JP6688450B2 - Laminate, electronic device, and flexible electronic device manufacturing method - Google Patents

Description

  The present invention provides a flexible electronic device by temporarily fixing a flexible polymer film and a glass plate to form a laminate, then forming various electronic devices on the polymer film, and then peeling the polymer film together with the electronic device section. Manufacturing technology to obtain. The present invention also relates to a technique for manufacturing a electronic device on the glass plate surface side by fixing a flexible polymer film and a glass plate as a laminate.

  Functional elements (devices) such as semiconductor elements, MEMS elements, and display elements are used as electronic components in information communication equipment (broadcast equipment, mobile radio, mobile communication equipment, etc.), radar, high-speed information processing equipment, etc. Conventionally, it has been generally formed or mounted on an inorganic substrate such as glass, a silicon wafer, or a ceramic substrate. However, in recent years, with the demand for lighter weight, smaller size, thinner thickness, and greater flexibility of electronic components, attempts have been made to form various functional elements on a polymer film.

  When forming various functional elements on the surface of the polymer film, it is ideal to perform processing by a so-called roll-to-roll process, which utilizes the flexibility which is a characteristic of the polymer film. However, in the industries such as the semiconductor industry, the MEMS industry, and the display industry, process technology for a rigid flat substrate such as a wafer base or a glass plate base has been the mainstream. Therefore, in order to form various functional elements on the surface of the polymer film by utilizing the existing infrastructure, a polymer solution or a rigid support made of an inorganic material (glass plate, ceramic plate, silicon wafer, metal plate, etc.) is used. The precursor solution is applied and dried to form a film, on which the desired element is formed and then peeled from the support, or the film is temporarily fixed to a support made of an inorganic material, and the desired element is formed into a film. A process of peeling from the support after being formed has been developed (Patent Documents 1 to 3).

  Generally, a relatively high temperature is often used in the process of forming the functional element. For example, a temperature range of about 120 to 500 ° C. is used in forming a functional element such as polysilicon or an oxide semiconductor. When manufacturing a low temperature polysilicon thin film transistor, heating at about 450 ° C. may be necessary for dehydrogenation. A temperature range of about 150 to 250 ° C. is required also for manufacturing a hydrogenated amorphous silicon thin film. Although the temperature range illustrated here is not so high for an inorganic material, it must be said that it is a considerably high temperature for a polymer film or an adhesive generally used for bonding polymer films. I don't get it. In the method of sticking the polymer film to the inorganic substrate described above and peeling it after forming the functional element, sufficient heat resistance is required for the polymer film used, the adhesive used for bonding, and the adhesive. However, as a practical matter, polymer films that can be practically used in such a high temperature range are limited. In addition, it is the current situation that there are very few conventional adhesives and pressure-sensitive adhesives for bonding which have sufficient heat resistance.

  A polymer film or a precursor solution is applied to a support made of an inorganic material as described above to form a film by drying, and a desired element is formed on the support, followed by peeling from the support. This is a technology devised because a heat-resistant adhesive means for temporarily adhering a resin to an inorganic substrate cannot be obtained. However, since the polymer film obtained by such means is intimately adhered to the inorganic substrate, even if it is peeled from the inorganic substrate, it is fragile and easily torn, so that the functional element is destroyed when peeled from the inorganic substrate. It often happens. Particularly, peeling a large-area device is extremely difficult and the productivity is not sufficient.

  In view of such circumstances, the inventors of the present invention, as a laminate of a polymer film and a support for forming a functional element, a polyimide film having excellent heat resistance, which is tough and can be thinned, and a coupling agent. It proposed the laminated body laminated | attached on the support body (inorganic layer) which consists of an inorganic material through (patent document 4-6).

  Since the polymer film is originally a flexible material, it does not hinder expansion and contraction or bending and stretching. On the other hand, electronic devices formed on polymer films often have a fine structure in which conductors and semiconductors made of inorganic substances are combined in a predetermined pattern, and stress due to minute expansion and contraction or bending and stretching. As a result, the structure is destroyed and the device characteristics are impaired. Such stress is likely to occur when the electronic device, together with the polymer film, is separated from the inorganic substrate.

  Therefore, the inventors of the present invention further improved and partially deactivated the coupling agent-treated inorganic substrate to form a high activity portion and a low activity portion of the coupling agent. When a molecular film is attached, a good adhesion part that is relatively difficult to peel off and an easy peeling part that is relatively easy to peel off are formed, and an electronic device is formed on the easy peeling part. A technique has been proposed in which a cut is made at the boundary with the adhesive portion and only the easily peelable portion is peeled off, so that peeling can be performed in a state in which stress applied to the electronic device is reduced (Patent Document 7).

  On the other hand, in recent years, a glass plate having a thickness of less than 100 μm has been developed and has attracted attention as a novel flexible substrate having transparency and heat resistance. Although such an ultra-thin glass plate is flexible, there is a risk of cracking, scattering of glass fragments, and the like when deformed to a bending radius of less than or equal to the limit. Bonding a shatterproof film, etc. is an effective method to reduce the risk regardless of the thickness of the glass plate, but a typical shatterproof film uses a glass plate with an adhesive or adhesive. Since the film and the film are adhered to each other, there are drawbacks such that they are not suitable for a processing process involving a high temperature step in a state in which the anti-scattering film is attached, and the operating temperature range is limited in the application of the product.

JP-A-58-91446 JP, 10-125930, A JP-A-2000-243943 JP, 2010-283262, A JP, 2011-11455, A JP, 2011-245675, A JP, 2013-010342, A

  According to the laminates described in Patent Documents 4 to 7 described above, the polymer film and the inorganic substrate can be bonded to each other without using a so-called adhesive or pressure-sensitive adhesive, and further, the laminate forms a thin film device. The polymer film does not peel when exposed to the high temperatures required to do so. Therefore, it becomes possible to subject the laminate to a conventional process for directly forming an electronic device on an inorganic substrate such as a glass plate or a silicon wafer. However, in such a technique, a vacuum plasma treatment is often used for the activation treatment of the film, and thus there are problems in productivity and processing cost. The wet treatment is advantageous in terms of cost, but in some polymer films, the alkaline component used in the wet treatment deteriorates the film itself and lowers the mechanical strength, and the adhesive strength with the support. Could become unstable and the film might come off during the process.

In this way, a method for producing a flexible electronic device by temporarily fixing a polymer film to a supporting substrate made of an inorganic material (hereinafter referred to as an inorganic substrate) to perform device processing, and peeling the polymer film from the inorganic substrate is Since the vacuum device is used during the surface activation treatment of the polymer film and the heating and pressurization of the polymer film and the inorganic substrate (eg glass plate), the productivity and processing cost are not sufficient, and the surface activation without using the vacuum device. It was desired to establish a treatment and heating / pressurizing method.
Therefore, the present invention does not require the use of a vacuum device at the time of surface activation treatment of a polymer film (also referred to as a condensation polymer film) or at the time of heating and pressurizing the polymer film and the glass plate. It is an object of the present invention to provide a method capable of stably adhering the laminated body of 1) and easily peeling the polymer film from the glass plate after mounting the electronic device.

  In order to solve the above problems, the present inventors have conducted extensive studies on wet processing, and as a result, have found that a processing solution that enables extremely stable bonding (temporary support) is used for a laminate, and the present invention is achieved. completed.

That is, the present invention has the following configurations.
[1] In a laminate comprising a condensation-type polymer film and a glass plate, a carboxyl group has 1.0 × 10 ^{3 to} 1.0 × 10 ^{8 on} the adhesive surface of the condensation-type polymer film to be bonded to the glass plate. A laminated body characterized by being present in an equivalent amount / cm ² .
[2] The carboxyl group is produced using an alkaline solution containing at least (a) an oxyalkylamine compound, and (b) ammonia and a compound selected from the ammonium hydroxide compounds represented by the general formula (1). The laminated body according to [1].
Formula ^{(1) {(R 1)} 3 -N + -R 2} · OH -
[In the formula, R ¹ represents H or a C1-8 alkyl group.
R ² represents H, a C1-8 alkyl group, or a C1-8 hydroxyalkyl group.
R ^{1 s} may be the same or different. ]
[3] The laminate according to [1] or [2], wherein the condensation polymer film is a polyimide film, a polyamide film, a polyamideimide film, a polybenzoxazole film, a polyester film, a polyethylene naphthalate film or a liquid crystal polymer film. body.
[4] The laminate according to any one of [1] to [3], wherein the condensation polymer film is a polyimide film.
[5] The laminate according to any one of [1] to [4], wherein the surface of the glass plate to be bonded to the condensation polymer film is surface-activated with a silane coupling agent.
[6] The laminate according to any one of [1] to [5], wherein the surface of the condensation-type polymer film to be bonded to the glass plate is surface-activated with a silane coupling agent.
[7] When the glass plate is treated with a silane coupling agent, the adhesive strength in 90 ° peeling after heat treatment of the glass plate and the condensation polymer film is 1.0 N / cm or more and 10 N / cm or less. The laminate according to any one of [1] to [6].
[8] The adhesive strength in 90 ° peeling after heat treatment of the glass plate and the condensation-type polymer film when the glass plate is not treated with a silane coupling agent is 0.03 N / cm or more and less than 1.0 N / cm The laminated body according to any one of [1] to [4] and [6].
[9] An electronic device formed by printing or using a thin film on the glass plate surface of the laminate according to any one of [1] to [8].
[10] It is characterized in that the condensation-type polymer film and the glass plate are separated after forming an electronic device on the surface of the condensation-type polymer film of the laminate described in any one of [1] to [8]. Flexible electronic device manufacturing method.

  According to the present invention, it is not necessary to use a vacuum device at the time of surface activation treatment of a polymer film or at the time of heating and pressurizing the polymer film and the glass plate, and the laminate of the polymer film and the glass plate can be stably bonded. In addition, the polymer film can be easily peeled from the glass plate after mounting the electronic device.

  The laminate of the present invention, the polymer film, at least the surface used for adhesion to the glass plate to generate a carboxyl group by surface treatment, the physical group or a chemical bond between the carboxyl group and the functional group on the glass plate surface to form both. Obtained by gluing. Carboxyl groups are relatively easy to generate by oxidation or hydrolysis reaction of polymer compounds. Particularly in condensation type polymers represented by polyimide, polyamide, polyester, etc., the present invention is effectively applied because carboxyl groups are relatively easily generated on the surface of the polymer film by a wet treatment containing alkali. be able to.

  Since the present invention can preferably use a wet treatment under normal pressure with a chemical solution containing an ammonium hydroxide compound or a chemical solution containing an oxyalkylamine, a relatively inexpensive apparatus can be used.

  Further, in the present invention, the adhesive force between the polymer film of the laminate and the glass plate can be controlled by the amount of carboxyl groups produced. When the adhesive strength is controlled weakly, the stress on the polymer film when peeling the polymer film after forming the electronic device from the glass plate of the laminate can be kept small, so the yield and reliability of the electronic device can be reduced. Is improved. On the other hand, when the adhesive force is strongly controlled, for example, when a device is formed on the glass plate side and the polymer film on the opposite surface is used as a glass plate reinforcement or a shatterproof film.

  The carboxyl group generated by the surface treatment using an alkaline solution containing ammonia and / or the ammonium hydroxide compound represented by the general formula (1) is formed by hydrogen bonding with a polar component present on the surface of the glass plate or a functional group such as a hydroxyl group. It is also possible to bond them and further to modify them into chemical bonds with covalent bonds such as ester bonds, amide bonds and imide bonds by post-treatment such as heating.

  Due to such effects, the polymer film laminated to the glass plate does not peel off even if exposed to conditions such as heating, depressurization, alkali treatment, acid treatment, washing with an organic solvent at the time of device formation, and device formation does not occur. Since it is possible, the device can be formed on both the film surface side and the glass plate surface side.

  When it is necessary to peel off the polymer film after the device is formed, it can be peeled off by means involving laser irradiation from the back surface of the glass plate, flash lamp irradiation, or the like. Also, by strongly adhering the area around the film attachment surface and keeping the adhesive force in the device formation area near the center of the film weak, the boundary between the strong adhesion portion and the weak adhesion portion is cut after device formation, It is also possible to peel off only the formation region. The strength of the adhesive force can be realized by patterning the adhesive surface of the film or the glass plate side.

The laminate of the present invention is a laminate comprising a condensation-type polymer film and a glass plate, wherein a predetermined amount of carboxyl groups is present per cm ² on the adhesive surface of the condensation-type polymer film to be bonded to the glass plate. Characterize.

<Glass plate>
In the present invention, a glass plate is used as a bonding partner of the polymer film. As the glass, quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), borosilicate Glass (microsheet), aluminosilicate glass, etc. are included. Among these, those having a linear expansion coefficient of 5 ppm / ° C. or less are desirable, and if they are commercially available products, “Corning (registered trademark) 7059” and “Corning (registered trademark) 1737” manufactured by Corning, which are glass for liquid crystal, “EAGLE”, “AN100” manufactured by Asahi Glass Co., Ltd., “OA10” manufactured by Nippon Electric Glass Co., Ltd., “AF32” manufactured by SCHOTT Co., etc. are preferable.

It is desirable that the flat part of the glass plate is sufficiently flat. Specifically, the surface roughness Ra is, for example, 10 nm or less, preferably 3 nm or less, and more preferably 0.9 nm or less. The PV value of the surface roughness is, for example, 50 nm or less, preferably 20 nm or less, more preferably 5 nm or less. If it is rougher than this, the adhesive strength between the polymer film and the glass plate may be insufficient.
The thickness of the glass plate is not particularly limited, but from the viewpoint of handleability, the thickness is preferably 10 mm or less, more preferably 3 mm or less, and further preferably 1.3 mm or less. The lower limit of the thickness is not particularly limited, but for example, 0.07 mm or more, preferably 0.15 mm or more, more preferably 0.3 mm or more is used.

The glass plate in the present invention preferably has a size of at least 4900 cm ² or more. The glass plate of the present invention preferably has a substantially rectangular shape with at least 700 mm on the short side. In the present invention, the area of the glass plate is preferably 5000 cm ² or more, more preferably 10000 cm ² or more, still more preferably 18000 cm ² or more. Further, the length of the short side of the rectangle of the glass plate in the present invention is preferably 730 mm or more, more preferably 840 mm or more, and further preferably 1000 mm or more.

  The term “substantially rectangular” means that the corners R, cutouts, notches, orientation flats, etc. of the rectangle are allowed. In the flat panel display industry according to the present invention, a 680 × 880 mm to 730 × 920 mm glass plate called the 4th generation, a 1000 × 1200 mm to 1100 × 1250 mm to 1300 × 1500 mm glass plate called the 5th generation, and a 6th generation Called 1370x1670mm to 1500x1800mm glass plate, called 7th generation 1870x2200mm glass plate, called 8th generation 2160x2460mm to 2200x2500mm glass plate, called 9th generation 2400x2800mm A glass plate, a 2880 × 3130 mm glass plate called the 10th generation, a 3320 × 3000 mm glass plate called the 11th generation, or a glass plate having a size larger than this corresponds to this “substantially rectangular”. . However, the present invention is not limited to the application to the glass plate having the area, size, and the shorter side length of the rectangle illustrated here.

  In the present invention, an ultrathin glass sheet or roll having a glass plate thickness of, for example, 200 μm or less, preferably 110 μm or less, more preferably 55 μm or less, and further preferably 33 μm or less can be used as the glass plate.

<Polymer film>
The polymer film in the present invention is a film made of a polymer formed by a polycondensation reaction such as an ester bond, an amide bond, an imide bond, a benzazole bond and an ether bond. Polymers preferably used in the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, wholly aromatic polyester, other copolyesters, polycarbonate, polyamide, polysulfone, polyether sulfone, polyether ketone, polyamide imide, Polyetherimide, aromatic polyimide, alicyclic polyimide, fluorinated polyimide, cellulose acetate, cellulose nitrate, aromatic polyamide, polyphenol, polyarylate, polyphenylene sulfide, polyphenylene oxide, phenol resin, urea resin, melamine resin, polycarbonate resin, A film such as a liquid crystal polymer can be used. In the present invention, among the polymer films obtained by these polycondensation reactions, a polymer having a heat resistance of 100 ° C. or higher, that is, a so-called engineering plastic film, is particularly effective and useful. Here, heat resistance means a glass transition temperature or a heat distortion temperature. The condensation polymer film preferably used in the present invention is polyester, polyamide, polyamideimide, polyimide, polybenzazole, polyimidebenzazole, polyethylene naphthalate film, liquid crystal polymer film, more preferably polyimide film, polyethylene naphthalate film. Alternatively, it is a liquid crystal polymer film.

The Young's modulus (tensile elastic modulus) of the polymer film of the present invention is preferably 2 GPa or more, more preferably 3.5 GPa or more, still more preferably 6 GPa or more, even more preferably 7.4 GPa or more, and particularly preferably 8 It is not less than 0.2 GPa, most preferably not less than 9.1 GPa. Young's modulus is the Young's modulus obtained by pulling. If the Young's modulus is less than this range, the elongation of the polymer film becomes large when the polymer film is peeled from the glass plate, and the electronic device is likely to be broken.
In the present invention, the upper limit of the Young's modulus is not particularly limited, but is actually about 15 GPa. A material having a too high Young's modulus is not suitable as a base material for a flexible electronic device because the film is often brittle and easily broken.

  The lower limit of the thickness of the polymer film of the present invention is not particularly limited, but it is preferably 4.5 μm or more in order to maintain the minimum mechanical strength as a base material of an electronic device. In the present invention, the thickness of the polymer film is more preferably 12 μm or more, further preferably 24 μm or more, still more preferably 45 μm or more. Although the upper limit of the thickness of the polymer film is not particularly limited, it is preferably 250 μm or less, more preferably 150 μm or less, and further preferably 90 μm or less for the flexible electronic device.

  The polymer film particularly preferably used in the present invention is a polyimide film, and aromatic polyimide, alicyclic polyimide, polyamideimide, polyetherimide and the like can be used. When the present invention is particularly used for manufacturing a flexible display element, it is preferable to use a polyimide resin film having a colorless transparency, but particularly in the case of forming a rear element of a reflective or self-luminous display, Not limited to this.

  In general, a polyimide film is obtained by applying a polyamic acid (polyimide precursor) solution obtained by reacting a diamine and a tetracarboxylic acid in a solvent onto a support for polyimide film production, and drying the green film (“precursor film”). Or "polyamic acid film"), and is further obtained by performing a dehydration ring-closing reaction by heat-treating the green film at high temperature on a support for producing a polyimide film or in a state of being peeled from the support.

  The diamines that compose the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like that are commonly used in polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among the aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, high heat resistance, high elastic modulus, low heat shrinkability, and low linear expansion coefficient can be exhibited. The diamines may be used alone or in combination of two or more.

  The aromatic diamines having a benzoxazole structure are not particularly limited and include, for example, 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-phenylene bis (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 -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 can be mentioned.

  Examples of aromatic diamines other than the aromatic diamines having a benzoxazole structure described above include 2,2′-dimethyl-4,4′-diaminobiphenyl and 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] prene Bread, 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'-diaminophen Zophenone, 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-amino) Phenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminopheno) Si) 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-f Xafluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) 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-aminophenoxy) 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) benzo ]] Diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4, 4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, 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-fur Orofenoxy) -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'-dia No-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-bi Phenoxybenzophenone, 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-biphenoxybenzoyl) 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 part or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are halogen atoms, alkyl groups or alkoxy groups having 1 to 3 carbon atoms, or cyano groups. Or an aromatic diamine substituted with a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxyl group in which some or all of the hydrogen atoms of the alkyl group or alkoxyl group are substituted with halogen atoms.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 1,8-diaminooctane.
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 of all diamines, more preferably 10% by mass or less, and further preferably 5% by mass or less. Is. In other words, the aromatic diamine content is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more of the total diamines.

  The tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including their acid anhydrides), aliphatic tetracarboxylic acids (including their acid anhydrides), and alicyclic tetracarboxylic acids that are usually used in polyimide synthesis. Acids (including its acid anhydride) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and alicyclic rings from the viewpoint of light transmission. Group tetracarboxylic acids are more preferred. When these are acid anhydrides, the number of anhydride structures may be one or two in the molecule, but those having two anhydride structures (dianhydride) are preferable. Good. The tetracarboxylic acids may be used alone or in combination of two or more.

Examples of alicyclic tetracarboxylic acids include alicyclic tetracarboxylic acids such as cyclobutane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, and 3,3 ′, 4,4′-bicyclohexyl tetracarboxylic acid. Carboxylic acids, and their acid anhydrides. Among these, a dianhydride having two anhydride structures (for example, cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Bicyclohexyl tetracarboxylic acid dianhydride and the like) are preferable. The alicyclic tetracarboxylic acids may be used alone or in combination of two or more.
When importance is attached to transparency, the alicyclic tetracarboxylic acids are, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more of the total tetracarboxylic acids.

The aromatic tetracarboxylic acid is not particularly limited, but is preferably a pyromellitic acid residue (that is, one having a structure derived from pyromellitic acid), and 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, and 3 , 3 ', 4,4'-Benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-Diphenylsulfone tetracarboxylic dianhydride, 2,2-bis [4- (3,4-di) Carboxyphenoxy) phenyl] propanoic anhydride and the like.
When the heat resistance is important, the aromatic tetracarboxylic acids are, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more of the total tetracarboxylic acids.

  The glass transition temperature of the polyimide film of the present invention is, for example, 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or it is preferable that the glass transition temperature is not observed in the region of 500 ° C. or lower. The glass transition temperature is determined by differential thermal analysis (DSC).

  The linear expansion coefficient (CTE) of the polymer film of the present invention is preferably −5 ppm / ° C. to +45 ppm / ° C., more preferably −5 ppm / ° C. to +40 ppm / ° C., and further preferably +1 ppm / ° C. to +35 ppm. / ° C, and even more preferably +1 ppm / ° C to +10 ppm / ° C. When the CTE is in the above range, the difference in linear expansion coefficient from a general support can be kept small, and peeling between the polyimide film and the support made of an inorganic material can be avoided even when subjected to a process of applying heat. .

  The tensile rupture strength of the polymer film in the present invention is, for example, 60 MPa or more, preferably 120 MPa or more, more preferably 240 MPa or more. There is no upper limit to the tensile breaking strength, but it is practically less than about 1000 MPa. Here, the tensile breaking strength of the polymer film means an average value in the MD direction and the TD direction of the polymer film.

  The tensile elongation at break of the polymer film in the present invention is, for example, 10% to 200%, preferably 20% to 160%, more preferably 40% to 150%. Here, the tensile elongation at break of the polymer film means an average value in the MD direction and the TD direction of the polymer film.

  The heat shrinkage rate of the polymer film of the present invention is preferably 0.5% or less when heated at 400 ° C. for 1 hour. Such characteristics are obtained by using pyromellitic acid as a tetracarboxylic dianhydride in an amount of 50 mol% or more and simultaneously using diamine having a paraphenylenediamine or a benzoxazole structure in an amount of 50 mol% or more among the raw materials of the polyimide film. It can be obtained by using tetracarboxylic acid anhydride having 1 to 2 rings and paraphenylenediamine as a diamine component in an amount of 85 mol% or more.

The thickness unevenness of the polymer film in the present invention is preferably 0.1% or more and 20% or less, more preferably 12% or less, further preferably 7% or less, and particularly preferably 4% or less. If the thickness unevenness exceeds 20%, it tends to be difficult to apply it to a narrow portion. The unevenness of the film thickness can be obtained based on the following formula by randomly extracting about 10 points from the film to be measured with a contact type film thickness meter and measuring the film thickness.
Film thickness unevenness (%) = 100 × (maximum film thickness−minimum film thickness) ÷ average film thickness

  In a polymer film, in order to ensure handling and productivity, it is possible to add / contain a lubricant (particles) in the film to impart fine irregularities to the surface of the polymer film to ensure slipperiness. preferable. The lubricant (particles) is preferably fine particles made of an inorganic material, such as metal, metal oxide, metal nitride, metal carbonide, metal salt, phosphate, carbonate, talc, mica, clay, etc. Particles made of clay mineral or the like can be used. Preferably, metal oxides such as silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, phosphates and carbonates can be used. Only one kind of lubricant may be used, or two or more kinds thereof may be used.

  The volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 μm, preferably 0.03 to 2.5 μm, more preferably 0.05 to 0.7 μm, and further preferably 0.05 to It is 0.3 μm. The volume average particle diameter is based on the measured value obtained by the light scattering method. If the particle size is smaller than the lower limit, industrial production of the polymer film becomes difficult, and if it exceeds the upper limit, surface irregularities become too large and the attachment strength becomes weak, which may cause a practical problem.

  The amount of the lubricant added is, for example, 0.02 to 5% by mass, preferably 0.04 to 1% by mass, and more preferably 0.08 to 0. It is 4% by mass. If the amount of lubricant added is too small, it is difficult to expect the effect of lubricant addition, and the slipperiness may not be secured so much, which may interfere with polymer film production.If it is too large, the surface irregularities of the film will become too large. Therefore, even if the slipperiness is ensured, the smoothness may be lowered, the breaking strength and the breaking elongation of the polymer film may be lowered, and the CTE may be increased.

  When the lubricant (particles) is added to and contained in the polymer film, it may be a single-layer polymer film in which the lubricant is uniformly dispersed. For example, one surface is a polymer film containing the lubricant. A multi-layered polymer film composed of a polymer film having the other surface containing no lubricant or containing a small amount of lubricant even if the other surface is contained may be used. In such a multilayer polymer film, fine irregularities are provided on the surface of one layer (film) to ensure slipperiness in the layer (film), thus ensuring good handleability and productivity. it can.

  In the case of a film produced by a melt-stretching film forming method, for example, a multilayer polymer film is first formed into a film using a polymer film raw material that does not contain a lubricant, and at least one surface of the film is coated with the lubricant during the process. It can be obtained by applying the contained resin. Of course, on the contrary, a polymer film raw material containing a lubricant is used to form a film, and a polymer film raw material containing no lubricant is applied during the process or after the film formation is completed to obtain a film. You can also do it.

  The same applies to the case of a polymer film obtained by using a solution casting method such as a polyimide film. For example, as a polyamic acid solution (precursor solution of polyimide), a lubricant (preferably an average particle diameter of 0.05 to About 2.5 μm) to 0.02% by mass to 50% by mass (preferably 0.04 to 3% by mass, more preferably 0.08 to 1.2% by mass) based on the polymer solid content in the polyamic acid solution. Polyamic acid solution contained and no lubricant or a small amount thereof (preferably less than 0.02% by mass, more preferably less than 0.01% by mass with respect to the polymer solid content in the polyamic acid solution) It can be manufactured using two types of polyamic acid solutions.

The method for forming a multilayer (lamination) of the multilayer polymer film is not particularly limited as long as there is no problem in the adhesion of both layers, and any method may be used as long as it adheres without an adhesive layer or the like.
In the case of a polyimide film, for example, i) a method of producing one polyimide film and then continuously applying the other polyamic acid solution on the polyimide film to imidize, ii) casting one polyamic acid solution After producing a polyamic acid film, continuously coating the other polyamic acid solution on this polyamic acid film, and then imidizing, iii) coextrusion method, iv) no lubricant or its content is An example is a method of applying a polyamic acid solution containing a large amount of a lubricant by spray coating, T-die coating or the like on a film formed with a small amount of polyamic acid solution to imidize the film. In the present invention, it is preferable to use the above methods i) to ii).

  The thickness ratio of each layer in the multilayer polymer film is not particularly limited, but the polymer layer containing a large amount of lubricant (a) layer, the polymer containing no lubricant or a small amount thereof When the layer is the (b) layer, the thickness ratio of the (a) layer / (b) layer is preferably 0.05 to 0.95. If the thickness ratio of the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost, while if it is less than 0.05, the effect of improving the surface properties tends to be insufficient. Lubricity may be lost.

  The polymer film in the present invention is preferably one obtained in the form of a long film having a width of 300 mm or more and a length of 10 m or more at the time of its production, and a roll-shaped polyimide wound on a winding core. More preferably, it is in the form of a film.

It is essential that carboxyl groups are present in an amount of 1.0 × 10 ^{3 to} 1.0 × 10 ⁸ equivalents / cm ^{2 on} the adhesive surface of the condensation-type polymer film that is bonded to the glass plate in the present invention. The carboxyl group is preferably present in an amount of 3.0 × 10 ^{3 to} 1.0 × 10 ⁷ equivalents / cm ² , more preferably 1.0 × 10 ^{4 to} 3.0 × 10 ⁶ equivalents / cm ^2. It is more preferable that 3.0 × 10 ^{4 to} 1.0 × 10 ⁶ equivalents / cm ^{2 be} present.
The amount of carboxyl groups can be quantified by IR analysis or a chemical modification method. IR analysis is effective when the amount of carboxyl groups is relatively large. The chemical modification method is effective when the amount of carboxyl groups is relatively small. The chemical modification method may be either a wet method or a dry method.

As the analysis method, for example, trifluoroethanol _{(TFE: CF 3 CH 2 OH} ), di -t- butyl carbodiimide (Di-t-BuC: ( CH 3) 3 C = NC = NC (CH 3) 3) , Pyridine (C ₆ H ₅ N) is used, phenyl is used as a catalyst to add —CH ₂ CF ₃ of trifluoroethanol to the carboxyl group, and the amount of the added elemental fluorine can be quantified by XPS, ESCA or the like. .

<Surface activation treatment of polymer film>
The surface treatment for generating a carboxyl group on the surface of the polymer film is at least (a) an oxyalkylamine compound, and (b) an alkaline compound containing a compound selected from ammonia and the ammonium hydroxide compound represented by the general formula (1). A surface treatment using a solution can be exemplified.
Formula ^{(1) {(R 1)} 3 -N + -R 2} · OH -
[In the formula, R ¹ is H or a C 1-8 alkyl group.
R ² is H, a C1-8 alkyl group, or a C1-8 hydroxyalkyl group.
R ¹ may be the same or different. ]

The alkyl group of R ¹ and R ² has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms.
The carbon number of the hydroxyalkyl group of R ² may be the same as the carbon number of the alkyl group.

The ammonium hydroxide compound preferably used in the present invention, ammonium hydroxide, monomethylammonium hydroxide, dimethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, With alkylammonium hydroxide compounds such as trioctylmethylammonium hydroxide, triethylmethylammonium hydroxide, trimethylethylammonium hydroxide, and (hydroxyalkyl) alkylammonium hydroxide compounds such as N- (2-hydroxyethyl) trimethylammonium hydroxide. is there.
The ammonium hydroxide compounds particularly preferably used in the present invention are ammonia, tetramethylammonium hydroxide and N- (2-hydroxyethyl) trimethylammonium hydroxide. Similarly, ammonia is also particularly preferably used in the present invention.

An aqueous solution, an alcohol solution, and a solvent solution are preferably used as the alkaline solution containing ammonia and / or ammonium hydroxide compound in the present invention, and the alcohol solution is a methanol solution, an ethanol solution, an isopropanol solution, a normal propanol solution, or a butanol solution. . As the solvent solution, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like can be used.
Among them, the alkaline solution is preferably an aqueous solution from the viewpoint of workability.

  The content of ammonia and / or ammonium hydroxide compound in the alkaline solution of the present invention is not particularly limited, and a stock solution of ammonia and / or ammonium hydroxide compound may be used. However, from the viewpoint of workability, the content of ammonia and / or ammonium hydroxide compound is preferably 1 to 45% by mass, more preferably 2 to 25% by mass, in 100% by mass of the alkaline solution. , 2 to 15 mass% is more preferable, and 2 to 10 mass% is even more preferable.

In the present invention, an oxyalkylamine compound can be added to the alkaline solution in addition to the compound selected from the group consisting of ammonia and ammonium hydroxide compounds. The oxyalkylamine is preferably at least one selected from the group consisting of monooxymonoamine and monoaminopolyhydric alcohol.
Examples of the oxyalkylamine include ethanolamine, propanolamine, butanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-ethylethanolamine, triethanolamine, N, N-dimethylethanolamine, Monooxymonoamines such as N, N-diethylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine and N, N-dipropylpropanolamine; monoaminopolyhydric alcohols such as diethanolamine and dipropanolamine Examples of oxyalkylamines particularly preferably used in the present invention include ethanolamine and propanolamine.
The content of the oxyalkylamine compound in the present invention is, for example, 3 to 40% by mass, preferably 5 to 25% by mass, more preferably 7 to 18% by mass in 100% by mass of the alkaline solution.

  By adding an appropriate amount of the oxyalkylamine compound, the effect of removing the extra swelling layer generated by hydrolysis is promoted, and good adhesive strength and adhesive strength durability can be obtained.

  In addition to these components, a known surfactant or the like may be added for the purpose of adjusting the wettability of the alkaline solution with respect to the polymer film.

<Protective film>
In the present invention, a protective film can be used if necessary. The protective film literally plays a role of protecting the main object to be protected from contamination and scratches, but in the present invention, the divided polymer films are further combined and attached to a glass plate. It is responsible for labor saving in the matching process.

  The protective film of the present invention may be composed of a base film and an adhesive. As the base film, in addition to general PET film, PEN film, polypropylene film, nylon film, etc., heat resistant super engineering plastic film such as PPS film, PEEK film, aromatic polyamide film, polyimide film, polyimide benzathol film, etc. Can be used.

  The base material of the protective film preferably used in the present invention is a PET film that has been subjected to an annealing treatment for improving dimensional stability, a PEN film that has also been subjected to an annealing treatment, or a polyimide film.

  As the pressure-sensitive adhesive used in the protective film of the present invention, known pressure-sensitive adhesives such as silicone-based, acrylic-based, and polyurethane-based can be used. The protective film of the present invention protects the device forming surface of the polymer film that is the base material of the flexible electronic device. Therefore, it is preferable to use a pressure-sensitive adhesive of a type in which the transfer of the pressure-sensitive adhesive component is minimized or the transfer component is dry or can be easily removed by wet cleaning. In the present invention, for example, a pressure-sensitive adhesive using a side-chain crystalline polymer having a property that the adhesive force is reduced by cooling can be used.

<Means for bonding glass plate and polymer film>
In the present invention, the means for adhering the glass plate and the polymer film include (1) a means for adhering the polymer film and the glass plate by surface-activating the surface of the polymer film to be bonded with the glass plate with the alkaline solution. (2) A means for adhering the polymer film and the glass plate by treating the surface of the glass plate to be adhered with the polymer film with a silane coupling agent, and (3) adhering the polymer film and the glass plate with an adhesive or an adhesive. Means may be used, or these may be used in combination.
In the present invention, the means for adhering the glass plate and the polymer film uses (1) as an essential means, and (1) and (2), (1) and (3), or (1) and the above. A combination of (2) and (3) may be used, and (2) and / or (3) may be performed after (1).

Adhesion of Glass Plate and Polymer Film with Alkaline Solution The surface of the polymer film to be bonded to the glass plate is preferably coated with the alkaline solution, and the polymer film is preferably immersed in the alkaline solution.

  As a coating method, a general liquid coating such as a spin coating method, a curtain coating method, a dip coating method, a slit die coating method, a gravure coating method, a bar coating method, a comma coating method, an applicator method, a screen printing method and a spray coating method. A method can be illustrated. When the coating method in the liquid phase is used, it is preferable that the coating is dried immediately after coating and further heat treatment (drying treatment) is performed at about 90 ± 30 ° C. for several tens of seconds to 10 minutes.

Examples of the dipping method include a method in which a predetermined container is filled with the alkaline solution, and the polymer film is dipped at a predetermined temperature for a predetermined time while stirring the alkaline solution. The temperature is, for example, 0 to 80 ° C, preferably 10 to 60 ° C, more preferably 15 to 38 ° C, and even more preferably 15 to 30 ° C. If the temperature exceeds this range, the polymer film may be dissolved. On the other hand, if the temperature does not reach the predetermined range, the treatment becomes insufficient, and uneven adhesion strength is likely to occur.
The time is, for example, 1 second to 30 minutes, preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. If the processing time exceeds a predetermined time, the film may be dissolved and the strength may be deteriorated. If the processing time is less than the predetermined range, the processing becomes non-uniform and spots are likely to occur. When the dipping method is used, it is preferable to carry out a heat treatment (drying treatment) at 90 ± 30 ° C. for several tens of seconds to 10 minutes, after rinsing with water for several times.

  As the ammonium hydroxide compound in the present invention, an ammonium hydroxide compound obtained by a caustic decomposition method in which an ammonium chloride compound and potassium hydroxide are mixed in anhydrous methanol can be used. Further, in the present invention, an ammonium hydroxide compound having a high purity obtained by an electrolysis method of an ammonium chloride compound using a cation exchange membrane, or an electrodialysis method can be used. According to the latter manufacturing method, the amount of inorganic impurities such as alkali metal is small, and it can be preferably used when applied to the manufacturing method of a device including a semiconductor element.

  In the present invention, it is preferable that after the surface activation treatment with an alkaline solution, the excess solution is washed off and dried. From these points, water or a solvent having a low boiling point can be used for the alkaline solution. The drying may be air drying with an air knife or the like, but heating drying is preferably used. The drying temperature is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, even more preferably 80 ° C. or higher, 105 ° C. or higher, 140 ° C. or higher, or 175 ° C. or higher. Regarding the drying time, for example, 1 minute or more and about 3 to 45 minutes are sufficient. Ammonia, ammonium hydroxide compounds, and oxyalkylamines contained in the alkaline solution in the present invention can be removed by drying, so that the present invention can be applied to device formation without causing problems in the subsequent steps.

Adhesion of Glass Plate and Polymer Film by Silane Coupling Agent The silane coupling agent in the present invention acts to physically or chemically intervene between the temporary support and the polymer film to enhance the adhesive force between them. A compound having
Specific preferred examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and 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, vinyltriethoxysila , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyl Remethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate , Chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenethyltrimethoxysilane, aminophenylaminomethylphenethyltrimethoxysilane, and hexamethyldisilazane.

  In addition, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenyl. Silane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, Triethoxyethylsilane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxyphenylsilane, Tilttriethoxysilane, Pentyltrichlorosilane, Triacetoxymethylsilane, Trichlorohexylsilane, Trichloromethylsilane, Trichlorooctadecylsilane, Trichloropropylsilane, Trichlorotetradecylsilane, Trimethoxypropylsilane, Allyltrichlorosilane, Allyltriethoxysilane, Allyl Trimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trichloro-2-cyanoethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxy Propyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysila , And the like can also be used.

  Among such silane coupling agents, the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure having one silicon atom per molecule of the coupling agent.

Particularly preferred silane coupling agents 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, aminophenyltrimethoxysilane, Aminophenethyltrimethoxysilane, amino Such as E sulfonyl aminomethyl phenethyltrimethoxysilane the like. When particularly high heat resistance is required in the process, it is desirable to connect Si and an amino group with an aromatic group.
In the present invention, a phosphorus-based coupling agent, a titanate-based coupling agent, etc. may be used in combination, if necessary.

<How to apply silane coupling agent>
As the coating method of the silane coupling agent in the present invention, a coating method in a liquid phase or a coating method in a gas phase can be used.
As the coating method in the liquid phase, using a solution prepared by diluting a silane coupling agent with a solvent such as alcohol, a spin coating method, a curtain coating method, a dip coating method, a slit die coating method, a gravure coating method, a bar coating method, Typical liquid application methods such as a comma coat method, an applicator method, a screen printing method and a spray coat method can be exemplified. When the coating method in the liquid phase is used, it is preferable that the coating is dried immediately after coating and further heat-treated at about 100 ± 30 ° C. for several tens of seconds to 10 minutes. By the heat treatment, the silane coupling agent and the surface of the coated surface are bonded by a chemical reaction.

  Examples of the coating method in the vapor phase include a method of exposing the 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 of 40 ° C. to a boiling point of the silane coupling agent. The boiling point of the silane coupling agent varies depending on the chemical structure, but is generally in the range of 100 to 250 ° C. However, heating at 200 ° C. or higher is not preferable because it may cause a side reaction on the organic group side of the silane coupling agent.

  The environment for heating the silane coupling agent may be under pressure, at about normal pressure, or at reduced pressure. However, in order to promote vaporization of the silane coupling agent, it is preferably at about normal pressure or under reduced pressure. Since many silane coupling agents are flammable liquids, it is preferable to carry out vaporization work in a closed container after replacing the container with an inert gas.

  The time for exposing the glass plate to the silane coupling agent is not particularly limited, but is, for example, 20 hours or less, preferably 60 minutes or less, more preferably 15 minutes or less, and further preferably 1 minute or less.

  The glass plate temperature during the exposure of the glass plate to the silane coupling agent is controlled to an appropriate temperature between -50 ° C and 200 ° C depending on the type of the silane coupling agent and the desired thickness of the silane coupling agent layer. It is preferable.

  The glass plate exposed to the silane coupling agent is preferably heated to 70 ° C to 200 ° C, more preferably 75 ° C to 150 ° C after the exposure. By such heating, the hydroxyl groups and the like on the surface of the glass plate react with the alkoxy groups and silazane groups of the silane coupling agent, and the silane coupling agent treatment is completed. The time required for heating is 10 seconds or more and 10 minutes or less. If the temperature is too high or the time is too long, the coupling agent may deteriorate. If it is too short, the treatment effect cannot be obtained. If the substrate temperature during exposure to the silane coupling agent is already 80 ° C. or higher, post-heating can be omitted.

It is preferable that the surface of the glass plate on which the silane coupling agent is applied is held downward and exposed to the silane coupling agent vapor. In the liquid phase coating method, the coated surface of the glass plate inevitably faces upward during the coating and before and after the coating, so that floating foreign substances under the working environment may be deposited on the surface of the glass plate. However, since the glass plate can be held downward by the vapor phase coating method, it is possible to greatly reduce the adhesion of foreign matter in the environment.
In addition, it is preferable to clean the surface of the glass plate before the treatment with the silane coupling agent by a means such as short wavelength UV / ozone irradiation or a liquid cleaning agent.

  The coating amount (thickness) of the silane coupling agent is theoretically sufficient to be one molecular layer, and a mechanically designable level of thickness is sufficient. Generally, the thickness of the silane coupling agent layer is less than 400 nm (less than 0.4 μm), preferably 200 nm or less (0.2 μm or less), and more preferably 100 nm or less (0.1 μm or less) in practice. The thickness is more preferably 50 nm or less, still more preferably 10 nm or less. However, in the case of a region of 5 nm or less in calculation, it is assumed that the silane coupling agent does not form a uniform coating film but clusters, which is not preferable. The film 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.

  A glass plate that has been treated with a silane coupling agent, or a glass plate that has not been treated, and a glass plate that has been washed with ultrapure water or the like and that has been activated by UV ozone treatment are used. be able to. The UV ozone treatment in the present invention means a treatment of irradiating ultraviolet rays having a wavelength of, for example, 270 nm or less, preferably 210 nm or less, more preferably 180 nm or less in the presence of oxygen at a relatively short distance. Short-wavelength ultraviolet rays turn oxygen in the atmosphere into ozone, and the ultraviolet rays themselves are attenuated. Therefore, the effect cannot be obtained when the distance between the light source and the object to be treated is increased. In the present invention, the distance between the light source and the object to be processed is, for example, 30 mm or less, preferably 16 mm or less, and more preferably 8 mm or less.

  In the present invention, only the treatment with the silane coupling agent may cause the adhesive force between the glass plate and the polymer film to become too strong, which may cause a problem in peeling. Adjustment is possible by reducing the coating amount of the silane coupling agent, but since treatment unevenness is likely to occur, in the present invention, after the silane coupling agent treatment, UV ozone treatment or the like is performed to introduce the silane coupling agent. The method of deactivating the functional group is recommended.

  In the present invention, the treated surface of the polymer film surface-treated with an alkaline solution may be treated with a silane coupling agent. The treatment of the polymer film with the silane coupling agent can be performed in the same manner as the treatment of the glass plate with the silane coupling agent.

Adhesion of Glass Plate and Polymer Film with Adhesive or Adhesive As the adhesive or the adhesive, known adhesives or adhesives such as silicone resin, epoxy resin, acrylic resin, polyester resin can be used. In the present invention, for example, a pressure-sensitive adhesive using a side-chain crystalline polymer having a property that the adhesive force is reduced by cooling can be used.
The adhesion means preferable in the present invention may be an adhesion means with an adhesive / adhesive having a thickness of 5 μm or less, or an adhesion means without using an adhesive / adhesive.

  In the present invention, the glass plate side is subjected to silane coupling agent treatment, organic ozone treatment such as UV ozone treatment, and activation treatment, and similarly to the polymer film side, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, A joining method can be used in which activation treatment such as flame treatment, itro treatment, UV ozone treatment, and exposure treatment to an active gas is performed, and both treatment surfaces are brought into close contact with each other and pressure and heat treatment are performed.

<Film laminating method>
In the present invention, at least the surface of the glass plate and the surface of the activated polymer film are overlapped with each other, and heat and pressure can be applied to perform the adhesion.
The bonding of the glass plate and the polymer film is preferably performed by heating and pressurizing the glass plate that has been surface-activated and the polymer film that has been surface-activated. In this case, the surface of the glass plate to be attached to the polymer film is preferably treated with a silane coupling agent. On the other hand, a surface-activated glass plate or a glass plate not surface-activated and a surface-activated polymer film are attached to each other via a pressure-sensitive adhesive layer or adhesive layer having a thickness of 5 μm or less. Good.
The pressurization / heat treatment may be performed, for example, under atmospheric pressure or in a vacuum while pressing, laminating, roll laminating or the like while heating. A method of applying pressure and heating in a flexible bag can also be applied. From the viewpoint of improving the productivity and reducing the processing cost brought about by the high productivity, press or roll lamination in the atmosphere is preferable, and a method using rolls (roll lamination etc.) is particularly preferable.

The pressure during the heat treatment under pressure is preferably 0.1 MPa to 10 MPa, more preferably 0.3 MPa to 5 MPa. If the pressure is too high, the support may be damaged, and if the pressure is too low, some portions may not adhere to each other, resulting in insufficient adhesion.
The temperature for the pressure heat treatment is in the range not exceeding the heat resistant temperature of the polymer film used. In the case of a non-thermoplastic polyimide film, it is preferably treated at 80 ° C to 400 ° C, more preferably 90 ° C to 350 ° C.

  The pressure heat treatment can be performed separately in a pressure process and a heating process. In this case, first, the polymer film and the glass plate are pressed (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, less than 120 ° C., preferably a temperature of 95 ° C. or less) to secure the adhesion between them. Then, at a low pressure (preferably less than 0.2 MPa, more preferably 0.1 MPa or less) or at a relatively high temperature (eg 120 ° C. or higher, preferably 120 to 250 ° C., more preferably 150 to 230 ° C.) at normal pressure. By heating, the chemical reaction at the adhesion interface is promoted and the polymer film and the temporary supporting glass plate can be laminated.

  In the present invention, it is preferable to control the moisture absorption rate of the polymer film when the polymer film and the glass plate are bonded together to be 1.8% or less. The moisture absorption rate of such a polymer film means the moisture absorption rate immediately before the polymer film and the glass plate are pressure-bonded. The moisture absorption rate of the polymer film depends on the temperature and humidity inside the room where the polymer film is left. Further, since it takes time to absorb and release moisture, it is important to perform the measurement after leaving it for a sufficiently long time under a certain condition for at least 24 hours or more.

  If the amount of the absorbed moisture is too large, it causes blisters when heat is applied in the subsequent step. On the other hand, if the amount is too small, the adhesiveness to the glass plate may become stable. That is, the chemical reaction on the surface of each of the polymer film and the glass plate is influenced by the moisture contained in the polymer film. The moisture absorption rate of the polymer film is, for example, 1.5% or less, preferably 1.2% or less. The lower limit of the moisture absorption rate of the polymer film is, for example, 0.1%, preferably 0.2%, more preferably 0.4%.

<Manufacturing means for flexible electronic devices>
When the laminate of the present invention is used, an electronic device is formed on the polymer film of the laminate using the existing equipment and process for manufacturing an electronic device, and the polymer film is peeled from the laminate, thereby providing a flexible structure. Electronic devices can be made.
On the other hand, an electronic device formed by printing or using a thin film on the surface of the glass plate of the laminate of the present invention is also included in the present invention.
The electronic device in the present invention includes a wiring board that carries electric wiring, active elements such as transistors and diodes, and electronic circuits including passive devices such as resistors, capacitors, and inductors, as well as pressure, temperature, light, humidity, and the like. A sensor element, a light emitting element, an image display element such as a liquid crystal display, an electrophoretic display, and a self-luminous display, a wireless or wired communication element, an arithmetic element, a memory element, a MEMS element, a solar cell, a thin film transistor, and the like.

<Means for peeling the polymer film from the glass plate>
The means for peeling the polymer film from the support is not particularly limited, and a known method may be used. As a method of peeling the polymer film from the laminate, a method of irradiating strong light from the glass plate side to thermally decompose the adhesive site between the glass plate and the polymer film or peeling it by photodecomposing the adhesive strength in advance. After weakening, peeling the polymer film with a force less than the elastic strength limit of the polymer film, exposing it to heated water, heated steam, etc. to weaken the bond strength between the glass plate and the polymer film interface and peel it off. Can be illustrated.

  Other peeling methods include a method of rolling from the end with tweezers, a method of sticking an adhesive tape on one side of a cut portion of a polymer film with a device and then rolling from the tape portion, a polymer film with a device. A method of vacuum suctioning one side of the notched part and then winding it from that part, or by not adhering part of the polymer film to the inorganic plate beforehand, or by extruding part of the polymer film from the glass plate to obtain a gripping white A method etc. can be adopted.

In the present invention, it is preferable that the adhesive strength at 90 ° peeling between the glass plate and the polymer film is within a predetermined range. When a thermoplastic film such as a PET film is used as the polymer film, it is assumed that amorphous silicon or an organic semiconductor is used as the semiconductor. Therefore, adhesive strength in 90 degree peeling after heat treatment at 140 ° C. for 30 minutes is considered. May be evaluated as
On the other hand, when a polyimide film is used as the polymer film, it is evaluated as the adhesive strength in 90 degree peeling after heat treatment at 420 ° C. for 30 minutes in that a dehydrogenation step and a polycrystallization step of amorphous silicon are assumed. Good. When a polyethylene naphthalate film is used as the polymer film, it may be evaluated as the adhesive strength in 90 degree peeling after heat treatment at 250 ° C. for 30 minutes. When an LCP film is used as the polymer film, it may be evaluated as the adhesive strength in 90 degree peeling after heat treatment at 300 ° C. for 30 minutes.
The adhesive strength between the glass plate and the polymer film at 90 ° peeling is, for example, 0.03 N / cm or more and less than 10 N / cm, preferably 0.1 N / cm or more and 9 N / cm or less, more preferably 0.3 N / cm or more and 8 N or more. / Cm or less, more preferably 0.35 N / cm or more and 7 N / cm or less.
Heat treatment of the glass plate and the polymer film when the glass plate is treated with a silane coupling agent (for example, 140 ° C. for 30 minutes for polyethylene terephthalate film, 420 ° C. for 30 minutes for polyimide film, 250 ° C. for 30 minutes for polyethylene naphthalate). For a liquid crystal polymer, the adhesive strength in 90 ° peeling after 300 ° C. for 30 minutes) is, for example, 1.0 N / cm or more and 10 N / cm or less, preferably 1.5 N / cm or more, more preferably 2.0 N / cm or more. , And more preferably 2.5 N / cm or more.
When the glass plate is treated with the silane coupling agent, the adhesion strength between the glass plate and the polymer film at 90 ° peeling after the heat treatment is preferably lower than the adhesion strength before the heat treatment (initial adhesion strength).
When the glass plate is not treated with the silane coupling agent, the adhesive strength in 90 degree peeling after heat treatment of the glass plate and the polymer film is, for example, 0.03 N / cm or more and less than 1.0 N / cm, preferably 0.1 N / cm. cm or more, more preferably 0.2 N / cm or more, still more preferably 0.3 N / cm or more.
When the glass plate is not treated with the silane coupling agent, the adhesive strength of the glass plate and the polymer film at 90 ° peeling after the heat treatment is preferably higher than the adhesive strength before the heat treatment (initial adhesive strength).

  In the present invention, it is recommended that the peeling angle at the time of peeling is π / 6 radians (30 degrees) or less, more preferably π / 12 radians (15 degrees) or less, and further π / 24 radians ( It is even more preferable to set it to 7.5 degrees or less. When the lower limit of the peeling angle is 0, it corresponds to spontaneous peeling, and in this case, troubles such as blister generation and film peeling are likely to occur in the electronic device processing step. The lower limit of the peeling angle of the present invention is 1.0 degree, more preferably about 2 degrees.

  In the present invention, it is also useful to attach another reinforcing base material to the part to be peeled off in advance and peel the whole reinforcing base material. When the flexible electronic device to be peeled is the backplane of the display device, it is possible to obtain the flexible display device by pasting the front plane of the display device in advance, integrating them on the glass plate, and then peeling them off at the same time. is there.

  In the present invention, the patterning treatment can be performed on the glass plate side, the polymer film side, or both. The patterning in the present invention means controlling the degree of surface treatment of a polymer film, a glass plate, or both (for example, surface activation treatment with an alkaline solution, surface activation treatment with a silane coupling agent), It means to create a part where the adhesive force is relatively strong and a part where the adhesive force is relatively weak. In the present invention, an electronic device is formed in a region where the adhesive force between the polymer film and the glass plate is weakened by the patterning treatment (referred to as an easily peelable portion), and then a cut is made in the outer peripheral portion of the region to form the polymer film. A flexible electronic device can be obtained by peeling the area where the electronic device is formed from the glass plate. This method makes it easier to separate the polymer film and the glass plate.

  As a method of making a notch in the polymer film along the outer periphery of the easily peelable portion of the laminate, a method of cutting the polymer film with a cutting tool such as a blade or a method of relatively scanning the laser and the laminate can be used. A method of cutting a molecular film, a method of cutting a polymer film by relatively scanning a water jet and a laminate, a method of cutting a polymer film while slightly cutting a glass layer by a dicing device for a semiconductor chip, etc. be able to. Further, a combination of these methods, a method of superimposing an ultrasonic wave on the cutting tool, and a method of improving the cutting performance by adding a reciprocating motion or a vertical motion may be appropriately adopted.

  When making a notch in the polymer film on the outer periphery of the easily peelable portion of the laminate, the position at which the notch is made may include at least a part of the easily peelable portion, and basically the cutting may be performed according to a predetermined pattern. It may be appropriately selected from the viewpoints of error absorption, productivity, and the like.

  Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. The methods for evaluating physical properties in the following examples are as follows.

<Reduced viscosity of polyamic acid solution>
The solution dissolved in N, N-dimethylacetamide so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube.

<Thickness of polymer film>
The thickness of the polymer film was measured using a micrometer (“Millitron 1245D” manufactured by Fine Luff).

<Tensile elastic modulus, tensile strength and tensile elongation at break of polymer film>
From the polymer film to be measured, strip-shaped test pieces of 100 mm x 10 mm in the flow direction (MD direction) and the width direction (TD direction) were cut out, and a tensile tester ("Autograph (registered by Shimadzu Corporation)"(Trademark); model name AG-5000A "), tensile modulus, tensile breaking strength, and tensile breaking elongation were measured in the MD direction and the TD direction, respectively, under the conditions of a tensile speed of 50 mm / min and a chuck distance of 40 mm. .

<Coefficient of linear expansion (CTE) of polymer film>
With respect to the flow direction (MD direction) and the width direction (TD direction) of the polymer film to be measured, the expansion / contraction rate was measured under the following conditions, and the intervals of 15 ° C (30 ° C to 45 ° C, 45 ° C to 60 ° C, .) Was measured up to 300 ° C., and an average value of all measured values measured in the MD direction and the TD direction was calculated as a coefficient of linear expansion (CTE).
Device name: MAC Science "TMA4000S"
Sample length: 20 mm
Sample width: 2 mm
Temperature rising start temperature: 25 ° C
Temperature rise end temperature: 400 ° C
Temperature rising rate; 5 ° C./min. Atmosphere; Argon initial load; 34.5 g / mm ²

<Heat shrinkage of polymer film>
It was measured by a method specified in IEC 61189-2, Test 2X02, with heating conditions of 400 ° C. for 1 hour.

<Moisture absorption rate of polymer film>
It was measured by the A method specified in JIS K7251.

<Adhesive strength 90 degree peeling method>
From the laminated plate, a portion to be used for measurement was cut out into about 100 mm square, and the adhesive strength between the glass plate and the polymer film was measured under the following conditions according to the 90 ° peeling method described in JIS C6481.
Device name: "Autograph (registered trademark) AG-IS" manufactured by Shimadzu Corporation
Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Atmospheric measurement sample width: 10 mm

<Measurement of carboxyl group amount on polymer film surface after surface activation treatment>
A film of 30 mm × 30 mm after the surface activation treatment was used as a sample. Glass sample bottle having an inner volume of 250 ml, trifluoroethanol _{(TFE: CF 3 CH 2 OH} ) 3.0ml, di -t- butyl carbodiimide (Di-t-BuC: ( CH 3) 3 C = NC = NC ( CH ₃ ) ₃ ) 1.0 ml and pyridine (C ₆ H ₅ N) 1.2 ml were added, and the sample was kept in a sample bottle so as not to come into direct contact with the reagent liquid, sealed and placed in a constant temperature bath at 50 ° C. After leaving for 24 hours, surface modification was carried out by addition reaction of trifluoroethanol with the carboxyl group on the sample surface.
Then, the amount of fluorine on the surface of the surface-modified film was quantified by ESCA analysis to determine the amount of carboxyl groups.

<Production of polyimide film>
[Production Example 1]
(Preparation of polyamic acid solution)
After nitrogen-substituting the inside of a reaction vessel equipped with a nitrogen introducing tube, a thermometer, and a stirring rod, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and paraphenylenediamine ( 147 parts by mass of PDA) dissolved in 4600 parts by mass of N, N-dimethylacetamide and added, and a dispersion obtained by dispersing colloidal silica as a lubricant in dimethylacetamide (“Snowtex (registered trademark of Nissan Chemical Industries)”). ) DMAC-ST30 ") is added so that silica (lubricant) is 0.08 mass% with respect to the total amount of polymer solids in the polyamic acid solution, and the mixture is stirred at a reaction temperature of 25 ° C for 24 hours, and then added to Table 1. A brown viscous polyamic acid solution V1 having the reduced viscosity shown in Table 1 was obtained.

(Preparation of polyimide film)
The polyamic acid solution V1 obtained above was applied to a final film thickness (non-slip surface) of a long polyester film having a width of 1500 mm (“A-4100” manufactured by Toyobo Co., Ltd.) using a slit die ( It was applied so that the film thickness after imidization) would be 25 μm, dried at 105 ° C. for 20 minutes, and then peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 1420 mm.

  Then, the obtained self-supporting polyamic acid film was stretched 1.1 times in the length direction due to the speed difference of the transport rolls, and then 1.05 times in the width direction with a pin tenter, and the temperature was 150 ° C to 420 ° C. The temperature is raised stepwise in the area (180 ° C x 5 minutes for the 1st step, 270 ° C x 10 minutes for the 2nd step, 420 ° C x 5 minutes for the 3rd step) to imidize, and the pin gripping parts at both ends Was dropped through a slit to obtain a long polyimide film F1 (1000 m roll) having a width of 1290 mm. The characteristics of the obtained film F1 are shown in Table 2.

[Production Example 2]
(Preparation of polyamic acid solution)
After nitrogen-substituting a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) and N, N-dimethylacetamide 4416 And 217 parts by mass of pyromellitic dianhydride (PMDA), and then colloidal silica as a lubricant is dispersed in dimethylacetamide (Nissan Chemical Industry "Snowtex"). (Registered trademark) DMAC-ST30 ") and silica (lubricant) are added so that the total polymer solid content in the polyamic acid solution is 0.09% by mass, and the mixture is stirred at a reaction temperature of 25 ° C for 36 hours. A brown viscous polyamic acid solution V2 having the reduced viscosity shown in Table 1 was obtained.

<Production of polyimide film>
The polyamic acid solution V2 obtained above was used instead of the polyamic acid solution V1, and a smooth surface (non-slip material) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) with a width of 800 mm was formed using a slit die. On the surface) so that the final film thickness (film thickness after imidization) is 38 μm, and is dried at 105 ° C. for 25 minutes, then peeled from the polyester film, and the first step is carried out at 150 ° C. with a pin tenter. × 5 minutes, 2nd step 220 ° C. × 5 minutes, 3rd step 495 ° C. × 10 minutes, imidized by heat treatment, the pin grip parts on both ends are dropped by slits, and a long polyimide film F2 (width 645 mm) 1000 m roll) was obtained. The characteristics of the obtained film F2 are shown in Table 2.

<Other polymer films>
The following were used as other polymer films. Kapton H was a commercial product manufactured by Toray DuPont, PEN film was manufactured by Teijin DuPont, and LCP film was a commercial product by Kuraray.

<Preparation of alkaline solution for surface activation treatment>
Tetramethylammonium hydroxide (7 parts by mass) and deionized water (93 parts by mass) were mixed and stirred to prepare an alkaline solution A1. 5 parts by mass of tetramethylammonium hydroxide, 15 parts by mass of ethanolamine, and 80 parts by mass of deionized water were mixed to obtain an alkaline solution A2. Tetrabutylammonium hydroxide (5 parts by mass) and deionized water (95 parts by mass) were mixed and stirred to prepare an alkaline solution A3. 5 parts by mass of ammonia, 20 parts by mass of ethanolamine, and 75 parts by mass of deionized water were mixed and stirred to obtain an alkaline solution A4. N- (2-hydroxyethyl) trimethylammonium hydroxide (5 parts by mass) and deionized water (95 parts by mass) were mixed and stirred to prepare an alkaline solution A5. 5 parts by mass of sodium hydroxide was dissolved in 95 parts by mass of deionized water to obtain an alkaline solution A6. As a general rule, the compounds used in the alkaline solution were first-class reagents.

<Production of surface activated polymer film>
The film F1 was cut into 300 mm × 420 mm, fixed on a stainless steel metal frame, filled with an alkaline solution (treatment chemical solution) whose temperature was adjusted to a predetermined temperature shown in Table 3, and gently stirred in a water tank for a predetermined time. Immediately after soaking and pulling up, soak in a water tank filled with deionized water for 10 seconds, drain sufficiently, then soak in another deionized water tank for 10 seconds, drain thoroughly, wash with running water, and warm at 145 ° C. It was dried in a dryer for 3 minutes and surface-activated (Example 1). Hereinafter, the same operation was performed except that the polymer film, the alkaline solution (treatment chemical solution), the treatment temperature, and the treatment time were changed to those shown in Table 3 (Examples 2 to 25, Comparative Examples 1 to 5).

<Glass plate>
370 × 470 mm, 0.7 mm thick Lotus Glass made by Corning Co., Ltd. using UV / O ₃ cleaning and reforming apparatus made by Run Technical Service Co., Ltd., and UV from a distance of about 20 mm from the UV lamp in the atmosphere. Irradiation was carried out for 5 minutes. This glass plate was used as an untreated substrate. The UV lamp emits bright lines with wavelengths of 185 nm (a short wavelength capable of generating ozone that promotes the inactivation treatment) and 254 nm, and at this time, the illuminance was measured by an illuminometer “UV-M03AUV (OR of 254 nm)”. Measured at wavelength) "was 20 mW / cm ² .

  The untreated substrate was subjected to silane coupling agent treatment (SC agent treatment) by vapor phase coating. 100 parts by mass of a silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) was charged in an evaporation vat inside the chamber so that the oxygen concentration was 0.1% or less at atmospheric pressure. Nitrogen gas was introduced until the temperature reached 80 ° C., and the temperature of the vat charged with the silane coupling agent was raised to 80 ° C. Next, the untreated substrate was held horizontally at a position 100 mm vertically away from the liquid surface of the silane coupling agent, and was gently transported at a speed of 7 mm / sec for exposure to the silane coupling agent vapor. The glass plate temperature was controlled between 95 ° C. and 105 ° C. by heating with far infrared rays, and heat treatment was performed for about 3 minutes. This substrate was used as an SC agent-coated inorganic substrate.

<Coating silane coupling agent on surface activated polymer film>
The surface activation treatment is performed using an alkaline solution, and the dried film F1 is fixed to the stainless steel metal frame used for the surface treatment, and then treated with a silane coupling agent by the vapor phase coating method like the glass plate. It was

Example 1
The surface-activated polymer film and the SC agent-coated inorganic substrate (SC agent-coated glass plate) were superposed so that the treated surfaces were aligned with each other, and a glass plate side temperature of 100 ° C. and a roll pressure of 5 kgf / cm using a MCK roll laminator. ^2. Temporary lamination was performed at a roll speed of 5 mm / sec. The polymer film after the temporary lamination cannot be peeled off by its own weight, but the adhesiveness was such that it was easily peeled off when scratching the edge of the film. Then, the obtained temporary laminate substrate was put in a clean oven, heated at 120 ° C. for 30 minutes, and then allowed to cool to room temperature to obtain a laminated body L1.
The resulting laminate was evaluated for 90 ° peel adhesive strength between the film and the substrate, and also for appearance quality after heat treatment in an oven and 90 ° peel adhesive strength. The results are shown in Table 3. The heat treatment was performed at 420 ° C. for 30 minutes.
The laminate is manufactured in a laboratory where the temperature is kept at 25 ° C ± 2 ° C and the humidity is 55% ± 3%, and the surface-activated polymer film is laminated in this laboratory after being left for 24 hours or more. I went.

Examples 2 to 25
A surface activated polymer film, an alkaline solution (treatment liquid), coating of a silane coupling agent and a glass plate were changed, and the same operation as in Example 1 was carried out to obtain a laminate. The obtained laminated body was evaluated in the same manner as in Example 1. The results are shown in Table 3. When the PEN film was used, the heat treatment condition was 250 ° C. for 30 minutes, and when the LCP film was used, the heat treatment condition was 300 ° C. for 30 minutes.

Comparative Examples 1-5
The surface activation-treated polymer film, the alkaline solution (treatment chemical solution), and the glass plate were changed, and the same operation as in Example 1 was carried out to obtain a laminate. The obtained laminated body was evaluated in the same manner as in Example 1. The results are shown in Table 3. When the PEN film was used, the heat treatment condition was 250 ° C. for 30 minutes, and when the LCP film was used, the heat treatment condition was 300 ° C. for 30 minutes.

Application examples 1 to 25
Each of the laminates obtained in Examples 1 to 25 was fixed to a substrate holder in a sputtering device by covering a stainless frame having an opening. Fix the substrate holder and the support surface so that they are in close contact with each other. Therefore, the temperature of the film can be set by flowing the cooling medium into the substrate holder. The substrate temperature was set to 2 ° C. Then, the plasma treatment of the film surface was performed. The plasma treatment conditions were such that the frequency was 13.56 MHz, the output was 200 W, and the gas pressure was 1 × 10 ⁻³ Torr in argon gas, the temperature during the treatment was 2 ° C., and the treatment time was 2 minutes. Then, a frequency of 13.56 MHz, an output of 450 W, a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10% by mass) alloy target, and a DC magnetron sputtering method in an argon atmosphere at 1 nm / sec. A nickel-chromium alloy film (underlayer) having a thickness of 11 nm is formed at a rate of, and then the backside of the sputter surface of the substrate is temperature controlled to 3 ° C so that the temperature of the substrate is set to 2 ° C. Sputtering was performed in a state of being in contact with the flown SUS plate of the substrate holder. Copper was vapor-deposited at a rate of 10 nm / sec to form a copper thin film having a thickness of 0.22 μm. A base metal thin film-forming film was obtained from each film. The thickness of the copper and NiCr layers was confirmed by the fluorescent X-ray method.

Then, the laminated plate with the underlying metal thin film forming film from each film was fixed to a frame made of Cu, and a thick copper layer was formed using a copper sulfate plating bath. The electrolytic plating conditions were immersion in an electrolytic plating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, a small amount of a brightener), and a current of 1.5 A / dm ² was applied. Thus, a thick copper plating layer (thick layer) having a thickness of 4 μm was formed and subsequently heat-treated and dried at 120 ° C. for 10 minutes to obtain a metallized polymer film / glass laminate.

Using each of the obtained metallized polymer films / glass laminates, a photoresist: FR-200, manufactured by Shipley Co., Ltd. was applied and dried, and then contact exposure was carried out with a glass photomask, and further 1.2% by mass KOH aqueous solution was used. Developed. Next, after etching with a cupric chloride etching line containing HCl and hydrogen peroxide at a spraying pressure of ² kgf / cm ² at 40 ° C., a line array of line / space = 20 μm / 20 μm was formed as a test pattern. Electroless tin plating was performed to a thickness of 0.5 μm. After that, an annealing treatment was performed at 125 ° C. for 1 hour. The dripping of the test pattern, the remaining pattern, and the peeling of the pattern were observed with an optical microscope.

The polymer film / glass laminates of Examples 1 to 25 gave good test patterns without sagging and no pattern peeling.
Further, in a muffle furnace in which the polymer film / glass laminates obtained in Examples 1 to 3, Examples 6 to 8, Examples 11 to 13, Examples 16 to 18, and Examples 21 to 25 were replaced with nitrogen. Even when the temperature was raised to 400 ° C. at a heating rate of 10 ° C./min, the temperature was kept at 400 ° C. for 1 hour, and then the temperature was naturally lowered, swelling and peeling did not occur.
On the other hand, in all of the polymer films / glass laminates of Comparative Examples 1 to 5, film peeling occurred, and no good test pattern was obtained.

Application example 26
A laminate was obtained in the same combination as in Example 22, except that ultrathin glass (100 mm × 100 mm, thickness 50 μm) made by Nippon Electric Glass was used as the glass plate. The glass plate surface of the obtained laminate was processed by the same process as the film surface of Application Examples 1 to 25, and the pattern was formed in the same manner.

  The film and the glass plate were not peeled off during processing, and the obtained pattern was a good test pattern with no sagging, no pattern remained, and no pattern peeling. Similarly, even if the temperature is raised to 400 ° C. at a heating rate of 10 ° C./min in a muffle furnace with nitrogen substitution and then kept at 400 ° C. for 1 hour and then naturally cooled, swelling and peeling do not occur, and it is extremely thin. Despite being a glass plate, I was able to work without damage during handling.

  According to the method for manufacturing a flexible electronic device of the present invention, it is possible to temporarily fix a polymer film subjected to a surface activation treatment to a glass plate for bonding (temporary support) without using a vacuum device. In particular, the contribution to the industry is extremely large as a temporary fixing technology when manufacturing a flexible electronic device.

Claims (11)

In a laminate comprising a condensation-type polymer film and a glass plate, a carboxyl group has 1.0 × 10 ^{3 to} 1.0 × 10 ⁸ equivalents / cm on the adhesive surface of the condensation-type polymer film to be bonded to the glass plate. ² exist ,
The carboxyl group, the general formula laminate, wherein Rukoto such is produced using an alkaline solution containing at least an ammonium hydroxide compound represented by (1).
Formula ^{(1) {(R 1)} 3 -N + -R 2} · OH -
[In the formula, R ¹ represents H or a C1-8 alkyl group.
R ² represents H, a C1-8 alkyl group, or a C1-8 hydroxyalkyl group.
R ^{1 s} may be the same or different. ] R in the general formula (1) ¹ Represents a C1-2 alkyl group, R ² Is a C1-2 alkyl group, The laminated body of Claim 1.   The laminate according to claim 1 or 2, wherein the condensation polymer film is a polyimide film, a polyamide film, a polyamideimide film, a polybenzoxazole film, a polyester film, a polyethylene naphthalate film or a liquid crystal polymer film.   The laminate according to claim 1, wherein the condensation polymer film is a polyimide film.   The laminate according to any one of claims 1 to 4, wherein a surface of the glass plate to be bonded to the condensation polymer film is surface-activated with a silane coupling agent. The laminate according to any one of claims 1 to 4, wherein the surface of the glass plate to be attached to the condensation polymer film is not surface-activated with a silane coupling agent. The surface of the condensation polymer film bonded to a glass plate, the laminated body according to any one of claims 1 to 6 which is surface-treated activated with a silane coupling agent. The adhesive strength in 90 degree peeling after heat treatment of the glass plate and the condensation polymer film when the glass plate is treated with a silane coupling agent is 1.0 N / cm or more and 10 N / cm or less. ~ The laminated body according to any one of 5 and 7 . The adhesive strength in 90 degree peeling after heat treatment between the glass plate and the condensation-type polymer film when the glass plate is not treated with a silane coupling agent is 0.03 N / cm or more and less than 1.0 N / cm. Item 1. The laminated body according to any one of items 1 to 4 , 6 and 7 . Claim 1-9 electronic device formed using a printing or thin film on a glass plate surface of the laminated body described in any one of. Fabrication of flexible electronic devices and separating the condensed polymer film and the glass plate after forming the electronic device to the condensation polymer film surface of the laminate according to any of claims 1-9 Method.