JP7167693B2 - LAMINATED FILM, LAMINATE, AND LAMINATE MANUFACTURING METHOD - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminated film, a laminate, and a method for producing a laminate.

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.

Polymer films used for the above applications should be covered with a protective film on either side or one side until just before use to prevent dust from entering between the support and the polymer film when they are attached to the support. is covered with (for example, see Patent Document 1).

WO2016/031746

The polymer film described above is supplied in the form of being wound into a roll with protective films attached to both sides thereof. When the polymer film is attached to the support, first, the polymer film, to which the protective film is attached, is cut into a desired size and shape using a knife such as a Thomson type. After that, the protective film is peeled off and the laminate is attached to the support.

Cutting with a blade as described above deforms the cut portion because it is press cutting. However, the peel strength between the polymer film and the protective film is set to be small so as not to leave adhesive residue on the polymer film after the protective film is peeled off. Therefore, there is a problem that peeling occurs between the protective film and the polymer film due to deformation caused by cutting with a knife.
In addition, there is a demand to cut out a large-area polymer film and attach it to a large-area support. There is also a problem.

Therefore, the present inventors have investigated cutting a laminated film of a protective film and a polymer film with a laser. However, smears (residues of resin or the like) may occur at the interface between the protective film and the polymer film, causing peeling. In addition, the cut surface may be scorched, and the cross section may not be generally uniform.

In this regard, the present inventors have conducted intensive research. As a result, if a protective film having a first adhesive layer containing an ultraviolet absorber provided on a substrate made of a polyester film is used and cut with an ultraviolet laser, the protective film and the polymer film can be suitably cut. The present inventors have found that separation of the protective film and the polymer film at the cut surface can be suppressed, and have completed the present invention.

That is, the laminated film according to the present invention is
a heat-resistant polymer film;
a first protective film laminated on one surface of the heat-resistant polymer film;
a second protective film laminated on the other surface of the heat-resistant polymer film,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first adhesive layer contains an ultraviolet absorber,
It is characterized by being cut by an ultraviolet laser before being used.

According to the above configuration, the first protective film and the heat-resistant polymer film can be suitably cut by irradiating the ultraviolet laser from the first protective film side, and the first protective film and the heat-resistant polymer film are separated from each other at the cut surface. Peeling can be suppressed. This is also clear from the examples.
The inventors presume the reason for this as follows.
When an ultraviolet laser is irradiated from the first protective film side, the ultraviolet laser passes through the first base material, but does not pass through the first adhesive layer containing the ultraviolet absorber. Ultraviolet rays are absorbed at the interface with 1 base material, and the temperature rises locally. After that, first, the first substrate is perforated. That is, a hole is opened first from the interface, which has reached a high temperature, toward the first substrate. This is because the first base material and the first pressure-sensitive adhesive layer are bonded relatively firmly (the peel strength between the first base material and the first pressure-sensitive adhesive layer is large), so the heat from the ultraviolet laser causes the first pressure-sensitive adhesive layer to adhere to the first pressure-sensitive adhesive layer. This is because the first substrate evaporates without separating the first substrate and the first pressure-sensitive adhesive layer. After that, the first pressure-sensitive adhesive layer and the heat-resistant polymer film are heated to a high temperature and evaporate. As a result, the first protective film and the heat-resistant polymer film are cut. The evaporated and scattered smear does not remain on the side surface of the cut surface, but scatters outward from the first substrate from the surface on the side of the first substrate.
As described above, the protective film and the polymer film are suitably cut without being deformed or scorched. Moreover, peeling of the protective film and the polymer film at the cut surface is suppressed.

In the above configuration, the 90° peel strength between the heat-resistant polymer film and the first protective film is preferably 0.002 N/cm or more and 0.3 N/cm or less.

When the 90° peel strength is 0.3 N/cm or less, the first protective film can be suitably peeled off when using a heat-resistant polymer film. Further, when the 90° peel strength is 0.002 N/cm or more, the first protective film is unintentionally separated from the heat-resistant polymer film in a stage prior to using the heat-resistant polymer film (for example, during transportation). Exfoliation can be suppressed.

The said structure WHEREIN: It is preferable that a said 1st base material is a polyethylene terephthalate film.

When the first base material is a polyethylene terephthalate film, it has appropriate hardness and flexibility for protecting the heat-resistant polymer film, and is suitable as a base material for the first protective film. In addition, although the polyethylene terephthalate film does not transmit ultraviolet rays (does not absorb them greatly), by combining it with an adhesive layer containing an ultraviolet absorber, it is possible to cut the first base material with an ultraviolet laser suitable for cutting heat-resistant polymer films. Good cutting is possible, including This mechanism is as described above. If the first base material is made of a material that does not transmit ultraviolet rays, the first base material absorbs a large amount of the energy of the ultraviolet laser, and it takes a long time to cut the protective film and the polymer film in a short time. may not be cut economically.

In the above configuration, the heat-resistant polymer film is preferably a polyimide film. When the heat-resistant polymer film is a polyimide film, it has excellent heat resistance. Moreover, when the heat-resistant polymer film is a polyimide film, it can be suitably cut with an ultraviolet laser.

Further, the laminate according to the present invention is
An inorganic substrate, a silane coupling agent layer, a heat-resistant polymer film, and a first protective film are laminated in this order,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first pressure-sensitive adhesive layer is characterized by containing an ultraviolet absorber.

According to the above configuration, the first protective film has at least a first base material made of a polyester film and a first adhesive layer provided on the polyester film, and the first adhesive layer contains UV absorbers. The heat-resistant polymer film and the first protective film can be suitably cut into a desired size by using an ultraviolet laser without being deformed or scorched. Moreover, peeling of the first protective film and the heat-resistant polymer film at the cut surface can be suppressed. Therefore, even in the laminate having the heat-resistant polymer film and the first protective film, peeling between the first protective film and the heat-resistant polymer film can be suppressed.

Further, the method for manufacturing a laminate according to the present invention includes:
Step A of preparing a first laminate having an inorganic substrate and a silane coupling agent layer;
A step B of preparing the laminated film;
a step C of irradiating the laminated film with an ultraviolet laser from the side of the first protective film to cut the first protective film and the heat-resistant polymer film into a predetermined shape;
After the step C, a step D of peeling the second protective film from the heat-resistant polymer film;
After the step D, the silane coupling agent layer and the heat-resistant polymer film of the first laminate are bonded together to obtain the inorganic substrate, the silane coupling agent layer, the heat-resistant polymer film, and a step E of obtaining a laminate in which the first protective film and the first protective film are laminated in this order.

According to the above configuration, the laminate film is irradiated with an ultraviolet laser from the first protective film side, and the first protective film and the heat-resistant polymer film are cut into a predetermined shape (step C). . The first protective film has a first substrate made of a polyester film and a first adhesive layer provided on the polyester film, and the first adhesive layer contains an ultraviolet absorber. Therefore, the first protective film and the heat-resistant polymer film can be suitably cut by the ultraviolet laser, and peeling of the first protective film and the heat-resistant polymer film at the cut surface can be suppressed.
After the step C, the second protective film is peeled off from the heat-resistant polymer film (step D), and the silane coupling agent layer of the first laminate and the heat-resistant polymer film are bonded together. to obtain a laminate in which the inorganic substrate, the silane coupling agent layer, the heat-resistant polymer film, and the first protective film are laminated in this order (step E). In the laminate thus obtained, peeling between the first protective film and the heat-resistant polymer film is suppressed.

According to the present invention, the first protective film and the heat-resistant polymer film can be suitably cut with an ultraviolet laser, and peeling of the first protective film and the heat-resistant polymer film on the cut surface and adhesion of smears can be suppressed. A laminated film can be provided. Moreover, it is possible to provide a laminate in which peeling between the first protective film and the heat-resistant polymer film at the cut surface is suppressed. Moreover, the manufacturing method of the said laminated body can be provided.

It is a schematic diagram of an experimental apparatus for applying a silane coupling agent to a glass substrate. It is a top view for demonstrating the manufacturing method of the laminated body which concerns on this embodiment. 2B is a side cross-sectional view of FIG. 2A; FIG. It is a side sectional view for explaining a manufacturing method of a layered product concerning this embodiment. It is a side sectional view for explaining a manufacturing method of a layered product concerning this embodiment. It is a side sectional view for explaining a manufacturing method of a layered product concerning this embodiment.

Embodiments of the present invention will be described below.

<Laminated film>
The laminated film according to this embodiment comprises a heat-resistant polymer film, a first protective film laminated on one side of the heat-resistant polymer film, and a second protective film laminated on the other side of the heat-resistant polymer film. a film;

<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). When the melting point exceeds 500° C., it may be determined whether or not the melting point has been reached by visually 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 it is assumed that the polymer film is used in a process involving heat treatment at 300° C. or higher, the examples of polymer films that can be actually applied are limited. 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.

In this embodiment, the polymer film is preferably a polyimide film. When the polymer film is a polyimide film, it has excellent heat resistance. Moreover, when the polymer film is a polyimide film, it can be suitably cut with an ultraviolet laser.

The thickness of the polymer film is preferably 3 μm or more, more preferably 7 μm or more, still more preferably 14 μm or more, and still more preferably 20 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 100 μm or less, and still more preferably 50 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.

<First protective film>
The first protective film has a first substrate made of a polyester-based film and a first pressure-sensitive adhesive layer provided on the polyester-based film.

(First base material)
A said 1st base material consists of a polyester-type film. As used herein, a polyester-based film refers to a film formed with a polyester resin as a main component.

Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polymethylene terephthalate. Examples of copolymer components include diol components such as diethylene glycol, neopentyl glycol and polyalkylene glycol, dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. is mentioned.

Among the above polyester resins, polyethylene terephthalate is preferred. That is, it is preferable that the first base material is a polyethylene terephthalate film. When the first base material is a polyethylene terephthalate film, it has appropriate hardness and flexibility for protecting the heat-resistant polymer film, and is suitable as a base material for the first protective film. In addition, although the polyethylene terephthalate film does not transmit ultraviolet rays (does not absorb them greatly), by combining it with an adhesive layer containing an ultraviolet absorber, it is possible to cut the first base material with an ultraviolet laser suitable for cutting heat-resistant polymer films. Good cutting is possible, including This mechanism is as described above. If the first base material is made of a material that does not transmit ultraviolet rays, the first base material absorbs a large amount of the energy of the ultraviolet laser, and it takes a long time to cut the protective film and the polymer film in a short time. may not be cut economically.

The first substrate may be a single layer, may be a laminate of a plurality of layers having the same composition, or may be a laminate of a plurality of layers having different compositions. . Each layer may be a layer having known functions such as antistatic and adhesion prevention.

If necessary, the first base material may contain various additives in the polyester resin. Examples of the additives include fillers, antioxidants, light stabilizers, anti-gelling agents, organic wetting agents, antistatic agents, and surfactants. However, it is preferable that the first base material satisfies the following numerical range in the ultraviolet transmittance measurement. It is preferable that the first base material does not contain an ultraviolet absorber. Examples of the ultraviolet absorber include those described later.

The first substrate preferably has a transmittance of 70% or more, more preferably 80% or more, and 90% or more at a wavelength of 355 nm in an ultraviolet transmittance measurement (UV transmittance measurement). is more preferable, and 95% or more is particularly preferable. When the transmittance of the first base material at a wavelength of 355 nm is 70% or more, the first protective film and the heat-resistant polymer film can be more preferably cut with an ultraviolet laser.

Although the thickness of the first base material is not particularly limited, it can be arbitrarily determined according to the standard used, for example, within the range of 12 μm or more and 500 μm or less. More preferably, the thickness of the first base material is 25 μm or more and 350 μm or less. When the thickness of the first base material is 500 µm or less, it is possible to suppress deterioration of productivity and handling properties. Moreover, if the thickness of the first base material is 12 μm or more, the mechanical strength deficiency of the first base material can be reduced, and breakage during peeling can be prevented.

The first base material can be formed into a film by a conventionally known film forming method. Examples of the film-forming method include a calendar film-forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method, and the like.

(First adhesive layer)
The first pressure-sensitive adhesive layer is not particularly limited, and known ones such as acrylic, silicone, rubber, and polyester can be used. Acrylic resins and silicone resins are preferable from the viewpoint of handleability.

The acrylic resin is obtained by polymerizing a monomer such as (meth)acrylic acid alkyl ester. Specific examples of the monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, ) Alkyl ( meth)acrylate compounds. A plurality of these can also be copolymerized as needed.

The first pressure-sensitive adhesive layer contains an ultraviolet absorber. A known ultraviolet absorber can be used as the ultraviolet absorber. Examples of the UV absorber include organic UV absorbers and inorganic UV absorbers, but organic UV absorbers are preferred from the viewpoint of transparency.

Examples of the organic ultraviolet absorbent include benzotriazole-based, benzophenone-based, cyclic iminoester-based, and combinations thereof. Among them, benzotriazole-based and cyclic iminoester-based are particularly preferable from the viewpoint of durability.

Examples of the benzotriazole-based ultraviolet absorbers include 2-[2′-hydroxy-5′-(methacryloyloxymethyl)phenyl]-2H-benzotriazole and 2-[2′-hydroxy-5′-(methacryloyloxyethyl). Phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyhexyl)phenyl] -2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert- Butyl-3′-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2 '-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzo triazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2′-hydroxy-5′-(methacryloyloxyethyl)phenyl] -5-nitro-2H-benzotriazole and the like.

Examples of the benzophenone-based UV absorbers include 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'- dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone disodium salt and the like.

Examples of the cyclic iminoester-based UV absorber include 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine- 4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzo Oxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl- 3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o -methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4 -one, 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazinone-4-one) 2,2′-bis(3,1-benzoxazin-4-one), 2,2′-ethylenebis(3,1-benzoxazin-4-one), 2,2′-tetramethylenebis(3,1-benzoxazin-4-one), 2,2′-decamethylenebis ( 3,1-benzoxazin-4-one), 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1-benzoxazin-4-one) -4-one), 2,2′-(4,4′-diphenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2,6- or 1,5-naphthalene) Bis(3,1-benzoxazin-4-one), 2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2- nitro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2, 2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one), 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)benzene, etc. is mentioned.

Also, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, and 2,4,6-tri(3,1-benzoxazin-4-one-2-yl ) naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d′)bis-(1,3)-oxazine-4,6-dione, 2,7-dimethyl- 4H,9H-benzo(1,2-d;5,4-d′)bis-(1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2 -d;5,4-d')bis-(1,3)-oxazine-4,6-dione,2,7-diphenyl-4H,9H-benzo(1,2-d;5,4-d' ) bis-(1,3)-oxazine-4,6-dione, 6,6′-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-bis(2 -ethyl-4H,3,1-benzoxazin-4-one), 6,6′-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6′-methylenebis(2 -methyl-4H,3,1-benzoxazin-4-one), 6,6′-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6′-ethylenebis( 2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-ethylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6′-butylenebis (2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-oxybis (2-methyl-4H,3,1-benzoxazin-4-one), 6,6′-oxybis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6′-sulfonyl Bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6' -carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 7, 7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 7, 7′-bis(2-methyl-4H,3 ,1-benzoxazin-4-one), 7,7′-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7′-oxybis(2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7′-carbonylbis(2-methyl- 4H,3,1-benzoxazin-4-one), 6,7′-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7′-bis(2-phenyl- 4H,3,1-benzoxazin-4-one), 6,7′-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7′-methylenebis(2-phenyl- 4H,3,1-benzoxazin-4-one) can also be used as a cyclic iminoester UV absorber.

Although the content of the ultraviolet absorber is not particularly limited, it is preferable that the measured value is within the following numerical range in the ultraviolet transmittance measurement (UV transmittance measurement) of the first protective film. For example, the content of the ultraviolet absorber is preferably 0.1 to 10% by weight, and 0.3 to 3% by weight, when the entire first pressure-sensitive adhesive layer is 100% by weight. is more preferred.

Although the thickness of the first pressure-sensitive adhesive layer is not particularly limited, it is usually 3 to 200 μm, preferably 5 to 30 μm.

The first pressure-sensitive adhesive layer is obtained by applying a pressure-sensitive adhesive composition solution on the first substrate to form a coating film, and then drying the coating film under predetermined conditions. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, gravure coating, and the like. The drying conditions are, for example, a drying temperature of 80 to 150° C. and a drying time of 0.5 to 5 minutes. Alternatively, the pressure-sensitive adhesive composition may be applied on the separator to form a coating film, and then the coating film may be dried under the drying conditions described above to form the first pressure-sensitive adhesive layer. After that, the first pressure-sensitive adhesive layer is pasted together with the separator onto the first substrate. A 1st protective film is obtained by the above.

The first protective film preferably has a transmittance of 30% or less, more preferably 20% or less, and 15% or less at a wavelength of 355 nm in an ultraviolet transmittance measurement (UV transmittance measurement). is more preferred. When the transmittance of the first protective film at a wavelength of 355 nm is 30% or less, the first protective film and the heat-resistant polymer film can be more suitably cut with an ultraviolet laser.

The 90° peel strength between the heat-resistant polymer film and the first protective film is preferably 0.002 N/cm or more and 0.3 N/cm or less, and more preferably 0.003 N/cm or more and 0.2 N/cm or less. It is more preferable to have When the 90° peel strength is 0.3 N/cm or less, the first protective film can be suitably peeled off when using a heat-resistant polymer film. Further, when the 90° peel strength is 0.002 N/cm or more, the first protective film is unintentionally separated from the heat-resistant polymer film in a stage prior to using the heat-resistant polymer film (for example, during transportation). Exfoliation can be suppressed.

<Second protective film>
The second protective film is attached to the other surface of the heat-resistant polymer film until the heat-resistant polymer film is used. The configuration of the second protective film is not particularly limited as long as it can be peeled off from the heat-resistant polymer film when the heat-resistant polymer film is used. As said 2nd protective film, the structure which has a 2nd base material and the 2nd adhesive layer provided on said 2nd base material is mentioned, for example.

(Second base material)
Examples of the material of the second base material include polyester resins described in the section of the first base material, polyolefin resins such as polyethylene and polypropylene, and polyamide resins such as nylon 6 and nylon 66. These may be used in combination.

As with the first base material, the second base material may contain various additives in the resin, if necessary. Examples of the additive include those described in the section on the first base material. In addition, in the said 2nd base material, you may contain an ultraviolet absorber. Examples of the ultraviolet absorber include those described in the section of the first pressure-sensitive adhesive layer.

(Second adhesive layer)
As said 2nd adhesive layer, the thing similar to said 1st adhesive layer can be employ|adopted. However, the second pressure-sensitive adhesive layer may not contain an ultraviolet absorber.

A method for producing the laminated film is not particularly limited, and a known method can be adopted. For example, a first protective film, a second protective film, and a polymer film are prepared separately, and the first protective film is attached to one surface of the polymer film, and the second protective film is attached to the other surface. The laminated film can be obtained by

The 90° peel strength between the heat-resistant polymer film and the second protective film is preferably 0.002 N/cm or more and 0.3 N/cm or less, and more preferably 0.003 N/cm or more and 0.2 N/cm or less. It is more preferable to have When the 90° peel strength is 0.3 N/cm or less, the second protective film can be suitably peeled off when using a heat-resistant polymer film. In addition, when the 90° peel strength is 0.002 N/cm or more, the second protective film is unintentionally peeled off from the heat-resistant polymer film in a stage prior to using the heat-resistant polymer film (for example, during transportation). Exfoliation can be suppressed.

The laminated film according to the present embodiment has been described above.

Next, the laminate according to this embodiment will be described.

<Laminate>
In the laminate according to the present embodiment, an inorganic substrate, a silane coupling agent layer, a heat-resistant polymer film, and a first protective film are laminated in this order,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first pressure-sensitive adhesive layer contains an ultraviolet absorber.

Since the heat-resistant polymer film and the first protective film have been described in the section on the laminated film, description thereof will be omitted here.

<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 preferable.

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 polymer film, 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.
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.

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.

According to the laminate according to the present embodiment, the first protective film has a first substrate made of a polyester film and a first adhesive layer provided on the polyester film, and the first adhesive layer is provided on the polyester film. One pressure-sensitive adhesive layer contains an ultraviolet absorber. Therefore, in the laminate having the heat-resistant polymer film and the first protective film, peeling between the first protective film and the heat-resistant polymer film is suppressed.

<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:
Step A of preparing a first laminate having an inorganic substrate and a silane coupling agent layer;
A step B of preparing a laminated film;
a step C of irradiating the laminated film with an ultraviolet laser from the side of the first protective film to cut the first protective film and the heat-resistant polymer film into a predetermined shape;
After the step C, a step D of peeling the second protective film from the heat-resistant polymer film;
After the step D, the silane coupling agent layer and the heat-resistant polymer film of the first laminate are bonded together to obtain the inorganic substrate, the silane coupling agent layer, the heat-resistant polymer film, and a step E of obtaining a laminate in which the first protective film and the first protective film are laminated in this order.

Hereinafter, a method for manufacturing a laminate according to this embodiment will be described with reference to the drawings. FIG. 2A is a plan view for explaining the method for manufacturing a laminate according to this embodiment, and FIG. 2B is a side cross-sectional view thereof. 3 to 5 are side cross-sectional views for explaining the method of manufacturing a laminate according to this embodiment.

<Process A>
In step A, a first laminate 120 having an inorganic substrate 122 and a silane coupling agent layer 124 is prepared (see FIG. 5). Although the method of preparing the first laminate is not particularly limited, the first laminate can be obtained by forming a silane coupling agent layer on an inorganic substrate. 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.

<Process B>
In step B, a laminated film 100 is prepared (see FIGS. 2A and 2B). The laminated film 100 includes a polymer film 102, a first protective film 104 laminated on one side of the polymer film 102, and a second protective film 106 laminated on the other side of the polymer film 102. . The laminated film 100 can be obtained, for example, by the method described in the section on the method for producing the laminated film.

<Process C>
In step C, the laminate film 100 is irradiated with an ultraviolet laser from the first protective film 104 side, and the first protective film 104 and the polymer film 102 are cut into a predetermined shape. It is preferable that the ultraviolet laser irradiation be performed in a state in which the second protective film 106 is not peeled off from the polymer film 102 . As in the present embodiment, if the ultraviolet laser is irradiated in a state in which the second protective film 106 is not peeled off from the polymer film 102, the peripheral portions of the first protective film 104 and the polymer film 102 cut by the ultraviolet laser can be removed. , can be easily peeled off together with the second protective film 106 (see FIG. 4). In addition, the surface (the other surface) of the polymer film 102 can be protected after irradiation with the ultraviolet laser until just before bonding to the inorganic substrate.

The ultraviolet laser preferably has a wavelength of 310 nm to 450 nm, more preferably 340 nm to 380 nm. By setting the wavelength to 450 nm or less, it becomes possible to suitably cut the first protective film and the polymer film. Moreover, by setting the wavelength to 310 nm or more, the ultraviolet absorber can suitably absorb the ultraviolet laser, and it becomes possible to suitably cut the first protective film and the polymer film.
The shape (predetermined shape) to be cut by the ultraviolet laser is not particularly limited, and examples thereof include a rectangular shape and a circular shape. In addition, it may be formed into a shape including an orientation flat or a notch that conforms to the standard of the inorganic substrate. The predetermined shape can be appropriately set according to the arrangement and shape of the device to be formed on the polymer film.
The size of the predetermined shape is preferably smaller than that of the inorganic substrate, since it is assumed that the substrate is attached to the inorganic substrate. For example, on the premise that it does not protrude from the inorganic substrate, it is preferably about 70 to 98% of the area of the inorganic substrate. However, there is also a method of using a plurality of polymer films laminated on an inorganic substrate. When two sheets of the polymer film are laminated on an inorganic substrate, the area may be, for example, about 35 to 49% of the area of the inorganic substrate.

The cutting trace by the ultraviolet laser has a tapered shape. In press cutting with a knife such as the Thomson type, the cut portion is deformed and does not have a tapered shape. Therefore, if the cutting traces of the outer peripheral portions of the first protective film 104 and the polymer film 102 are tapered, it can be said that they have been cut by the ultraviolet laser.

<Process D>
In step D, the second protective film 106 is peeled off from the polymer film 102 . The method for peeling the second protective film 106 from the polymer film 102 is not particularly limited. For example, as shown in FIGS. A method of lifting and peeling the laminate from the second protective film 106 with a vacuum pad 130 can be used.

<Process E>
In step E, the silane coupling agent layer 124 of the first laminate 120 and the polymer film 102 of the laminate are laminated together to form the inorganic substrate 122, the silane coupling agent layer 124, and the polymer film 102. , and the first protective film 104 are laminated in this order. Specifically, the silane coupling agent layer 124 formed on the inorganic substrate 122 and the polymer film 122 are used as bonding surfaces, and 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 150° C., more preferably room temperature (35° C. or less and 5° C. or more)). Ensure close contact between the two, then, at low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or at normal pressure at relatively high temperature (eg 80 ° C. or higher, more preferably 100 to 250 ° C., more preferably By heating at 110 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 126 in which the inorganic substrate 122 and the polymer film 102 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 silane coupling agent layer may be formed on a heat-resistant polymer film, and then an inorganic substrate may be attached to the silane coupling agent layer.

According to the method for producing a laminate according to the present embodiment, the first protective film has a first substrate made of a polyester film and a first adhesive layer provided on the polyester film. , Since the first adhesive layer contains an ultraviolet absorber, the first protective film and the heat-resistant polymer film are suitably cut by an ultraviolet laser, and the first protective film and the heat-resistant polymer film at the cut surface Detachment from the film can be suppressed.
Moreover, in the laminate obtained by the method for producing a laminate according to the present embodiment, peeling between the first protective film and the heat-resistant polymer film is suppressed.

The method for manufacturing a laminate according to this embodiment has been described above.

<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 method for producing a device structure in the present specification, after peeling the first protective film from the laminate produced by the method described above, a device is formed on the polymer film, and then the polymer film is attached to the inorganic Peel off from the substrate.

The method for 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, forming a peeling portion between the inorganic substrate and the polymer film, and then forming the peeling portion A method can be adopted in which an adhesive tape is adhered to the surface and then rolled up from the tape portion, or a cut portion of the polymer film is vacuum-adsorbed and then rolled up from that portion. 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. do not have. 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.

<Preparation of polyimide film>
[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.

<Thickness measurement of polyimide film>
The thicknesses of the polyimide films 1 to 3 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 3 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 3 are measured for expansion ratio under the following conditions in the machine direction (MD direction) and width direction (TD direction). 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; 20mm
Sample width; 2 mm
Heating start temperature; 25°C
Heating end temperature; 400°C
Temperature rise rate; 5°C/min
atmosphere; argon

<Production of protective film>
[Polyethylene terephthalate film]
The following polyethylene terephthalate film (hereinafter also referred to as PET film) was prepared.
PET film 1: A4100 manufactured by Toyobo Co., Ltd.
PET film 2: E4100 manufactured by Toyobo Co., Ltd.
PET film 3: PET film 1 to which an ultraviolet absorber (Cyasorb UV-3638 (manufactured by CYTEC)) is added by dyeing (obtained from Tochisen Co.)

<Measurement of UV transmittance of PET film>
UV transmittance measurements were performed on PET films 1-3. Specifically, the UV transmittance was measured by a transmission method using UV-3150 manufactured by Shimadzu Corporation. At that time, the transmittance (%) at a wavelength of 355 nm was 73% for PET film 1, 71% for PET film 2, and 74% for PET film 3.

[Adhesive composition]
An adhesive composition was prepared as follows.

[Production Example 7 (Preparation of Adhesive Composition A1)]
70 parts of isononyl acrylate as an acrylic monomer and 0.07 of a photopolymerization initiator (trade name: Irgacure 2020, manufactured by Ciba Specialty Chemicals Co., Ltd.) were placed in a reaction vessel equipped with a cooling pipe, a thermometer, and a stirrer. part, 24.4 parts of polytetramethylene ether glycol (trade name: PTMG1000, manufactured by Mitsubishi Chemical Corporation) as a diol, 0.05 part of dibutyltin dilaurate as a urethane reaction catalyst, and an ultraviolet absorber (Cyasorb UV- 3638 (manufactured by CYTEC)), and then 5.60 parts of 1,3-bis(isocyanatomethyl)cyclohexane (trade name: Takenate 600, manufactured by Mitsui Takeda Chemicals Co., Ltd.) as an isocyanate are stirred. It was added dropwise while stirring, and reacted at 65° C. for 2 hours. Further, 0.30 part of 2-hydroxyethyl acrylate was added to obtain PSA composition A1 (polyurethane-acrylic monomer mixture). The amount of the polyisocyanate component and the polyol component used was [NCO]/[OH]=1.25 in terms of equivalent ratio. The photopolymerization initiator is 80% by weight of 2-hydroxy-2-methyl-1-femyl-1-propanone and 20% by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. A mixture.

[Production Example 8 (Preparation of Adhesive Composition A2)]
A pressure-sensitive adhesive composition A2 (polyurethane-acrylic monomer mixture) was obtained in the same manner as the pressure-sensitive adhesive composition A1, except that the amount of the ultraviolet absorber added was 0.3 parts.

[Production Example 9 (Preparation of Adhesive Composition B)]
An adhesive composition B was obtained by mixing the following.
Linear polyorganosiloxane having vinyl groups only at both ends (solvent-free type, Mw: 80,000): 68.30 parts Organohydrogenpolysiloxane (solvent-free type, Mw: 2,000): 0.41 Parts platinum catalyst (manufactured by Shin-Etsu Chemical, PL-56): 1.00 parts UV absorber (Cyasorb UV-3638 (manufactured by CYTEC)): 0.3 parts Reaction controller (3-methyl-1-butyne-3 - all): 0.10 parts toluene: 30.19 parts

[Production Example 10 (Preparation of Adhesive Composition C)]
A pressure-sensitive adhesive composition C was obtained in the same manner as the pressure-sensitive adhesive composition A1, except that no ultraviolet absorber was added.

[Production Example 11 (Preparation of Adhesive Composition D)]
A pressure-sensitive adhesive composition D was obtained in the same manner as the pressure-sensitive adhesive composition B, except that no ultraviolet absorber was added.

<Production of protective film>
[Preparation of protective film 1]
PET film 1 was subjected to corona treatment as a base treatment, and PET film 1 was coated with adhesive composition A1 immediately after the corona treatment. The coating was performed in an environment of 25° C. and 85% RH, and the thickness after drying was 15 μm. After that, it was heated in an oven at 150° C. for 100 seconds for cross-linking to obtain an adhesive layer. As described above, protective film 1 was obtained.

[Preparation of Protective Films 2, 3 and 7]
Protective films 2, 3, and 7 were obtained in the same manner as protective film 1 above, except that the combination of the PET film and the adhesive composition was changed to the combination shown in Table 2.

[Preparation of protective film 4]
A coating liquid B was prepared by adding 3.5 parts of an isocyanate cross-linking agent (trade name: Coronate L) to the pressure-sensitive adhesive composition B. The PET film 1 was subjected to corona treatment as a base treatment, and the coating solution B was applied immediately after the corona treatment. The coating was performed in an environment of 25° C. and 85% RH, and the thickness after drying was 15 μm. After that, an ultraviolet curing device (manufactured by Eye Graphics Co., Ltd., product name: US2-0401, output: 150 mW/cm ² ) was irradiated for 5 minutes to obtain an adhesive layer. A protective film 4 was obtained as described above.

[Preparation of Protective Films 5, 6, 8 and 9]
Protective films 5, 6, 8, and 9 were obtained in the same manner as protective film 4 above, except that the combination of the PET film and the adhesive composition was changed to the combination shown in Table 2. When using the adhesive composition D, a coating liquid D is prepared by adding 3.5 parts of an isocyanate cross-linking agent (trade name: Coronate L) to the adhesive composition D, and this coating liquid is prepared. D was applied to a PET film.

<UV transmittance measurement of protective film>
A separator (polyethylene terephthalate film (no UV absorber added, thickness: 50 μm) is attached to the surface of the prepared protective films 1 to 9 on which the adhesive layer is exposed, and then the protective film with the separator. UV transmittance measurement was performed on the first base material and the second base material of the present invention. Specifically, the UV transmittance measurement was performed in the same manner as in the “UV transmittance measurement of PET film.” The results are shown in Table 2.

<Production of laminated film>
[Preparation of laminated film 1]
(Example 1)
The protective film 1 obtained in Production Example 12 was attached to both surfaces of the polyimide film 1 obtained in Production Example 4 to obtain the laminated film 1 according to Example 1. The bonding was specifically performed by lamination in a clean environment. Lamination was performed between a metal roll and a rubber roll, and the temperature during lamination was normal temperature of 22° C. and 52% RH, and the sheets were successively attached one by one. The unwinding tension at this time was 120N for the polyimide film and 160N for the protective film. Almost the same tension was applied to the winding side.

[Preparation of laminated films 2 to 15]
Laminated film 1 was produced in the same manner as in the above laminated film 1, except that the combination of the protective film used as the first protective film, the protective film used as the second protective film, and the polyimide film was changed to the combination shown in Table 3. Laminated films 2 to 15 were obtained. The bonding method and conditions were the same as in Example 1.

<Measurement of 90° peel strength between polyimide film and first protective film>
The 90° peel strength between the polyimide film and the first protective film was measured for the laminated film obtained in the production of the laminated film. Table 3 shows the results.
The conditions for measuring the 90° peel strength are as follows.
The polyimide film is peeled off at an angle of 90° with respect to the first protective film.
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; 5 cm

<Production of laminate>
(Example 1)
First, 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. Next, a silane coupling agent (SCA) was applied onto the glass substrate by a vapor phase coating method to form a silane coupling agent layer, thereby obtaining a first laminate (step A). 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.

On the other hand, the laminate film 1 prepared above was irradiated with an ultraviolet laser from the first protective film side so as to have a size of 70 mm×70 mm. The irradiation with the ultraviolet laser was performed in a state in which the first protective film and the second protective film were not peeled off from the polyimide film. The ultraviolet laser used is a pulsed laser with a wavelength of 355 nm manufactured by Takei Electric. The same place was scanned three times at a power of 8.5 W, a pulse frequency of 100 kHz, and a scanning speed of 500 mm/sec. As a result, the first protective film and the polyimide film were cut into a size of 70 mm×70 mm (step C).

Here, the smear width was measured after UV laser irradiation. Specifically, the laser-irradiated surface (first protective film surface) of the laminated film 1 was observed with an optical microscope. Since a black powdery substance was observed, the distance in the orthogonal direction from the laser-cut portion of the black powdery portion was obtained, and the maximum value was taken as the smear width. The results are shown in Tables 4-7.
Also, the peel width between the first protective film and the polyimide film was measured. Specifically, the laser-irradiated surface (first protective film surface) of the laminated film 1 was observed with an optical microscope. Since peeling was observed between the first protective film and the polyimide film, the distance in the orthogonal direction from the laser-cut part of the peeled portion was obtained, and the maximum value of this width was the peeling between the first protective film and the polyimide film. width. The results are shown in Tables 4-7.

Since at least the first protective film and the polyimide film of the laminated film 1 were cut into a size of 70 mm×70 mm by irradiation with the ultraviolet laser, the second protective film was peeled off from the polyimide film (step D).

Next, the silane coupling agent layer and the polyimide film of the first laminate are laminated together, and the glass substrate, the silane coupling agent layer, the polyimide film, and the first protective film are laminated in this order. A laminated body was obtained (step E). 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 laminated film 2 was used instead of the laminated film 1.

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

(Example 4)
A laminate was obtained in the same manner as in Example 3, except that a silicon wafer was used instead of the glass substrate and the method of applying the silane coupling agent (SCA) was changed to spin coating.
Specifically, spin coating was performed as follows.
First, 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.
Next, the silicon wafer was placed on a spin coater (MSC-500S, manufactured by Japan Create Co., Ltd.), isopropyl alcohol was dropped, and then the silicon wafer was rotated at 1000 rpm to spread over the entire surface and then dry. was taken as the final wash.
After that, 5 mL of the solution is dropped on the silicon wafer, and the silicon wafer is rotated at 500 rpm to spread it over the entire surface of the silicon wafer. A ring agent layer was formed.

(Example 5)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 4 was used instead of the laminated film 1.

(Example 6)
A laminate was obtained in the same manner as in Example 3 except that the laser oscillation period of the ultraviolet laser was changed to picoseconds (specifically, the oscillation frequency was 1000 kHz, 15 psec).

(Example 7)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 5 was used instead of the laminated film 1.

(Example 8)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 6 was used instead of the laminated film 1.

(Example 9)
A laminate was obtained in the same manner as in Example 7 except that the laser oscillation period of the ultraviolet laser was changed to picoseconds (specifically, the oscillation frequency was 1000 kHz, 15 psec).

(Example 10)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 7 was used instead of the laminated film 1.

(Example 11)
A laminate was obtained in the same manner as in Example 10, except that a silicon wafer was used instead of the glass substrate.

(Example 12)
The procedure was the same as in Example 1, except that the laminated film 8 was used instead of the laminated film 1, and the laser oscillation period of the ultraviolet laser was changed to picoseconds (specifically, the oscillation frequency was 1000 kHz, 15 psec). to obtain a laminate.

(Example 13)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 9 was used instead of the laminated film 1.

(Example 14)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 10 was used instead of the laminated film 1 and that a silicon wafer was used instead of the glass substrate.

(Example 15)
The procedure was the same as in Example 1 except that the laminated film 11 was used instead of the laminated film 1, and the laser oscillation period of the ultraviolet laser was changed to picoseconds (specifically, the oscillation frequency was 1000 kHz and 15 psec). to obtain a laminate.

(Comparative example 1)
A laminate was obtained in the same manner as in Example 1, except that the laminate film 12 was used instead of the laminate film 1, and that mechanical cutting with a Thomson blade was used instead of ultraviolet laser cutting.

(Comparative example 2)
A laminate was obtained in the same manner as in Example 1, except that the laminated film 13 was used instead of the laminated film 1.

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

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

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.

<Peeling Width Between Inorganic Substrate and Polyimide Film>
For the produced laminate, the peel width between the inorganic substrate and the polyimide film was measured (only examples and comparative examples in which the inorganic substrate was a glass substrate). Specifically, the produced laminate was observed with an optical microscope from the inorganic substrate side. Since peeling was observed between the inorganic substrate and the polyimide film, the width of the peeled portion (the width in the direction perpendicular to the laser cutting portion) was obtained, and the maximum value of this width was the distance between the first protective film and the polyimide film. The stripping width is defined as the stripping width. The results are shown in Tables 4-7.

<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 4-7.
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

(result)
In laminated films 1 to 11 in which a protective film containing an ultraviolet absorber is used as the first protective film in the adhesive layer (first adhesive layer), the first protective film and the polyimide film are preferably separated by an ultraviolet laser. was able to cut to That is, the smear width of the cut portion was narrow and the shape of the cross section was regular. Moreover, it was confirmed that the separation width between the first protective film and the polyimide film at the cut surface was narrow, and that separation could be suppressed.

(Reference example 1)
Laminated film 1 was mechanically cut with a Thomson blade so as to have a size of 70 mm×70 mm. The peeling width between the first protective film and the polyimide film was measured in the same manner as above, and was 300 μm.

(Reference example 2)
The laminate film 1 was irradiated with a CO ₂ laser from the first protective film side so as to have a size of 70 mm×70 mm. The CO ₂ laser irradiation was performed in a state in which the first protective film and the second protective film were not separated from the polyimide film. The CO ₂ laser used is from Coherent with a wavelength of 10.6 μm. Scanning was performed once under the conditions of an oscillation frequency of 100 kHz, 15 kW, and a scan speed of 300 mm/sec. As a result, the first protective film and the polyimide film were cut into a size of 70 mm×70 mm in the same manner as described above. When the peel width between the first protective film and the polyimide film was measured, it was 1900 μm. Further, when the smear width after CO ₂ laser irradiation was measured in the same manner as above, it was 2450 μm.

REFERENCE SIGNS LIST 100 laminated film 102 polymer film 104 first protective film 106 second protective film 120 first laminate 122 inorganic substrate 124 silane coupling agent layer 126 laminate 130 vacuum pad

Claims (8)

a heat-resistant polymer film;
a first protective film laminated on one surface of the heat-resistant polymer film;
a second protective film laminated on the other surface of the heat-resistant polymer film,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first adhesive layer contains an ultraviolet absorber,
The ultraviolet absorber is a cyclic imino ester system,
The heat-resistant polymer film has a melting point of 400° C. or higher and a glass transition temperature of 250° C. or higher,
A laminated film characterized by being cut by an ultraviolet laser before use. a heat-resistant polymer film;
a first protective film laminated on one surface of the heat-resistant polymer film;
a second protective film laminated on the other surface of the heat-resistant polymer film;
with
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first adhesive layer contains an ultraviolet absorber,
The ultraviolet absorber is a cyclic imino ester system,
The heat-resistant polymer film is a polyimide resin film,
A laminated film characterized by being cut by an ultraviolet laser before use. 3. The laminated film according to claim 1, wherein the 90° peel strength between the heat-resistant polymer film and the first protective film is 0.002 N/cm or more and 0.3 N/cm or less. 4. The laminated film according to any one of claims 1 to 3, wherein the first base material is a polyethylene terephthalate film. The laminate film according to any one of claims 1 to 4 , wherein the heat-resistant polymer film is a polyimide film. An inorganic substrate, a silane coupling agent layer, a heat-resistant polymer film, and a first protective film are laminated in this order,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first adhesive layer contains an ultraviolet absorber ,
A laminate, wherein the heat-resistant polymer film has a melting point of 400° C. or higher and a glass transition temperature of 250° C. or higher . An inorganic substrate, a silane coupling agent layer, a heat-resistant polymer film, and a first protective film are laminated in this order,
The first protective film has a first substrate made of a polyester film and a first pressure-sensitive adhesive layer provided on the first substrate,
The first adhesive layer contains an ultraviolet absorber,
A laminate, wherein the heat-resistant polymer film is a polyimide resin film. Step A of preparing a first laminate having an inorganic substrate and a silane coupling agent layer;
A step B of preparing the laminated film according to any one of claims 1 to 5 ;
a step C of irradiating the laminated film with an ultraviolet laser from the side of the first protective film to cut the first protective film and the heat-resistant polymer film into a predetermined shape;
After the step C, a step D of peeling the second protective film from the heat-resistant polymer film;
After the step D, the silane coupling agent layer and the heat-resistant polymer film of the first laminate are bonded together to obtain the inorganic substrate, the silane coupling agent layer, the heat-resistant polymer film, and a step E of obtaining a laminate in which the first protective film and the first protective film are laminated in this order.

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