 Pa (argon: oxygen = 3: 1), input power 2 kW, deposition time 30 minutes). Thus, a flexible device substrate was obtained.

  Next, a TFT having a bottom gate / bottom contact structure was fabricated on the flexible device substrate. First, an aluminum film having a thickness of 100 nm is formed as a gate electrode film, and then a resist pattern is formed by photolithography, and then wet etching with a phosphoric acid solution causes the substrate to be bent, and the aluminum film is patterned into a predetermined pattern. It was impossible to do.

DESCRIPTION OF SYMBOLS 1 ... Metal base material 2 ... Insulating layer 3 ... Electromagnetic wave peelable adhesion layer 10 ... Electromagnetic wave peelable flexible device substrate 11 ... Support substrate 20 ... TFT
DESCRIPTION OF SYMBOLS 21 ... Semiconductor layer 22S ... Source electrode 22D ... Drain electrode 23G ... Gate electrode 24 ... Gate insulating layer 25 ... Protective layer 30 ... TFT substrate 40 ... Organic EL element 41 ... Back electrode layer 42 ... EL layer 43 ... Transparent electrode layer

Claims (12)

A flexible metal substrate;
An insulating layer formed on at least one surface of the metal substrate;
An electromagnetic wave releasable pressure-sensitive adhesive layer comprising an electromagnetic wave releasable pressure-sensitive adhesive resin formed on the other surface of the metal substrate and having electromagnetic wave releasability;
An electromagnetic wave releasable flexible device substrate characterized by comprising:   The electromagnetic wave peelable pressure-sensitive adhesive resin includes any one of an acrylic pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyimide pressure-sensitive adhesive, an electromagnetic wave polymerizable monomer or an electromagnetic wave polymerizable oligomer, and an electromagnetic wave polymerization initiator. The electromagnetic wave peelable flexible device substrate according to claim 1.   The 1% weight reduction temperature of the said electromagnetic wave peelable adhesive resin is 200 degreeC or more, The board | substrate for electromagnetic wave peelable flexible devices of Claim 1 or Claim 2 characterized by the above-mentioned.   The said insulating layer contains a polyimide resin, The board | substrate for electromagnetic wave peelable flexible devices of any one of Claim 1- Claim 3 characterized by the above-mentioned. The said polyimide resin has a repeating unit represented by the following general formula (1), The board | substrate for electromagnetic wave peelable flexible devices of Claim 4 characterized by the above-mentioned.

(In Formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, and R ¹ and R ² that are repeated may be the same or different. n is a natural number of 1 or more.)   6. The electromagnetic wave releasable flexible device substrate according to claim 1, wherein a release film is formed on a surface of the electromagnetic wave releasable pressure-sensitive adhesive layer.   The substrate for electromagnetic wave peelable flexible devices according to any one of claims 1 to 5, wherein a support substrate is bonded to the electromagnetic wave peelable adhesive layer. A method of manufacturing an electronic device having a flexible metal substrate, an insulating layer formed on the metal substrate, and an electronic device portion formed on the insulating layer,
A preparation step of preparing the electromagnetic wave peelable flexible device substrate according to claim 7;
An electronic element part forming step of forming an electronic element part on the insulating layer of the electromagnetic wave peelable flexible device substrate;
An electromagnetic wave irradiation step of irradiating the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device substrate having the electronic element part with an electromagnetic wave;
A peeling step of peeling the support substrate from the electromagnetic wave peelable flexible device substrate after the electromagnetic wave irradiation step,
The manufacturing method of the electronic element characterized by having.   The said preparatory process bonds a support substrate to the electromagnetic wave peelable adhesive layer of the electromagnetic wave peelable flexible device board | substrate as described in the claim in any one of Claims 1-6. The manufacturing method of the electronic device of Claim 8.   The preparatory step is an electromagnetic wave releasability having an insulating laminate having an insulating layer formed on the metal base material and the metal base material, and an electromagnetic wave releasable adhesive layer formed on the support substrate and the support substrate. The support substrate is prepared, and the metal base material contained in the insulating laminate and the electromagnetic wave peelable adhesive layer contained in the electromagnetic wave peelable support substrate are bonded together. The manufacturing method of the electronic element of description.   The electronic element part is formed on the insulating layer, a back electrode layer, an electroluminescence layer formed on the back electrode layer and including at least an organic light emitting layer, and a transparent electrode formed on the electroluminescence layer It is an organic electroluminescent element which has a layer, The manufacturing method of the electronic element of any one of Claim 8-10 characterized by the above-mentioned.   The method of manufacturing an electronic device according to any one of claims 8 to 10, wherein the electronic device section is a thin film transistor formed on the insulating layer.

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