JP7205687B2 - LAMINATED PRODUCT, LAMINATED PRODUCTION METHOD, AND HEAT-RESISTANT POLYMER FILM WITH METAL-CONTAINING LAYER - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate, a method for producing the laminate, and a heat-resistant polymer film with a metal-containing layer.

In recent years, for the purpose of reducing the weight, size, thickness, and flexibility of functional elements such as semiconductor elements, MEMS elements, and display elements, the development of techniques for forming these elements on polymer films has been actively carried out. That is, conventionally, as a material for the base material of electronic parts such as information communication equipment (broadcasting equipment, mobile radio, portable communication equipment, etc.), radar, high-speed information processing equipment, etc., it has heat resistance and the signal of information communication equipment Ceramics have been used to support higher frequencies (up to the GHz band), but ceramics are not flexible and are difficult to thin. uses a polymer film as the substrate.

When forming functional elements such as semiconductor elements, MEMS elements, and display elements on the surface of a polymer film, it is ideal to use the so-called roll-to-roll process, which takes advantage of the flexibility that characterizes polymer films. It is said that However, in industries such as the semiconductor industry, the MEMS industry, the display industry, and the like, so far, process technologies have been established for rigid planar substrates such as wafer bases or glass substrate bases. Therefore, in order to form a functional element on a polymer film using the existing infrastructure, the polymer film is attached to a rigid support made of an inorganic material such as a glass plate, a ceramic plate, a silicon wafer, or a metal plate. , forming desired elements thereon, and then separating from the support.

By the way, in the process of forming a desired functional element in a laminate obtained by laminating a polymer film and an inorganic support, the laminate is often exposed to high temperatures. For example, formation of functional elements such as polysilicon and oxide semiconductors requires a process in a temperature range of about 200.degree. C. to 600.degree. In the production of a hydrogenated amorphous silicon thin film, a temperature of about 200 to 300° C. may be applied to the film. Heating may be required. Therefore, the polymer films constituting the laminate are required to have heat resistance, but as a matter of fact, only a limited number of polymer films can be put to practical use in such a high temperature range. In general, it is conceivable to use a pressure-sensitive adhesive or an adhesive for laminating a polymer film to a support. Adhesives) are also required to have heat resistance. However, since ordinary bonding adhesives and pressure-sensitive adhesives do not have sufficient heat resistance, bonding using adhesives or pressure-sensitive adhesives cannot be applied when the forming temperature of the functional element is high.

Since it is believed that there are no pressure-sensitive adhesives or adhesives with sufficient heat resistance, conventionally, in the above-mentioned applications, a polymer solution or a polymer precursor solution is coated on an inorganic substrate, and then the inorganic substrate is coated. A technique of drying and curing to form a film and using it for the application has been adopted. However, since the polymer film obtained by such means is fragile and easily torn, the functional element formed on the surface of the polymer film is often broken when peeled off from the inorganic substrate. In particular, it is extremely difficult to peel a large-area film from an inorganic substrate, and it is almost impossible to obtain an industrially viable yield.
In view of this situation, as a laminate of a polymer film and an inorganic substrate for forming a functional element, a polyimide film that has excellent heat resistance and is tough and can be thinned is applied to the inorganic substrate via a silane coupling agent. Laminates bonded to each other have been proposed (see, for example, Patent Documents 1 to 3).

Japanese Patent No. 5152104 Japanese Patent No. 5304490 Japanese Patent No. 5531781

In the laminate described above, by interposing a layer containing a silane coupling agent between the inorganic substrate and the polyimide film, the inorganic substrate is prevented from being peeled off from the polyimide film before or during device formation. After forming the device, the inorganic substrate can be easily peeled off from the polyimide film. That is, in the laminate described above, the silane coupling agent is physically or chemically interposed between the inorganic substrate and the polyimide film to increase the initial adhesive strength therebetween. Moreover, by using a silane coupling agent, it is possible to suppress the increase in adhesive strength between the two due to heat during device formation.

The present inventors have made intensive studies on the laminate described above. As a result, if the electrification (peeling electrification) when the polyimide film is peeled off from the inorganic substrate is suppressed, the device formed on the polyimide film is destroyed by the peeling electrification when the polyimide film is peeled off from the inorganic substrate. We thought that the possibility could be reduced.

Therefore, the present inventors have found that if a metal-containing layer (for example, an ITO (indium tin oxide) layer) containing a metal, metal oxide, or metal nitride is provided on a polyimide film, peeling electrification occurs. I thought it would be difficult. However, when the metal-containing layer is provided on the polyimide film, sufficient adhesion to the inorganic substrate cannot be obtained.

In this respect, the present inventors further conducted intensive research. As a result, it was found that sufficient initial adhesion between the polyimide film and the inorganic substrate can be obtained by setting the polar component ^γsh of the surface energy of the surface of the metal-containing layer within a predetermined range. was completed.

That is, the laminate according to the present invention is
An inorganic substrate, a silane coupling agent layer, a metal-containing layer containing a metal, a metal oxide, or a metal nitride, and a heat-resistant polymer film are laminated in this order,
The polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less.

According to the above configuration, since the metal-containing layer is laminated on the heat-resistant polymer film (for example, polyimide film), separation electrification is less likely to occur. Further, since the polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less, there is sufficient space between the heat-resistant polymer film and the inorganic substrate. Initial adhesion is obtained. This is also clear from the examples. In this regard, the present inventors found that when the polar component ^γsh of the surface energy obtained from the contact angle of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less, OH groups are formed on the surface of the metal-containing layer. It is speculated that the OH group and the silane coupling agent layer are bound by hydrogen bonding or chemical reaction, resulting in strong adhesion between the heat-resistant polymer film and the inorganic substrate.

In the above configuration, the metal oxide is preferably indium tin oxide (ITO).

When the metal oxide is indium tin oxide, the polar component ^γsh is easily set to 10 dyn/cm or more and 60 dyn/cm or less. In addition, it is easily available. Indium tin oxide is an inorganic mixture of indium oxide and tin oxide.

In the above configuration, the 90° initial peel strength between the heat-resistant polymer film and the inorganic substrate is preferably 0.05 N/cm or more.

When the 90° initial peel strength is 0.05 N/cm or more, peeling of the heat-resistant polymer film from the inorganic substrate before or during device formation can be suitably prevented.

In the above configuration, when the heat-resistant polymer film is peeled off from the inorganic substrate at a temperature of 21° C. and a humidity of 50% RH at a peeling angle of 90 degrees and a peeling speed of 20 mm/sec, the heat-resistant polymer film side surface is preferably 0.3 kV or less.

When the peeling electrification voltage is 0.3 kV or less, the possibility of the device formed on the heat-resistant polymer film being destroyed by peeling electrification when the heat-resistant polymer film is peeled off from the inorganic substrate is remarkably reduced. be able to.

Further, the method for manufacturing a laminate according to the present invention includes:
A step A of forming a silane coupling agent layer on an inorganic substrate to obtain a first laminate;
A step B of forming a metal-containing layer containing a metal, metal oxide, or metal nitride on the heat-resistant polymer film;
Step C of obtaining a second laminate by forming oxygen defects on the surface of the metal-containing layer such that the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less. When,
and a step D of bonding the first laminate and the second laminate together.

According to the said structure, the said laminated body can be obtained suitably. That is, since the laminate obtained by the method for producing the laminate has the metal-containing layer laminated on the heat-resistant polymer film, peeling electrification is less likely to occur. In addition, in the laminate obtained by the method for producing the laminate, the polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less. Sufficient initial adhesion is obtained between the polymer film and the inorganic substrate.

Further, the heat-resistant polymer film with a metal-containing layer according to the present invention is
a heat-resistant polymer film;
a metal-containing layer containing a metal, a metal oxide, or a metal nitride;
The polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less.

According to the above configuration, since the metal-containing layer is laminated on the heat-resistant polymer film, peeling electrification is less likely to occur when peeling after bonding to the inorganic substrate. In addition, since the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less, when it is attached to an inorganic substrate having a silane coupling agent layer formed on the surface, the inorganic Sufficient initial adhesion to the substrate can be obtained.

According to the present invention, it is possible to provide a laminate in which separation electrification is unlikely to occur and which has sufficient initial adhesive strength between the heat-resistant polymer film and the inorganic substrate. Moreover, the manufacturing method of the said laminated body can be provided. It is also possible to provide a heat-resistant polymer film with a metal-containing layer that can be used to produce the laminate.

It is a schematic diagram of an experimental apparatus for applying a silane coupling agent to a glass substrate.

Embodiments of the present invention will be described below.

The laminate according to this embodiment is
An inorganic substrate, a silane coupling agent layer, a metal-containing layer containing a metal, a metal oxide, or a metal nitride, and a heat-resistant polymer film are laminated in this order,
The polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less.

The heat-resistant polymer film with a metal-containing layer according to this embodiment is
a heat-resistant polymer film;
a metal-containing layer containing a metal, a metal oxide, or a metal nitride;
A polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less.

The heat-resistant polymer film with a metal-containing layer according to the present embodiment can be a layered product that does not have an inorganic substrate and a silane coupling agent layer in the laminate described below. Therefore, hereinafter, the laminate will be described, and the heat-resistant polymer film with the metal-containing layer will be described therein.

The laminate has a metal-containing layer laminated on a heat-resistant polymer film. Therefore, separation electrification is less likely to occur.

The laminated body was obtained by peeling the heat-resistant polymer film from the inorganic substrate at a temperature of 21° C. and a humidity of 50% RH at a peeling angle of 90 degrees and a peeling speed of 20 mm/sec. is preferably 0.3 kV or less, more preferably 0.2 kV or less, and even more preferably 0.1 kV or less. When the peeling electrification voltage is 0.3 kV or less, the possibility of the device formed on the heat-resistant polymer film being destroyed by peeling electrification when the heat-resistant polymer film is peeled off from the inorganic substrate is remarkably reduced. be able to. The details of the method for measuring the peeling electrification voltage are according to the method described in Examples.

As described above, in the laminate, the polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less. The polar component ^γsh is preferably 20 dyn/cm or more and 55 dyn/cm or less, more preferably 30 dyn/cm or more and 50 dyn/cm or less. Since the polar component ^γsh of the surface energy of the surface of the metal-containing layer on the front silane coupling agent layer side is 10 dyn/cm or more and 60 dyn/cm or less, there is sufficient initial energy between the heat-resistant polymer film and the inorganic substrate. Adhesive strength is obtained.

In the laminate, the 90° initial peel strength between the heat-resistant polymer film and the inorganic substrate is preferably 0.05 N/cm or more, more preferably 0.09 N/cm or more, and 0.05 N/cm or more. It is more preferably 1 N/cm or more. The 90° initial peel strength is preferably 0.25 N/cm or less, more preferably 0.2 N/cm or less. When the 90° initial peel strength is 0.05 N/cm or more, it is possible to prevent the heat-resistant polymer film from peeling off from the inorganic substrate before or during device formation. Further, when the 90° initial peel strength is 0.25 N/cm or less, the inorganic substrate and the heat-resistant polymer film are easily peeled off after device formation. That is, when the 90° initial peel strength is 0.25 N/cm or less, even if the peel strength between the inorganic substrate and the heat-resistant polymer film slightly increases during device formation, the two can be easily peeled off. Cheap.
In this specification, the 90° initial peel strength refers to the 90° peel strength between the inorganic substrate and the heat-resistant polymer film after the laminate is heat-treated at 200°C for 1 hour in an air atmosphere.

The measurement conditions for the 90° initial peel strength are as follows.
The heat-resistant polymer film is peeled off at an angle of 90° from the inorganic substrate.
Measurement is performed 5 times, and the average value is taken as the measured value.
Measurement temperature; room temperature (25°C)
Peeling speed; 100mm/min
Atmosphere; atmospheric measurement sample width; 2.5 cm
More specifically, according to the method described in Examples.

<Heat-resistant polymer film>
As used herein, the heat-resistant polymer is a polymer having a melting point of 400° C. or higher, preferably 500° C. or higher, and a glass transition temperature of 250° C. or higher, preferably 320° C. or higher, more preferably 380° C. or higher. . In the following, to avoid complication, it is simply referred to as a polymer. As used herein, the melting point and glass transition temperature are determined by differential thermal analysis (DSC). If the melting point exceeds 500° C., it may be determined whether or not the melting point has been reached by observing the thermal deformation behavior when heated at the relevant temperature.

Examples of the heat-resistant polymer film (hereinafter also simply referred to as a polymer film) include polyimide-based resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (eg, aromatic polyimide resin, alicyclic polyimide resin); polyethylene , polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate (for example, wholly aromatic polyester, semi-aromatic polyester); copolymerized (meth)acrylates represented by polymethyl methacrylate; polycarbonates cellulose acetate; cellulose nitrate; aromatic polyamide; polyvinyl chloride; polyphenol; polyarylate;
However, since the polymer film is assumed to be used in a process involving heat treatment at 450° C. or higher, the polymer films exemplified are limited in practical application. Among the polymer films, preferred are films using so-called super engineering plastics, and more specifically, aromatic polyimide films, aromatic amide films, aromatic amideimide films, aromatic benzoxazole films, aromatic group benzothiazole films, aromatic benzimidazole films, and the like.

The details of a polyimide resin film (also referred to as a polyimide film), which is an example of the polymer film, will be described below. In general, a polyimide resin film is prepared by applying a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent to a support for producing a polyimide film and drying it to form a green film (hereinafter referred to as (also referred to as "polyamic acid film"), and further subjecting the green film to a high-temperature heat treatment on a polyimide film-producing support or in a state in which the green film is peeled off from the support to cause a dehydration ring-closing reaction.

Application of the polyamic acid (polyimide precursor) solution includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, curtain coating, slit die coating, etc. Application of conventionally known solutions. means can be used as appropriate.

The diamines constituting the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like which are commonly used in polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferred, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferred. The use of aromatic diamines having a benzoxazole structure makes it possible to exhibit high heat resistance, high elastic modulus, low thermal shrinkage, and low coefficient of linear expansion. Diamines may be used alone or in combination of two or more.

Aromatic diamines having a benzoxazole structure are not particularly limited, and examples include 5-amino-2-(p-aminophenyl)benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole, 5 -amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzoxazole, 2,2'-p-phenylenebis(5-aminobenzoxazole), 2,2' -p-phenylenebis(6-aminobenzoxazole), 1-(5-aminobenzoxazolo)-4-(6-aminobenzoxazolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo [1,2-d:5,4-d′]bisoxazole, 2,6-(4,4′-diaminodiphenyl)benzo[1,2-d:4,5-d′]bisoxazole, 2, 6-(3,4′-diaminodiphenyl)benzo[1,2-d:5,4-d′]bisoxazole, 2,6-(3,4′-diaminodiphenyl)benzo[1,2-d: 4,5-d']bisoxazole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:5,4-d']bisoxazole, 2,6-(3,3' -diaminodiphenyl)benzo[1,2-d:4,5-d']bisoxazole and the like.

Examples of aromatic diamines other than the above aromatic diamines having a benzoxazole structure include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl )-2-propyl]benzene (bisaniline), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4 '-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl ] sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4' -diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[ 4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1, 2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,3- bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane , 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3 ,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1 , 1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-amino phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4- (4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl] ether, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-amino phenoxy)benzoyl]benzene, 4,4'-bis[(3-aminophenoxy)benzoyl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis[4-( 3-aminophenoxy)phenyl]propane, 3,4′-diaminodiphenyl sulfide, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane , bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane , bis[4-(3-aminophenoxy)phenyl]sulfoxide, 4,4′-bis[ 3-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethyl benzyl)phenoxy]benzophenone, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone , 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene , 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)- α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino- 6-cyanophenoxy)-α,α-dimethylbenzyl]benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4 '-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3 ,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino -4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3 ,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzoyl)benzene, 1,4-bis(3-amino-4-phenoxybenzoyl)benzene, 1,3 -bis(4-amino-5-phenoxybenzoyl)benzene, 1,4-bis(4-amino-5-phenoxybenzoyl)benzene, 1,3-bis(3-amino-4-biphenyl noxybenzoyl)benzene, 1,4-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,3-bis(4-amino-5-biphenoxybenzoyl)benzene, 1,4-bis(4- amino-5-biphenoxybenzoyl)benzene, 2,6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, and some of the hydrogen atoms on the aromatic rings of said aromatic diamines or all of which are halogen atoms, alkyl or alkoxyl groups having 1 to 3 carbon atoms, cyano groups, or halogen atoms having 1 to 3 carbon atoms in which some or all of the hydrogen atoms of an alkyl or alkoxyl group are substituted with halogen atoms and aromatic diamines substituted with alkyl groups or alkoxyl groups.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane and the like.
Examples of the alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(2,6-dimethylcyclohexylamine).
The total amount of diamines other than aromatic diamines (aliphatic diamines and alicyclic diamines) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of all diamines. is. In other words, aromatic diamines are preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of all diamines.

Tetracarboxylic acids constituting polyamic acid include aromatic tetracarboxylic acids (including their acid anhydrides), aliphatic tetracarboxylic acids (including their acid anhydrides), and alicyclic tetracarboxylic acids, which are commonly used in polyimide synthesis. Acids (including anhydrides thereof) can be used. Among them, aromatic tetracarboxylic anhydrides and alicyclic tetracarboxylic anhydrides are preferable, aromatic tetracarboxylic anhydrides are more preferable from the viewpoint of heat resistance, and alicyclic anhydrides are preferable from the viewpoint of light transmittance. Group tetracarboxylic acids are more preferred. When these are acid anhydrides, one or two anhydride structures may be present in the molecule, but preferably those having two anhydride structures (dianhydrides) are good. Tetracarboxylic acids may be used alone, or two or more of them may be used in combination.

Examples of alicyclic tetracarboxylic acids include alicyclic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3′,4,4′-bicyclohexyltetracarboxylic acid. Carboxylic acids, and their acid anhydrides. Among these, dianhydrides having two anhydride structures (for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4 '-bicyclohexyltetracarboxylic dianhydride) are preferred. The alicyclic tetracarboxylic acids may be used alone, or two or more of them may be used in combination.
The alicyclic tetracarboxylic acid is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of the total tetracarboxylic acids when transparency is important.

The aromatic tetracarboxylic acid is not particularly limited, but is preferably a pyromellitic acid residue (that is, having a structure derived from pyromellitic acid), more preferably an acid anhydride thereof. Examples of such aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 ,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis[4-(3,4-di carboxyphenoxy)phenyl]propanoic anhydride and the like.
The aromatic tetracarboxylic acid is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of the total tetracarboxylic acids when heat resistance is important.

The thickness of the polymer film is preferably 3 μm or more, more preferably 11 μm or more, still more preferably 24 μm or more, and still more preferably 45 μm or more. Although the upper limit of the thickness of the polymer film is not particularly limited, it is preferably 250 μm or less, more preferably 150 μm or less, and still more preferably 90 μm or less for use as a flexible electronic device.

The average CTE between 30° C. and 300° C. of said polymer film is preferably −5 ppm/° C. to +20 ppm/° C., more preferably −5 ppm/° C. to +15 ppm/° C., more preferably 1 ppm. /°C to +10 ppm/°C. When the CTE is within the above range, the difference in coefficient of linear expansion with a general support (inorganic substrate) can be kept small, and peeling of the polymer film and the inorganic substrate can be prevented even when subjected to a process of applying heat. can be avoided. Here, CTE is a factor representing reversible expansion and contraction with respect to temperature. The CTE of the polymer film refers to the average value of the CTE in the machine direction (MD direction) and the CTE in the width direction (TD direction) of the polymer film. The method for measuring the CTE of the polymer film is according to the method described in Examples.

The heat shrinkage of the polymer film between 30° C. and 500° C. is preferably ±0.9%, more preferably ±0.6%. Thermal shrinkage is a factor representing irreversible expansion and contraction with respect to temperature.

The tensile strength at break of the polymer film is preferably 60 MPa or more, more preferably 120 MPa or more, and still more preferably 240 MPa or more. Although the upper limit of the tensile strength at break is not particularly limited, it is practically less than about 1000 MPa. When the tensile strength at break is 60 MPa or more, it is possible to prevent the polymer film from breaking when peeled from the inorganic substrate. The tensile strength at break of the polymer film refers to the average value of the tensile strength at break in the machine direction (MD direction) and the tensile strength at break in the width direction (TD direction) of the polymer film. The method for measuring the tensile strength at break of the polymer film is according to the method described in Examples.

The tensile elongation at break of the polymer film is preferably 1% or more, more preferably 5% or more, and still more preferably 20% or more. When the tensile elongation at break is 1% or more, the handleability is excellent. The tensile elongation at break of the polymer film refers to the average value of the tensile elongation at break in the machine direction (MD direction) and the tensile elongation at break in the width direction (TD direction) of the polymer film. The method for measuring the tensile elongation at break of the polymer film is according to the method described in Examples.

The tensile modulus of the polymer film is preferably 3 GPa or more, more preferably 6 GPa or more, and still more preferably 8 GPa or more. When the tensile modulus is 3 GPa or more, the polymer film undergoes little elongation deformation when peeled from the inorganic substrate, and is excellent in handleability. The tensile modulus is preferably 20 GPa or less, more preferably 12 GPa or less, and even more preferably 10 GPa or less. When the tensile modulus is 20 GPa or less, the polymer film can be used as a flexible film. The tensile elastic modulus of the polymer film refers to the average value of the tensile elastic modulus in the machine direction (MD direction) and the tensile elastic modulus in the width direction (TD direction) of the polymer film. The method for measuring the tensile modulus of the polymer film is according to the method described in Examples.

The thickness unevenness of the polymer film is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. If the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow areas. The uneven thickness of the film can be obtained by measuring the thickness of the film by randomly extracting about 10 positions from the film to be measured using, for example, a contact-type film thickness meter, and calculating the thickness according to the following formula.
Film thickness unevenness (%)
= 100 x (maximum film thickness - minimum film thickness) / average film thickness

The polymer film is preferably obtained in the form of being wound up as a long polymer film with a width of 300 mm or more and a length of 10 m or more at the time of production. More preferred are those in the form of molecular films. When the polymer film is wound into a roll, it can be easily transported in the form of a heat-resistant polymer film wound into a roll.

In the polymer film, in order to ensure handleability and productivity, a lubricant (particles) having a particle diameter of about 10 to 1000 nm is added or contained in the polymer film in an amount of about 0.03 to 3% by mass. Therefore, it is preferable to provide the surface of the polymer film with fine irregularities to ensure the slipperiness.

<Metal-containing layer>
The polymer film is laminated with a metal-containing layer containing a metal, metal oxide, or metal nitride. The metal-containing layer is a layer having a certain degree of conductivity, and preferably has a composition that enables the peeling withstand voltage to be 0.3 kV or less.

The metal is not particularly limited as long as it has a certain degree of conductivity when formed into a metal-containing layer. Examples include Au, Ag, Cu, Pb, Zn, In, Sn, Fe, Al, Mo, W, Sb, Bi, Nb, Ti, etc. are mentioned.

The metal oxide and the metal nitride are not particularly limited as long as they have a certain degree of conductivity when formed into a metal-containing layer, and include indium tin oxide (ITO) and aluminum silicate. (Si--Al--O based composition), ZnO, Ga--Zn--O based, Sb--Zn--O based, TiN based, NbN based and the like.

<Method for Forming Metal-Containing Layer>
The metal-containing layer can be formed on the polymer film using a vapor deposition method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). As a result, a thin film having a uniform thickness of several nanometers to several tens of nanometers can be formed. Physical vapor deposition (PVD) includes vacuum deposition, sputtering, ion plating, MBE, laser ablation, and the like. Chemical vapor deposition (CVD) includes thermal CVD, plasma CVD, and the like. Among these, the sputtering method is particularly preferred from the viewpoints of obtaining a dense film and relatively easy film thickness control. The sputtering method includes a DC magnetron sputtering method, an RF magnetron sputtering method, and the like.
However, the method of forming the metal-containing layer in the present invention is not limited to this example, and is formed by applying a paste containing fine particles of the metal, metal oxide, or metal nitride, and then performing processing such as drying. You can also

The metal-containing layer has oxygen defects formed at least on its surface. As a result, the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less. Methods for forming oxygen vacancies in the metal-containing layer before oxygen vacancies are formed include, for example, UV/O3 irradiation _, atmospheric pressure plasma, vacuum plasma, flame treatment, electron beam treatment, and the like. The dose of UV/O ₃ and plasma can be appropriately adjusted so that the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less. Normally, when oxygen defects are not formed on the surface, the polar component ^γsh of the surface energy of the surface of the metal-containing layer does not fall within the range of 10 dyn/cm or more and 60 dyn/cm or less.

Since the metal-containing layer is subjected to a treatment (step C) for forming oxygen defects on the surface, the surface is cleaned by this treatment (UV/O3 irradiation _, atmospheric pressure plasma, vacuum plasma, etc.). . Therefore, in the laminate, contamination of foreign substances between the metal-containing layer and the silane coupling agent layer is suppressed. As a result, the laminate having the metal-containing layer can reduce the number of non-bonded portions (blister) having a diameter of 500 μm or more between the metal-containing layer and the silane coupling agent layer.

In addition, in the heating process for producing a polymer film, the heating temperature may vary depending on the position. For example, when a horizontally long polyimide film before heat curing is heated and cured, the degree of curing may differ between the central portion and both end portions due to the configuration of the heating furnace, etc. . Then, due to the difference in degree of curing, the central portion and both end portions may have different initial peel strengths to the inorganic substrate (distribution of the initial peel strength may occur). However, in this embodiment, a metal-containing layer having a relatively uniform thickness is laminated on the polymer film, and the inorganic substrate and the polymer film are bonded by the adhesive force between the metal-containing layer and the silane coupling agent layer. ing. Therefore, the initial peel strength distribution in the width direction can be reduced.

The absolute value of the difference between the CTE of the metal-containing layer and the CTE of the polymer film is preferably 20 ppm/°C or less, more preferably 12 ppm/°C or less, and 7 ppm/°C or less. More preferred. When the absolute value of the CTE difference is within the above numerical range, the warp of the polymer film is reduced and handling is facilitated.

<Inorganic substrate>
The inorganic substrate may be a plate-shaped substrate that can be used as a substrate made of an inorganic substance. , semiconductor wafers, and metal composites include laminates of these, those in which these are dispersed, and those in which these fibers are contained.

Examples of the glass plate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (no alkali), Borosilicate glass (microsheet), aluminosilicate glass, etc. are included. Among these, those having a coefficient of linear expansion of 5 ppm/K or less are desirable. "EAGLE", "AN100" manufactured by Asahi Glass Co., Ltd., "OA10" manufactured by Nippon Electric Glass Co., Ltd., "AF32" manufactured by SCHOTT Co., Ltd., and the like are desirable.

Examples of the semiconductor wafer include, but are not limited to, silicon wafer, germanium, silicon-germanium, gallium-arsenide, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, SiC, InP (indium phosphide), InGaAs, GaInNAs, Wafers of LT, LN, ZnO (zinc oxide), CdTe (cadmium telluride), ZnSe (zinc selenide), and the like can be mentioned. Among them, the wafer preferably used is a silicon wafer, and particularly preferably a mirror-polished silicon wafer having a size of 8 inches or more.

The metals include single element metals such as W, Mo, Pt, Fe, Ni, and Au, and alloys such as Inconel, Monel, Nimonic, carbon copper, Fe—Ni system Invar alloys, and Super Invar alloys. In addition to these metals, multi-layer metal plates obtained by adding other metal layers and ceramic layers are also included. In this case, if the overall coefficient of linear expansion (CTE) with the additional layer is low, Cu, Al, etc. may also be used for the main metal layer. The metal used for the additional metal layer is limited as long as it has properties such as strong adhesion to the polymer film, no diffusion, good chemical resistance and heat resistance. Suitable examples include Cr, Ni, TiN, Mo-containing Cu, etc., although they are not specific.

It is desirable that the planar portion of the inorganic substrate be sufficiently flat. Specifically, the PV value of surface roughness is 50 nm or less, more preferably 20 nm or less, still more preferably 5 nm or less. If it is coarser than this, the peel strength between the polymer film layer and the inorganic substrate may be insufficient.

Although the thickness of the inorganic substrate is not particularly limited, the thickness is preferably 10 mm or less, more preferably 3 mm or less, and even more preferably 1.3 mm or less from the viewpoint of handleability. Although the lower limit of the thickness is not particularly limited, it is preferably 0.07 mm or more, more preferably 0.15 mm or more, and still more preferably 0.3 mm or more.

<Silane coupling agent layer>
A silane coupling agent layer containing a silane coupling agent is provided on the inorganic substrate.

The silane coupling agent is physically or chemically interposed between the inorganic substrate and the metal-containing layer, and has the effect of increasing the adhesion between the inorganic substrate and the polymer film.
Although the coupling agent is not particularly limited, a silane coupling agent having an amino group or an epoxy group is preferable. Preferred specific examples of the silane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-( aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycid xypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane , 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris-(3-trimethoxysilane silylpropyl)isocyanurate, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and the like.

As the silane coupling agent, in addition to the above, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethylsilane, dimethoxy Dimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyllichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane, n-octyltrisilane Ethoxysilane, n-octyltrimethoxysilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, pentyltriethoxysilane, pentyltrichlorosilane, triacetoxymethylsilane, trichlorohexylsilane, trichloromethylsilane silane, trichlorooctadecylsilane, trichloropropylsilane, trichlorotetradecylsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, Vinyltris(2-methoxyethoxy)silane, trichloro-2-cyanoethylsilane, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, etc. can also be used. can.

Among the silane coupling agents, silane coupling agents having one silicon atom in one molecule are particularly preferred, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane and the like. If the process requires particularly high heat resistance, it is desirable to have an aromatic group connecting Si and an amino group.
As the coupling agent, in addition to the above, 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, butyl 3-mercaptopropionate, 3-(dimethoxymethylsilyl)- 1-propanethiol, 4-(6-mercaptohexaroyl) benzyl alcohol, 11-amino-1-undeceneol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoroacetic acid, 2,2′-( ethylenedioxy)diethanethiol, 11-mercaptoundecitri(ethylene glycol), (1-mercaptoundec-11-yl)tetra(ethyleneglycol), 1-(methylcarboxy)undec-11-yl)hexa(ethylene) glycol), hydroxyundecyl disulfide, carboxyundecyl disulfide, hydroxyhexadodecyl disulfide, carboxyhexadecyl disulfide, tetrakis(2-ethylhexyloxy)titanium, titanium dioctyloxybis(octylene glycolate), zirconium tributoxymonoacetylaceto zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate, 3-glycidyloxypropyltrimethoxysilane, 2,3-butanedithiol, 1-butanethiol, 2-butanethiol, cyclohexanethiol, cyclopentanethiol, 1-decanethiol, 1-dodecanethiol, 2-ethylhexyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 1-heptanethiol, 1-hexadecanethiol, hexyl Mercaptan, isoamyl mercaptan, isobutyl mercaptan, 3-mercaptopropionic acid, 3-methoxybutyl 3-mercaptopropionate, 2-methyl-1-butanethiol, 1-octadecanethiol, 1-octanethiol, 1-pentadecanethiol, 1 - pentanethiol, 1-propanethiol, 1-tetradecanethiol, 1-undecanethiol, 1-(12-mercaptododecyl)imidazole, 1-(11-mercaptoundecyl)imidazole, 1-(10-mercaptodecyl)imidazole, 1-(16-mercaptohexadecyl) imidazole, 1-(17-mercapto Heptadecyl)imidazole, 1-(15-mercapto)dodecanoic acid, 1-(11-mercapto)undecanoic acid, 1-(10-mercapto)decanoic acid and the like can also be used.

<Method for Forming Silane Coupling Agent Layer>
As a method for forming the silane coupling agent layer, a method of applying a silane coupling agent solution to the inorganic substrate, a vapor deposition method, or the like can be used. The silane coupling agent layer may be formed on the surface of the metal-containing layer.

Methods for applying the silane coupling agent solution include spin coating, curtain coating, dip coating, slit die coating, gravure coating, and bar coating using a solution of the silane coupling agent diluted with a solvent such as alcohol. Conventionally known means for applying a solution such as a coating method, a comma coating method, an applicator method, a screen printing method, and a spray coating method can be appropriately used.

The silane coupling agent layer can also be formed by vapor deposition, specifically, by exposing the inorganic substrate to the vapor of the silane coupling agent, that is, the silane coupling agent in a substantially gaseous state. . The vapor of the silane coupling agent can be obtained by heating the silane coupling agent in a liquid state to a temperature from 40° C. to about the boiling point of the silane coupling agent. The boiling point of the silane coupling agent varies depending on the chemical structure, but generally ranges from 100 to 250°C. However, heating at 200° C. or higher is not preferable because it may cause a side reaction on the side of the organic group of the silane coupling agent.
The environment in which the silane coupling agent is heated may be under pressure, under normal pressure, or under reduced pressure, but is preferably under normal pressure or under reduced pressure in order to promote vaporization of the silane coupling agent. Since many silane coupling agents are flammable liquids, it is preferable to carry out the vaporization operation in a sealed container, preferably after replacing the inside of the container with an inert gas.
Although the time for exposing the inorganic substrate to the silane coupling agent is not particularly limited, it is preferably within 20 hours, more preferably within 60 minutes, still more preferably within 15 minutes, and most preferably within 1 minute.
The temperature of the inorganic substrate while exposing the inorganic substrate to the silane coupling agent is an appropriate temperature between -50° C. and 200° C. depending on the type of silane coupling agent and the desired thickness of the silane coupling agent layer. is preferably controlled to

The film thickness of the silane coupling agent layer is extremely thin compared to inorganic substrates, polymer films, etc., and is negligible from the viewpoint of mechanical design. A thickness on the order of a molecular layer is sufficient. It is generally less than 400 nm, preferably 200 nm or less, more preferably 100 nm or less for practical use, more preferably 50 nm or less, still more preferably 10 nm or less. However, if the area is calculated to be 5 nm or less, the silane coupling agent layer may not form a uniform coating film but may exist in the form of clusters. The thickness of the silane coupling agent layer can be determined by ellipsometry or by calculation from the concentration and coating amount of the silane coupling agent solution at the time of coating.

<Method for manufacturing laminate>
A method for manufacturing a laminate according to this embodiment will be described below.
The method for manufacturing a laminate according to this embodiment includes:
A step A of forming a silane coupling agent layer on an inorganic substrate to obtain a first laminate;
A step B of forming a metal-containing layer containing a metal, metal oxide, or metal nitride on the heat-resistant polymer film;
A step of forming oxygen defects on the surface of the metal-containing layer so that the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less to obtain a second laminate. C and
At least a step D of bonding the first laminate and the second laminate.

<Process A>
In step A, a silane coupling agent layer is formed on an inorganic substrate to obtain a first laminate. Since the details of the method for forming the silane coupling agent layer on the inorganic substrate have already been explained, the explanation is omitted here.

<Step B>
In step B, a metal-containing layer is formed on the polymer film. Since the details of the method for forming the metal-containing layer on the polymer film have already been explained, the explanation is omitted here.

<Process C>
In step C, oxygen defects are formed on the surface of the metal-containing layer formed in step B to obtain a second laminate. The oxygen vacancies are formed so that the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less. Since the details of the method for forming oxygen defects on the surface of the metal-containing layer have already been explained, the explanation is omitted here.

<Process D>
In step D, the first laminate and the second laminate are bonded together. Specifically, the silane coupling agent layer formed on the inorganic substrate and the metal-containing layer formed on the polymer film are used as bonding surfaces, and they are bonded together under pressure and heat.

The pressurized heat treatment may be performed, for example, under atmospheric pressure or in a vacuum by pressing, laminating, roll laminating, or the like while heating. Alternatively, a method of pressurizing and heating while being placed in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing processing costs brought about by high productivity, press or roll lamination in an air atmosphere is preferred, and a method using rolls (roll lamination, etc.) is particularly preferred.

The pressure during the pressurized heat treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. When the pressure is 20 MPa or less, damage to the inorganic substrate can be suppressed. Further, when the pressure is 1 MPa or more, it is possible to prevent the occurrence of non-adhesive portions and insufficient adhesion. The temperature for the pressurized heat treatment is preferably 150°C to 400°C, more preferably 250°C to 350°C. When the polymer film is a polyimide film, if the temperature is too high, the polyimide film may be damaged, and if the temperature is too low, the adhesion tends to be weak.
The pressurized heat treatment can be performed in an atmospheric pressure atmosphere as described above, but is preferably performed in a vacuum in order to obtain a stable peel strength over the entire surface. At this time, the degree of vacuum obtained by a normal oil rotary pump is sufficient, and a degree of vacuum of about 10 Torr or less is sufficient.
As an apparatus that can be used for pressure heating treatment, for example, "11FD" manufactured by Imoto Seisakusho Co., Ltd. can be used for pressing in a vacuum, and a roll-type film laminator in a vacuum or a vacuum is used. For vacuum lamination using a film laminator or the like that applies pressure to the entire glass surface at once with a thin rubber film, for example, "MVLP" manufactured by Meiki Seisakusho Co., Ltd. can be used.

The pressurization and heat treatment can be performed separately into a pressurization process and a heating process. In this case, first, the polymer film and the inorganic substrate are pressurized (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, less than 120°C, more preferably 95°C or less) to ensure close contact between the two. Then, at low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or normal pressure at relatively high temperature (for example, 120 ° C. or higher, more preferably 120 to 250 ° C., more preferably 150 to 230 ° C. ), the chemical reaction at the adhesion interface is promoted, and the polymer film and the inorganic substrate can be laminated.

As described above, a laminate in which the inorganic substrate and the polymer film are bonded together can be obtained.
However, the method for manufacturing a laminate according to the present invention is not limited to this example. As another example, for example, a metal-containing layer is formed on a heat-resistant polymer film, and then the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less. forming oxygen vacancies on the surface of the metal-containing layer, forming a silane coupling agent layer on the metal-containing layer in which the oxygen vacancies are formed, and then placing an inorganic substrate on the silane coupling agent layer It is good also as pasting together.

<Method for manufacturing flexible electronic device>
When the laminate is used, an electronic device is formed on the polymer film of the laminate using existing equipment and processes for manufacturing electronic devices, and the polymer film is peeled off from the laminate to form a flexible electronic device. can be made.
In this specification, the electronic device means an electronic circuit including a wiring board having a single-sided, double-sided, or multilayer structure responsible for electrical wiring, active elements such as transistors and diodes, and passive devices such as resistors, capacitors, inductors, etc. Sensor elements that sense pressure, temperature, light, humidity, etc., biosensor elements, light emitting elements, liquid crystal displays, electrophoretic displays, image display elements such as self-luminous displays, wireless and wired communication elements, computing elements, memory elements, Refers to MEMS elements, solar cells, thin film transistors, and the like.

In the device structure manufacturing method of the present specification, after forming a device on the polymer film of the laminate produced by the method described above, the polymer film is peeled off from the inorganic substrate.

The method of peeling the polymer film with the device from the inorganic substrate is not particularly limited, but a method of rolling it up from the edge with tweezers or the like, making a cut in the polymer film, and attaching an adhesive tape to one side of the cut portion. A method of rolling up from the tape portion later, a method of vacuum-sucking one side of the notched portion of the polymer film and then rolling up from that portion, and the like can be employed. When peeling, if the cut portion of the polymer film bends with a small curvature, stress is applied to the device at that portion, which may destroy the device. is desirable. For example, it is desirable to wind the film while winding it on a roll having a large curvature, or to roll it using a machine configured so that the roll having a large curvature is positioned at the peeling portion.
The method of cutting the polymer film includes a method of cutting the polymer film with a cutting tool such as a knife, a method of cutting the polymer film by relatively scanning a laser and a laminate, and a method of cutting the polymer film with a water jet. There are a method of cutting the polymer film by relatively scanning the laminate, a method of cutting the polymer film while slightly cutting into the glass layer with a semiconductor chip dicing device, and the like, but the method is not particularly limited. Absent. For example, in adopting the above-described method, it is also possible to appropriately adopt techniques such as superimposing ultrasonic waves on the cutting tool or adding reciprocating motion or vertical motion to improve cutting performance.
It is also useful to attach another reinforcing base material in advance to the part to be peeled off, and peel off the entire reinforcing base material. If the flexible electronic device to be peeled is the backplane of the display device, it is also possible to obtain a flexible display device by first attaching the frontplane of the display device, integrating them on the inorganic substrate, and then peeling them off at the same time. be.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Production Example 1 (production of polyamic acid solution A)]
After purging the interior of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring bar, 223 parts by mass of 5-amino-2-(p-aminophenyl)benzoxazole (DAMBO), N, 4416 parts by mass of N-dimethylacetamide was added and dissolved completely. Next, together with 217 parts by mass of pyromellitic dianhydride (PMDA), Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries) in which colloidal silica (average particle size: 0.08 μm) is dispersed in dimethylacetamide is used as colloidal silica. is added so as to be 0.7% by mass with respect to the total polymer solid content in polyamic acid solution A, and stirred at a reaction temperature of 25 ° C. for 24 hours,
A brown and viscous polyamic acid solution A was obtained.

[Production Example 2 (production of polyamic acid solution B)]
After replacing the inside of a reaction vessel equipped with a nitrogen inlet tube, a thermometer, and a stirring rod with nitrogen, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 398 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were placed in the reaction vessel. , and 4,600 parts by mass of N,N-dimethylacetamide were added and stirred well so as to be uniform. Next, together with 147 parts by mass of paradianiline (PDA), Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries) in which colloidal silica (average particle size: 0.08 μm) is dispersed in dimethylacetamide is added to the colloidal silica polyamic acid solution. It was added so as to be 0.7% by mass with respect to the total polymer solid content in B, and stirred at a reaction temperature of 25° C. for 24 hours to obtain a brown and viscous polyamic acid solution B.

[Production Example 3 (production of polyamic acid solution C)]
After purging the interior of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring bar, pyromellitic anhydride (PMDA) and 4,4'-diaminodiphenyl ether (ODA) are placed in equivalent amounts in the reaction vessel, Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries) in which colloidal silica (average particle size: 0.08 μm) is dissolved in N,N-dimethylacetamide and dispersed in dimethylacetamide is added to polyamic acid solution C. It was added so as to be 0.7 mass with respect to the total solid content of the polymer, and stirred at a reaction temperature of 25° C. for 24 hours to obtain a brown and viscous polyamic acid solution C.

[Production Example 4 (Preparation of Polyimide Film 1)]
Using a die coater, the polyamic acid solution A obtained in Production Example 1 was applied onto an endless mirror-finished stainless steel endless belt (coating width: 1240 mm) and dried at 90 to 115° C. for 10 minutes. The polyamic acid film that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
The obtained green film was conveyed by a pin tenter so that the final pin sheet interval was 1140 mm, and heat-treated at 170 ° C. for 2 minutes in the first stage, 2 minutes at 230 ° C. in the second stage, and 6 minutes at 465 ° C. in the third stage. was applied to allow the imidization reaction to proceed. Thereafter, the film was cooled to room temperature for 2 minutes, and portions of both ends of the film having poor flatness were cut off with a slitter and rolled up into a roll to obtain a polyimide film 1 exhibiting a brown color.

[Production Example 5 (Preparation of polyimide film 2)]
A polyimide film 2 was obtained in the same manner as in Production Example 4 except that the polyamic acid solution B obtained in Production Example 2 was used.

[Production Example 6 (Preparation of polyimide film 3)]
A polyimide film 3 was obtained in the same manner as in Production Example 4 except that the polyamic acid solution C obtained in Production Example 3 was used and the heat treatment temperature in the third stage was set to 440°C.

[Production Example 7 (Preparation of polyimide film 4)]
A polyimide film 4 was obtained in the same manner as in Production Example 4, except that the heat treatment temperature in the third stage was 440°C.

[Production Example 8 (Preparation of polyimide film 5)]
A polyimide film 5 was obtained in the same manner as in Production Example 4, except that the heat treatment temperature in the third stage was 495°C.

<Thickness measurement of polyimide film>
The thicknesses of the polyimide films 1 to 5 were measured using a micrometer (Millitron 1245D manufactured by Finereuf Co., Ltd.). Table 1 shows the results.

<Tensile elastic modulus, tensile breaking strength, and tensile breaking elongation of polyimide film>
Polyimide films 1 to 5 were cut into strips of 100 mm×10 mm each in the machine direction (MD direction) and the width direction (TD direction) to obtain test pieces. A test piece was cut from the center portion in the width direction. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph (R), model name AG-5000A), the temperature is 25 ° C., the tensile speed is 50 mm / min, and the distance between chucks is 40 mm. Elastic modulus, tensile strength at break and tensile elongation at break were measured. Table 1 shows the results.

<Linear expansion coefficient (CTE) of polyimide film>
Polyimide films 1 to 5 are measured for expansion ratio under the following conditions in the machine direction (MD direction) and the width direction (TD direction), and are measured at intervals of 15 ° C. such as 30 ° C. to 45 ° C. and 45 ° C. to 60 ° C. This measurement was performed up to 300° C., and the average value of all measured values was calculated as CTE. Table 1 shows the results.
Equipment name; TMA4000S manufactured by MAC Science
Sample length; 20 mm
Sample width; 2 mm
Heating start temperature; 25°C
Heating end temperature; 400°C
Temperature rise rate; 5°C/min
atmosphere; argon

<Production of laminate>
(Example 1)
First, an ITO layer was formed on the polyimide film 1 obtained in Production Example 4 by a sputtering method. In this example, a roll-to-roll type sputtering apparatus was used. That is, in this embodiment, the polyimide film is unwound from the roll, moved to the unwinding chamber, the sputtering chamber, the pre-chamber, and the winding chamber to form an ITO layer on the polyimide film, and finally wound on the roll. adopted the take method. In the sputtering apparatus, the chambers are partitioned by slits. In the sputtering chamber, the film is in contact with a chill roll, and while being cooled by the chill roll (temperature: -5°C), a thin film is formed by an ITO target. Specifically, an ITO layer was formed on the polyimide film 1 as follows.

First, the polyimide film 1 obtained in Production Example 4 was slit to a width of 250 mm. Next, degassing was performed by unwinding the slitted 250 mm wide roll under vacuum and then winding it up again. Next, after waiting until the temperature became 3×10 ⁻⁶ Torr or less, a sputtering process was performed under the following conditions to form an ITO layer having a thickness of 15 nm on the polyimide film 1 . This step corresponds to step B of the present invention.
<Conditions during sputtering>
DC magnetron sputtering method Gas pressure: 2×10 ⁻³ Torr
Ar flow rate: 50SCCM
_O2 flow rate: 3SCCM
Composition of target ITO: tin oxide 20 wt% with respect to the entire ITO target (manufactured by Mitsui Kinzoku Co., Ltd., product name: ITO target)
Input power density to target: 2 W/cm ² for ITO target
Processing time: film feeding speed 0.1 m/min
Degree of vacuum when creating the ITO layer: 2×10 ⁻³ Torr

Next, the polyimide film with the ITO layer was cut into a size of 70 mm×70 mm.

Next, with the ITO layer facing upward, UV/O ₃ irradiation was performed for 3 minutes using a UV/O ₃ irradiator (SKR1102N-03 manufactured by LAN Technical). At this time, the distance between the UV/O3 lamp and the film was ₃₀ mm. This step corresponds to step C of the present invention.

On the other hand, a solution was prepared by diluting 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent (SCA) with isopropanol so as to contain 1.2% by mass.
Also, a glass substrate was prepared. The glass substrate is OA10G glass (manufactured by NEG Co., Ltd.) having a thickness of 0.7 mm cut into a size of 100 mm×100 mm. The glass substrate used was washed with pure water, dried, irradiated with a UV/O ₃ irradiation device (SKR1102N-03 manufactured by LAN Technical Co., Ltd.) for 1 minute, and then washed.
The glass substrate was placed on a spin coater (MSC-500S, manufactured by Japan Create Co., Ltd.) with the washed surface of the glass substrate facing upward. 5 mL of the solution is dropped on the glass substrate, the glass is rotated at 500 rpm to spread over the entire surface of the glass substrate, and then rotated at 2000 rpm to apply the solution to the glass substrate, forming a silane coupling agent layer. formed. This step corresponds to step A of the present invention.

Next, the polyimide film with the ITO layer prepared above and the glass substrate with the silane coupling agent layer were bonded together to obtain a laminate. The bonding was performed so that the ITO layer and the silane coupling agent layer were on the bonding surface. This step corresponds to step D of the present invention. A laminator (MRK-1000 manufactured by MCK Co.) was used for lamination, and the lamination conditions were air source pressure: 0.7 MPa, temperature: 22° C., humidity: 55% RH, and lamination speed: 50 mm/sec.

(Example 2)
A laminate was obtained in the same manner as in Example 1, except that the coating method of the silane coupling agent (SCA) on the glass substrate was changed to vapor phase coating. Specifically, the application of the silane coupling agent to the glass substrate was performed using the experimental apparatus shown in FIG. FIG. 1 is a schematic diagram of an experimental apparatus for applying a silane coupling agent to a glass substrate. 130 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was placed in a 1 L chemical solution tank, and the water bath outside was heated to 42°C. The emerging vapors were then sent into the chamber along with clean dry air. The gas flow rate was 22 L/min, and the substrate temperature was 21.degree. The temperature of clean dry air was 23° C. and 1.2% RH. Since the exhaust was connected to a negative pressure exhaust port, it was confirmed by a differential pressure gauge that the chamber had a negative pressure of about 10 Pa.

(Example 3)
A laminate was obtained in the same manner as in Example 2, except that the treatment method for the ITO layer (step C) was changed as follows.
<Processing method for ITO layer>
Using an atmospheric pressure plasma apparatus (AP-T05-S320) manufactured by Sekisui Chemical Co., Ltd., the ITO layer (before treatment) was subjected to plasma irradiation under the following plasma irradiation conditions.
<Plasma irradiation conditions>
Plasma mode: Remote plasma Distance between plasma head and substrate: 2 mm
Discharge voltage: 240V
Substrate moving speed: 1500mm/min
Gas used: Nitrogen (flow rate: 130 L/min) and clean air (0.65 L/min)
Processing atmosphere: Normal air atmosphere

(Example 4)
A laminate was obtained in the same manner as in Example 3 except that the substrate was changed from a glass substrate to a silicon wafer (dummy grade 4-inch wafer).

(Example 5)
A laminate was obtained in the same manner as in Example 2, except that the treatment method for the ITO layer (step C) was changed as follows.
<Processing method for ITO layer>
A vacuum plasma device (V1000 manufactured by Yamato Glass Co., Ltd.) was used. Electrodes were arranged in parallel in the vacuum chamber of the vacuum plasma apparatus, and the film was placed between the electrodes for processing. It was placed on the lower electrode with the ITO layer facing up, and the treatment was performed for 2 minutes under the conditions of power 700 W, gas pressure 10 Pa, and gas flow rate O ₂ : 200 SCCM.

(Example 6)
A laminate was obtained in the same manner as in Example 2, except that a Si-Al-O-based layer was formed on the polyimide film 1 by sputtering instead of the ITO layer. Specifically, a laminate was obtained in the same manner as in Example 2, except that the sputtering conditions were changed as follows. During sputtering, the Si metal target and the Al metal target are close to each other, and the irradiated atoms from both are mixed on the polyimide film 1 .
<Conditions during sputtering>
DC magnetron sputtering method Gas pressure: 2×10 ⁻³ Torr
Ar flow rate: 50SCCM
_O2 flow rate: 5SCCM
target:
Si metal target (manufactured by Mitsubishi Materials Corporation)
Al metal target manufactured by Sumitomo Chemical Co., Ltd.)
Input power density to the target:
2.5 W/cm ² for Si metal target
1.5 W/cm ² for Al metal target
Processing time: film feeding speed 0.1 m/min
Vacuum degree at the time of Si-Al-O-based layer creation: 2 × 10 ^-3 Torr

(Example 7)
A laminate was obtained in the same manner as in Example 6, except that the treatment method (step C) for the Si—Al—O-based layer was changed in the same manner as in Example 3.

(Example 8)
Same as Example 5 except that the inorganic substrate was changed from glass to a silicon wafer (dummy grade 4-inch wafer), and the ITO layer was replaced with the same Si—Al—O-based layer as in Example 6. Thus, a laminate was obtained.

(Example 9)
A laminate was obtained in the same manner as in Example 3, except that the silane coupling agent (SCA) was applied to the polyimide film 1 instead of applying it to the glass substrate. That is, in Example 9, a silane coupling agent layer was formed on the ITO layer.

(Example 10)
A laminate was obtained in the same manner as in Example 5 except that the polyimide film 2 was used instead of the polyimide film 1.

(Example 11)
A laminate was obtained in the same manner as in Example 3, except that the polyimide film 2 was used instead of the polyimide film 1.

(Example 12)
A laminate was obtained in the same manner as in Example 9 except that the inorganic substrate was changed from glass to a silicon wafer (dummy grade 4-inch wafer) and polyimide film 2 was used instead of polyimide film 1.

(Example 13)
A laminate was obtained in the same manner as in Example 5, except that the polyimide film 3 was used instead of the polyimide film 1.

(Example 14)
A laminate was obtained in the same manner as in Example 3, except that the polyimide film 3 was used instead of the polyimide film 1.

(Example 15)
A laminate was obtained in the same manner as in Example 4, except that the polyimide film 3 was used instead of the polyimide film 1.

(Example 16)
A laminate was obtained in the same manner as in Example 3, except that the polyimide film 4 was used instead of the polyimide film 1.

(Example 17)
A laminate was obtained in the same manner as in Example 3, except that the polyimide film 5 was used instead of the polyimide film 1.

(Comparative example 1)
A laminate was obtained in the same manner as in Example 2, except that the ITO layer was not provided and the ITO layer was not treated (process C).

(Comparative example 2)
A laminate was obtained in the same manner as in Example 16, except that the ITO layer was not provided and the ITO layer was not treated (step C).

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 17, except that the ITO layer was not provided and the ITO layer was not treated (step C).

(Comparative Example 4)
A laminate was obtained in the same manner as in Example 2, except that the ITO layer was not treated (step C).

(Comparative Example 5)
A laminate was obtained in the same manner as in Example 10, except that the ITO layer was not treated (step C).

The thickness of the silane coupling agent layer included in the laminates obtained in the above examples and comparative examples was in the range of 4 nm to 8 nm.

<Measurement of polar component ^γsh of surface energy of surface of metal-containing layer (ITO layer, Al—Si—O layer)>
As used herein, the surface energy (γsv: unit, dyne/cm) is defined by D.I. K. Owens:J. Appl. Polym. Sci. , Vol. 13, p. 1741 (1969), the following simultaneous equations are obtained from contact angles θ _H2O and θ _CH2I2 of pure water H ₂ O and methylene iodide CH ₂ I ₂ experimentally determined on a polyimide film. It is a value (γsv=γs ^d +γs ^h ) represented by the sum of γs ^d and γs ^h obtained from (a) and (b).
(a) 1+cos θ _H2O =2√γs ^d ( _√γH2O ^d / _γH2O ^v )+ ^2√γsh ( _√γH2O ^h / _γH2O ^v )
(b) 1+cos θ _CH2I2 = 2√γs ^d (√γ _CH2I2 ^d /γ _CH2I2 ^v )+2√γsh ( ^√γ _CH2I2 ^h /γ _CH2I2 ^v )
(where γ _H2O ^d =21.8, γ _H2O ^h =51.0, γ _H2O ^v =72.8, γ _CH2I2 ^d =49.5, γ _CH2I2 ^h =1.3, γ _CH2I2 ^v =50.8 and.)
That is, the polar component ^γsh of the surface energy can be obtained from the measured values of the contact angles θ _H2O and θ _CH2I2 and the above simultaneous equations (a) and (b). Therefore, the contact angles θ _H2O and θ _CH2I2 were measured as follows.
<Measurement of contact angle>
The contact angle was measured using an automatic contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. after the film was conditioned at 20° C. and a humidity of 26% RH for 1 hour or more. A droplet of 1.8 μl is dropped on the film to form a droplet, and the angle formed by the tangent to the liquid surface and the film surface at the point where the film and liquid contact, the angle on the side containing the liquid is measured as the contact angle. bottom. The contact angle was measured five times for one sample and one type of liquid, and the average value of the five times was taken as the above-described θ _H2O and θ _CH2I2 .
<Calculation of polar component γs ^h >
^γsh was obtained by substituting θ _H2O and θ _CH2I2 obtained by contact angle measurement into the above simultaneous equations (a) and (b). The results are shown in Table 2-5. The table also shows γs ^d .

<Measurement of 90° initial peel strength>
The layered product obtained in the production of the above layered product was heat-treated at 200° C. for 1 hour in an air atmosphere. After that, the 90° initial peel strength between the inorganic substrate (glass substrate or silicon wafer) and the polyimide film was measured. The results are shown in Tables 2-5.
The measurement conditions for the 90° initial peel strength are as follows.
The film is peeled off at an angle of 90° to the inorganic substrate.
Measurement is performed 5 times, and the average value is taken as the measured value.
Measuring device; Autograph AG-IS manufactured by Shimadzu Corporation
Measurement temperature; room temperature (25°C)
Peeling speed; 100mm/min
Atmosphere; atmospheric measurement sample width; 2.5 cm

<Initial peel strength position distribution>
Examples 1-8, 10, 11 and Comparative Examples 4 and 5 Using polyimide film rolls with a width of 730 mm, heat-resistant polymer films with metal-containing layers were produced in the same manner as in Examples and Comparative Examples.
Next, a sample of 70 mm in the longitudinal direction (MD direction) and 10 mm in the lateral direction (TD direction) was cut from the central portion in the width direction of the roll (hereinafter also referred to as sample A).
Further, a sample of the same size was cut from a portion shifted 300 mm laterally from the central portion in the width direction of the roll (hereinafter also referred to as sample B).
Using the cut samples, laminates were produced in the same manner as in Examples and Comparative Examples. The obtained laminate was heat-treated at 200° C. for 1 hour in an air atmosphere. After that, the 90° initial peel strength between the inorganic substrate (glass substrate or silicon wafer) and the polyimide film was measured.
Of the three samples obtained (one sample A and two samples B), the values obtained from the following formula using the values of the largest and smallest 90° initial peel strengths are used as the initial peel strength position distribution. bottom.
[((maximum peel strength) - (minimum peel strength)) / (minimum peel strength)] × 100
The results are shown in Tables 2-5.

- Examples 9 and 12 Using polyimide film rolls with a width of 730 mm, heat-resistant polymer films with a metal-containing layer were produced in the same manner as in Examples and Comparative Examples. Furthermore, a silane coupling agent layer was formed on the metal-containing layer in the same manner as in Examples.
Next, a sample of 70 mm in the longitudinal direction (MD direction) and 10 mm in the lateral direction (TD direction) was cut from the central portion in the width direction of the roll (hereinafter also referred to as sample A).
Further, a sample of the same size was cut from a portion shifted 300 mm laterally from the central portion in the width direction of the roll (hereinafter also referred to as sample B).
Using the cut sample, a laminate was produced in the same manner as in the example. The obtained laminate was heat-treated at 200° C. for 1 hour in an air atmosphere. After that, the 90° initial peel strength between the inorganic substrate (glass substrate or silicon wafer) and the polyimide film was measured. After that, the initial peel strength positional distribution was obtained in the same manner as described above.
The results are shown in Tables 2-5.

・Comparative Example 1-3 A polyimide film roll with a width of 730 mm was prepared.
Next, a sample of 70 mm in the longitudinal direction (MD direction) and 10 mm in the lateral direction (TD direction) was cut from the central portion in the width direction of the roll (hereinafter also referred to as sample A).
Further, a sample of the same size was cut from a portion shifted 300 mm laterally from the central portion in the width direction of the roll (hereinafter also referred to as sample B).
Using the cut sample, a laminate was produced in the same manner as in the comparative example. The obtained laminate was heat-treated at 200° C. for 1 hour in an air atmosphere. After that, the 90° initial peel strength between the inorganic substrate (glass substrate or silicon wafer) and the polyimide film was measured. After that, the initial peel strength positional distribution was obtained in the same manner as described above.
The results are shown in Tables 2-5.

<Blister evaluation>
The laminates of Examples and Comparative Examples were observed with an optical microscope from the inorganic substrate side. Focusing on the adhesion surface between the inorganic substrate and the polyimide film, an unbonded portion (blister) having a diameter of 500 μm or more was observed. Four regions of 50 mm×50 mm excluding the outer peripheral portion of the laminate were observed, and blisters observed in a total area of 10000 mm ² were visually counted. The results are shown in Tables 2-5.

<Measurement of peeling electrification voltage>
The laminates of Examples and Comparative Examples were partially peeled at 90 degrees, and the peeling electrification voltage was measured in that state. For the measurement, an electrostatic meter FMX-004 manufactured by SIMCO was used. The peeling conditions were as follows.
Measurement temperature: 21°C
Measurement humidity; 50% RH
Peeling: 90 degree Peeling speed: 20 mm/sec Atmosphere: Atmospheric measurement Sample width: 2.5 cm

Claims (6)

An inorganic substrate, a silane coupling agent layer, a metal-containing layer containing a metal oxide , and a heat-resistant polymer film are laminated in this order,
A laminate, wherein the polar component ^γsh of the surface energy of the surface of the metal-containing layer on the side of the silane coupling agent layer is 10 dyn/cm or more and 60 dyn/cm or less. 2. The laminate according to claim 1, wherein said metal oxide is indium tin oxide. 3. The laminate according to claim 1, wherein the 90° initial peel strength between the heat-resistant polymer film and the inorganic substrate is 0.05 N/cm or more. When the heat-resistant polymer film is peeled off from the inorganic substrate at a temperature of 21° C. and a humidity of 50% RH at a peeling angle of 90 degrees and a peeling speed of 20 mm/sec, the peeling electrification voltage on the surface of the heat-resistant polymer film is 4. The laminate according to any one of claims 1 to 3, wherein the voltage is 0.3 kV or less. A step A of forming a silane coupling agent layer on an inorganic substrate to obtain a first laminate;
A step B of forming a metal-containing layer containing a metal oxide on the heat-resistant polymer film;
A step of forming oxygen defects on the surface of the metal-containing layer so that the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less to obtain a second laminate. C and
A step D of bonding the first laminate and the second laminate together,
The step D is a step of bonding the silane coupling agent layer formed on the inorganic substrate and the metal-containing layer formed on the heat-resistant polymer film as bonding surfaces. A method for manufacturing a laminate. a heat-resistant polymer film;
a metal-containing layer containing a metal oxide ;
The heat-resistant polymer film is a polyimide resin film,
The metal constituting the metal oxide is one selected from the group consisting of Au, Ag, Cu, Pb, Zn, In, Sn, Fe, Al, Mo, W, Sb, Bi, Nb, and Ti. and
A heat-resistant polymer film with a metal-containing layer, wherein the polar component ^γsh of the surface energy of the surface of the metal-containing layer is 10 dyn/cm or more and 60 dyn/cm or less.

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