JP6907698B2 - Method for manufacturing laminates and flexible electronic devices - Google Patents

Description

The present invention relates to a method for manufacturing a laminate and a flexible electronic device.

As a method for manufacturing a flexible electronic device without causing malfunction in the mounted electronic device even when a high-definition conductor pattern is required, a polymer film is temporarily fixed to a hard support via an adhesive layer to achieve high height. A molecular film composite was formed, and a conductor pattern was printed on the polymer film-side surface of the polymer film composite using at least a contact-type printing method using metal nanoparticles ink, and the polymer film composite was finally subjected to a heating step. A method of peeling a polymer film from a support has been proposed (see, for example, Patent Document 1).

Further, in Patent Document 1, a flexible electronic device can be manufactured by using any one of polyimide, polyethylene naphthalate, polycarbonate and polyethylene terephthalate as a polymer film, and glass as a hard support for temporarily fixing the polymer film. It is specifically proposed.

Japanese Unexamined Patent Publication No. 2015-198176

However, in the combination of the polymer film and the hard support proposed in Patent Document 1, although it is possible to suppress the deformation of the polymer film by heat treatment or the like by temporarily fixing the polymer film. After peeling the hard support from the polymer film, the polymer film is deformed, and there is a problem that the dimensional stability is not good.
Further, when glass is used as the hard support, the glass is fragile and brittle, so it is desirable to use a hard support having more excellent mechanical properties in the manufacturing process of the flexible electronic device.

An object of the present invention is to provide a laminate in which the support has excellent mechanical properties and can suppress deformation of the polymer film after the support is peeled off, and a method for manufacturing a flexible electronic device using the laminate.

Specific means for achieving the above-mentioned problems are as follows.
<1> A polymer film having a glass transition temperature in the range of 50 ° C. to 200 ° C. determined by differential scanning calorimetry (DSC), and a support made of a metal or a metal compound and temporarily fixed to the polymer film. , Equipped with
The absolute value of the difference between the longitudinal temperature expansion coefficient of the support in the temperature region A from 30 ° C. to 120 ° C. and the longitudinal temperature expansion coefficient of the polymer film in the temperature region A, and the above. The absolute value of the difference between the temperature expansion coefficient in the width direction of the support in the temperature region A and the temperature expansion coefficient in the width direction of the polymer film in the temperature region A is 5 ppm / ° C. or less, and is flexible. A laminate used in the manufacture of electronic devices.

<2> The laminate according to <1>, wherein at least one of the coefficient of thermal expansion of the support and the coefficient of thermal expansion of the polymer film is 5 ppm / ° C. to 50 ppm / ° C.

<3> The laminate according to <1> or <2>, wherein the coefficient of thermal expansion of the polymer film is equal to or greater than the coefficient of thermal expansion of the support.

<4> The laminate according to any one of <1> to <3>, wherein the polymer film and the support are polyethylene terephthalate and aluminum, or polyethylene naphthalate and a stainless alloy.

<5> A manufacturing method for manufacturing a flexible electronic device using the laminate according to any one of <1> to <4>, wherein the polymer film is temporarily fixed to the support and the laminate is used. A method for manufacturing a flexible electronic device, which is a body, has a conductor pattern printed on a surface on the polymer film side, is heated, and then peels the polymer film from the support.

According to the present invention, it is possible to provide a laminate in which the support has excellent mechanical properties and can suppress deformation of the polymer film after the support is peeled off, and a method for manufacturing a flexible electronic device using the laminate.

6 is a graph (longitudinal direction) showing the relationship between the CTE of the CTE-support of the polymer film and the dimensional difference before and after peeling in Examples 1 to 3 and Comparative Examples 1 to 5. 6 is a graph (width direction) showing the relationship between the CTE of the CTE-support of the polymer film and the dimensional difference before and after peeling in Examples 1 to 3 and Comparative Examples 1 to 5.

Hereinafter, embodiments of the present invention will be described.
In the present disclosure, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present disclosure, the glass transition temperature (Tg) of the polymer film can be determined from the DSC curve obtained by differential scanning calorimetry (DSC).

<Laminated body>
The laminate according to the embodiment of the present invention comprises a polymer film having a glass transition temperature in the range of 50 ° C. to 200 ° C. determined by differential scanning calorific value measurement (DSC), and a metal or a metal compound. A support temporarily fixed to the film is provided, and the temperature expansion coefficient in the longitudinal direction of the support in the temperature region A from 30 ° C. to 120 ° C. and the temperature in the longitudinal direction of the polymer film in the temperature region A. The absolute value of the difference between the expansion coefficient and the temperature expansion coefficient in the width direction (direction orthogonal to the longitudinal direction) of the support in the temperature region A and the width direction of the polymer film in the temperature region A. The absolute value of the difference between the temperature expansion coefficient and the temperature expansion coefficient is 5 ppm / ° C. or less, and is used for manufacturing flexible electronic devices. That is, the laminate of the present embodiment is used in a state where the polymer film is temporarily fixed to the support in a part of the manufacturing process of the flexible electronic device, and a predetermined process such as a printing process and a heating process is completed. After that, the polymer film is peeled off from the support.

In the laminate of the present embodiment, the absolute value of the difference between the coefficient of thermal expansion of the polymer film in the temperature region A and the coefficient of thermal expansion of the support in the temperature region A is 5 ppm / ° C. or less. As a result, deformation of the polymer film after the support is peeled from the polymer film can be suppressed, and dimensional stability is improved. The reason for this is that the absolute value of the difference between the above-mentioned temperature expansion coefficient of the support and the above-mentioned polymer film is small to some extent, so that the support is high before being peeled from the polymer film. It is presumed that this is because residual stress is unlikely to occur in the molecular film, and deformation (for example, shrinkage) of the polymer film due to residual stress or the like is suppressed after the support is peeled from the polymer film.

Further, in the laminate of the present embodiment, the polymer film having a relatively large coefficient of thermal expansion is temporarily fixed to a support made of a metal or a metal compound having a relatively small coefficient of thermal expansion, so that the influence of humidity is mitigated. It also has the effect of being done. For example, in a polymer film formed of a polyester resin having a relatively large coefficient of thermal expansion, moisture release shrinkage occurs due to heat drying by a dryer, but the influence can be reduced in the laminate of the present embodiment.

Further, in the laminate of the present embodiment, a support made of a metal or a metal compound is used instead of the glass support normally used. Therefore, the support has excellent mechanical properties, and cracks and chips of the support are suitably suppressed in the manufacturing process of the flexible electronic device, so that the support is excellent in handleability.

(Polymer film)
The laminate of this embodiment includes a polymer film. The polymer film is not particularly limited as long as it satisfies the above-mentioned coefficient of thermal expansion in relation to the support, and examples thereof include a polymer film used for manufacturing an electronic device.

The coefficient of thermal expansion of the polymer film in the temperature region A (hereinafter, also referred to as “the coefficient of thermal expansion of the polymer film”) is from the viewpoint of balancing the coefficient of thermal expansion with the support in both the longitudinal direction and the width direction. It is preferably 5 ppm / ° C. to 50 ppm / ° C., preferably 10 ppm / ° C. to 40 ppm / ° C., and even more preferably 15 ppm / ° C. to 30 ppm / ° C. In the present disclosure, the coefficient of thermal expansion of the polymer film is the result of measurement by TMA based on the measurement method described later. The temperature is once raised to 180 ° C, cooled to 30 ° C, and then raised again. It is calculated from the dimensional change in the temperature region A at the time of. Further, the absolute value of the difference in the coefficient of thermal expansion of the polymer film in the longitudinal direction and the width direction is 9 ppm / ° C. or less, further 6 ppm / ° C. or less, particularly 3 ppm / ° C. from the viewpoint of balancing the coefficient of thermal expansion with the support. It is preferably ℃ or less.

The polymer film is not particularly limited as long as it is a film known per se or a film formed from a polymer that can be formed into a sheet, and the Tg required by DSC may be in the range of 50 ° C. to 200 ° C. The lower limit of Tg is preferably 55 ° C, more preferably 60 ° C. The upper limit of Tg is preferably 180 ° C, more preferably 160 ° C. When the Tg required by DSC is not less than the above lower limit, the heat resistance and dimensional stability required for the polymer film can be provided, while when the Tg is not more than the above upper limit, the film forming property and the film forming property to the film can be obtained. Excellent processability such as stretchability.
Specific resins for forming the polymer film include polyolefin resins such as polyethylene, polypropylene, and poly (4-methylpentene-1), ring-opened metathesis polymers of norbornenes, addition polymers, and other olefins. Cycloolefin polymers such as addition copolymers, biodegradable polymers such as polylactic acid and polybutylene succinate, polyamide resins such as nylon 6,11,12,66, aramid, polymethylmethacrylate, polyvinyl chloride, polyvinylidene chloride , Polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene / methyl methacrylate copolymer, polycarbonate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, nylon 6 , Nylon 66, poppolybutylene terephthalate, polyethylene-2,6-naphthalate, polycyclohexanedimethylene terephthalate and other polyester resins, polyether sulfone, polyether ketone, modified polyphenylene ether, polyphenylene sulfide, polyetherimide, polyarylate, 4 Those known per se, such as ethylene fluoride-6 fluorinated propylene copolymer, polyvinylidene fluoride, and acrylic nitrile / butadiene / styrene copolymer copolymer, can be used. Among these, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, nylon 6, nylon 66, polycyclohexanedimethylene terephthalate and the like can be mentioned from the viewpoint of the effect of the present invention, and the temperature expansion coefficient with the support can be mentioned. From the viewpoint of balancing, polyethylene terephthalate and polyethylene naphthalate are preferable.

Polyimide is often used as the polymer film, but polyimide is an expensive material and has problems that it is colored and easily cracked when curved. Therefore, it is used in flexible electronic devices using polyimide. There is a problem that is limited.

The thickness of the polymer film is not particularly limited, and is preferably 0.1 μm to 300 μm, more preferably 0.5 μm to 250 μm, and 1.0 μm from the viewpoint of mechanical strength and miniaturization. It is more preferably ~ 200 μm.

(Support)
The laminate of this embodiment is made of a metal or a metal compound, and includes a support that is temporarily fixed to a polymer film. The support is not particularly limited as long as it satisfies the above-mentioned coefficient of thermal expansion in relation to the polymer film.

The coefficient of thermal expansion of the support in the temperature region A (hereinafter, also referred to as “the coefficient of thermal expansion of the support”) is when the polymer film is bonded from the viewpoint of balancing the coefficient of thermal expansion with the polymer film. In addition, both the longitudinal direction and the direction indicating the same direction as the width direction of the polymer film are preferably 5 ppm / ° C. to 50 ppm / ° C., preferably 10 ppm / ° C. to 40 ppm / ° C., and 15 ppm / ° C. It is more preferably ~ 30 ppm / ° C.
In the present disclosure, the coefficient of thermal expansion of the support is the result measured by TMA based on the measurement method described later. The temperature was once raised to 180 ° C, cooled to 30 ° C, and then raised again. It is calculated from the dimensional change in the temperature region A at the time. The difference in the coefficient of thermal expansion of the support in the longitudinal direction and the width direction is 9 ppm / ° C or less, further 6 ppm / ° C or less, particularly 3 ppm / ° C or less from the viewpoint of balancing the coefficient of thermal expansion with the polymer film. It is preferable to have.

Examples of the support include those made of a metal or a metal compound. The metal may be a simple substance or an alloy. The metal in the present disclosure means an element on the diagonal line connecting aluminum and polonium in the periodic table of elements and an element on the lower left of the diagonal line. Examples of the metal compound include metal oxides, carbides, nitrides, borides and the like.

More specific examples of the support include aluminum, iron, copper, and stainless alloys, and among them, aluminum and stainless alloys are preferable.

The thickness of the support is not particularly limited, and is preferably 0.005 mm to 3.0 mm, more preferably 0.01 mm to 2.0 mm, from the viewpoint of handleability when formed into a laminated body. It is preferably 0.02 mm to 1.0 mm, and more preferably 0.02 mm to 1.0 mm.

The absolute value of the difference between the coefficient of thermal expansion of the support and the coefficient of thermal expansion of the polymer film may be 5 ppm or less, 4.5 ppm or less, or 4.0 ppm or less. .. The lower limit of the absolute value of the difference between the coefficient of thermal expansion of the support and the coefficient of thermal expansion of the polymer film is not particularly limited.

Further, the coefficient of thermal expansion of the polymer film may be equal to or higher than the coefficient of thermal expansion of the support, and is preferably larger than the coefficient of thermal expansion of the support. As a result, the deformation of the polymer film after the support is peeled from the polymer film can be further suppressed, and the dimensional stability tends to be better.

As the combination of the polymer film and the support, polyethylene terephthalate and aluminum or polyethylene naphthalate and stainless steel are preferable from the viewpoint of the balance of the coefficient of thermal expansion.

The laminate of the present embodiment may be one in which a polymer film is temporarily fixed to a support via an adhesive layer. The pressure-sensitive adhesive layer is not particularly limited as long as it is usually used for manufacturing a laminate used for manufacturing a flexible electronic device. For example, an adhesive sheet, an adhesive sheet, or the like may be attached to at least one of the support and the polymer film to form an adhesive layer, and an adhesive composition containing an adhesive component is applied to at least one of the support and the polymer film. The pressure-sensitive adhesive layer may be formed.

The pressure-sensitive adhesive layer may have a property of exhibiting adhesiveness at a predetermined temperature or higher and decreasing the adhesiveness at a temperature lower than a predetermined temperature. As a result, the polymer film can be suitably temporarily fixed to the support during predetermined steps such as a printing step and a heating step, and the polymer film can be easily peeled off from the support by cooling the laminate after the completion of the predetermined steps. can.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 0.01 μm to 50 μm, preferably 0.05 μm to 40 μm, from the viewpoint of alleviating unevenness on the surface of the support and suppressing unevenness derived from the pressure-sensitive adhesive layer. More preferably, it is more preferably 0.1 μm to 30 μm.

As described later, the laminate may have a conductor pattern formed on the surface on the polymer film side. For example, a thin film transistor (TFT), a transparent electrode, or the like is formed on the surface on the polymer film side. It may be a new one.

Further, in the laminate of the present embodiment, the absolute value of the dimensional difference before and after peeling of the polymer film is preferably 700 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, and further preferably 200 ppm. It is particularly preferably less than or equal to, and even more preferably 100 ppm or less. The dimensional difference before and after peeling of the polymer film is obtained by subtracting the dimension of the polymer film after peeling the polymer film from the support (dimension after peeling) from the dimension of the polymer film in the laminate (dimension before peeling). It can be calculated by dividing the subtracted value by the dimension before peeling and converting it to ppm unit. For example, as shown in Examples described later, a test pattern is printed on the polymer film surface of the laminate, and the dimensions of the test pattern before and after peeling of the polymer film are measured before and after peeling of the polymer film. The dimensional difference may be obtained.

<Manufacturing method of flexible electronic device>
A manufacturing method for manufacturing a flexible electronic device using the above-mentioned laminate is also included in the scope of the present invention. For example, in the method for manufacturing a flexible electronic device according to an embodiment of the present invention, a polymer film is temporarily fixed to a support to form a laminate, a conductor pattern is printed on the surface on the polymer film side, and the film is heated. A flexible electronic device is manufactured by peeling a polymer film from a support. In the method for manufacturing a flexible electronic device, the flexible electronic device may be manufactured using a cut sheet-like laminate, or the flexible electronic device may be continuously manufactured by roll-to-roll. Since the polymer film and the support used in the method for manufacturing the flexible electronic device are the same as the polymer film and the support used for the above-mentioned laminate, the description thereof will be omitted.

First, the method for manufacturing a flexible electronic device of the present embodiment includes a step (temporary fixing step) of temporarily fixing the polymer film to the support. As a result, a laminate in which the polymer film is temporarily fixed to the support can be obtained.

As a method of temporarily fixing the polymer film to the support, as described above, a method of temporarily fixing the polymer film to the support via an adhesive layer can be mentioned. As described above, an adhesive sheet, an adhesive sheet, or the like may be attached to at least one of the support and the polymer film to form an adhesive layer, and the attached adhesive layer may be attached to the other to form a laminate. Further, a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component may be applied to at least one of a support and a polymer film to form a pressure-sensitive adhesive layer, and the formed pressure-sensitive adhesive layer may be bonded to the other to form a laminate. When the pressure-sensitive adhesive layer is provided, it is preferable to clean the surface of the support in advance using a UV cleaning device or the like.
Further, it is preferable that the pressure-sensitive adhesive layer is provided on the support and then the pressure-sensitive adhesive layer is bonded to a polymer film to form a laminated body.

For example, as a method for bonding the polymer film to the support provided with the pressure-sensitive adhesive layer, a known bonding method can be appropriately adopted. Specific examples thereof include a roll laminating method, a pressing method, and a method of pressurizing with two rolls. The heating temperature when the polymer film is attached to the support provided with the pressure-sensitive adhesive layer may be, for example, about 30 ° C. to 100 ° C.

The method for manufacturing a flexible electronic device of the present embodiment includes a step (printing step) of printing a conductor pattern on the surface of the laminate on the polymer film side. The method for printing the conductor pattern is not particularly limited, but since the printing time is short and high-speed production of flexible electronic devices is possible, an ink containing metal particles, preferably an ink containing metal nanoparticles is used for printing. A contact-type printing method in which an intermediate medium such as a plate or a blanket is directly contacted with a polymer film as a final medium to transfer an image is preferable. Examples of the contact type printing method include letterpress printing, intaglio printing, lithographic printing, stencil printing, reverse offset printing, and the like.

The type of metal particles contained in the ink may be appropriately determined according to the required characteristics of the flexible electronic device, and examples thereof include platinum, gold, silver, copper, nickel, palladium, zinc, tin, and iron. The metal particles contained in the ink may be only one type or two or more types.

The average particle size of the metal particles is not particularly limited, and is preferably, for example, 1 nm to 500 nm, more preferably 1 nm to 200 nm, and further preferably 1 nm to 100 nm. The average particle size of the metal particles is the particle size (D50) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution measured by the laser diffraction method.

The method for manufacturing a flexible electronic device of the present embodiment includes a heating step of heating the laminate after the printing step. As a result, the metal nanoparticles printed on the polymer film are fired in the printing process, and the solvent contained in the ink can be removed.

The heating temperature in the heating step may be appropriately set according to the purpose, for example, preferably 80 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C., and 110 ° C. to 150 ° C. Is even more preferable.

The method for manufacturing a flexible electronic device of the present embodiment includes a peeling step of peeling a polymer film from a support after a heating step. At this time, it is preferable to peel off the polymer film from the support while cooling the laminate. For example, the surface on the support side is cooled instead of the entire laminate by a method such as bringing the surface on the support side into contact with the refrigerant. However, it is more preferable to peel off the polymer film from the support. By cooling the surface on the support side instead of the entire laminate, the occurrence of dew condensation on the polymer film side can be suppressed, and the problem caused by moisture can be suppressed.

The cooling temperature of the laminate, preferably the temperature of the refrigerant that comes into contact with the surface on the support side, is particularly high as long as the adhesiveness of the pressure-sensitive adhesive layer is reduced and the polymer film can be easily peeled off from the support. Not limited. For example, it may be equal to or lower than any of the melting point, the glass transition temperature, and the inflection point temperature of the storage elastic modulus in the pressure-sensitive adhesive layer.

The peeled surface when the polymer film is peeled from the support is preferably an interface between the polymer film and the pressure-sensitive adhesive layer from the viewpoint of suppressing the residual of the pressure-sensitive adhesive layer on the polymer film.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples. In addition, it is of course possible to carry out with appropriate modifications within a range that can be adapted to the gist of the present invention, and all of them are included in the technical scope of the present invention.
The method for evaluating the characteristics in the following examples is as follows. All operations and measurements for which temperature or humidity conditions were not described were carried out in an environment with a temperature of 23.0 ° C. ± 0.5 ° C. and a relative humidity of 50.0% ± 3.0%.

<Measurement of polymer film and support thickness>
A micrometer (“Millitron 1245D” manufactured by Fineryuf Co., Ltd.) was used to measure the thickness of the polymer film and the support, and the average value of 10 randomly selected points was calculated, and the average value was calculated as the polymer film. And the thickness of the support.

<Measurement of coefficient of thermal expansion (CTE) of polymer film>
For the polymer film, the change in the amount of expansion / contraction / temperature change in the temperature range from 30 ° C. to 120 ° C. was measured in the longitudinal direction and the width direction of the film under the following conditions. This measurement was repeated twice in each direction, and the average value was calculated as the coefficient of thermal expansion (CTE).
≪Conditions≫
Measuring device name: TMA / SS 7100 type manufactured by SII Nanotechnology Co., Ltd. Temperature rise / fall temperature; 30 ° C → (first temperature rise) → 180 ° C → (lower temperature) → 30 ° C → (second temperature rise) → 180 ° C (No holding time when the temperature reaches 180 ° C when the temperature rises and 30 ° C when the temperature drops)
Elevating temperature rate; 5 ° C / min atmosphere; nitrogen sample size; measuring direction 15 mm, width 2 mm
Distance between chucks; 10.0 mm
Initial load; 49.1 mN
CTE calculation method: Calculated from the amount of expansion / contraction / temperature change of the film at 30 ° C and 120 ° C at the second temperature rise.

<Measurement of coefficient of thermal expansion (CTE) of support>
The support was measured under the same conditions as the temperature expansion coefficient (CTE) measurement of the polymer film, in a direction coincident with the longitudinal direction and the width direction of the polymer films to be bonded. This measurement was repeated twice, and the average value was calculated as the coefficient of thermal expansion (CTE).

(Example 1)
<Adhesive sheet bonding>
A stainless steel plate (SUS304 steel plate, 300 mm × 220 mm, thickness 0.1 mm) used as a support was washed by irradiating it with UV light for 180 seconds with a UV cleaning device (SKT2005Y-01 manufactured by Takeden Co., Ltd.). Next, the protective film on one side of the double-sided cooling release sheet (Intellimer (registered trademark) tape cool-off type model number: CS2325NA4 manufactured by Nitta Corporation) of the same size (300 mm x 220 mm), which is an adhesive sheet, is peeled off, and the laminator device (climb) The adhesive sheet was attached to the stainless steel plate using SE 650 nH) manufactured by Products Co., Ltd.
Specifically, in the same laminator device, the stainless steel plate was adsorbed under reduced pressure through a stainless steel hot plate having holes, and the adhesive sheet side was adsorbed under reduced pressure via a 300 mesh stainless steel screen. The rubber hardness of the roller used was 70 degrees. The hot plate on the stainless steel plate side was set to 50 ° C. The stainless steel plate used as the support and the adhesive sheet are opposed to each other at a gap of 0.1 mm for 10 seconds, and then laminated at a roller supply pressure of 0.5 MPa, a pushing amount of 0.3 mm at the time of sticking, and a roller moving speed of 5.0 mm / sec. did.

<Attachment of polymer film>
Next, the polymer film was attached to the support to which the adhesive sheet was attached. As the polymer film, polyethylene naphthalate (PEN; manufactured by Teijin Film Solution Co., Ltd., Theonex (registered trademark) model number: Q65HA) was used. The bonding conditions and the like were the same as those for bonding the adhesive sheet described above.
As a result, a laminated body in which the polymer film and the support were bonded to each other via an adhesive sheet was obtained.

<Evaluation of dimensional difference before and after peeling>
A test pattern in which a high-definition printing machine (manufactured by Seputo Co., Ltd.), which is an inversion printing machine, is used on the polymer film surface of the laminate obtained as described above, and a square with an outer diameter of 150.000 mm is used with silver ink. Was printed and then dried at 120 ° C. for 60 minutes.
After that, the coordinate positions of each vertex of the square test pattern are measured using NEXIV VMR-6555 (manufactured by Nikon Corporation), the length of each side of the square is obtained from the coordinate positions, and the average value X of the four sides is calculated. did.

Next, the support surface of the laminated body is brought into contact with a cooling plate whose temperature has been adjusted to -10 ° C for 10 seconds, and then the edge of the polymer film is scratched to create a trigger for peeling so that the peeling angle becomes about 45 degrees as it is. The polymer film was peeled off from the support by pulling the polymer film.
After peeling, the length of each side of the square was obtained using NEXIV VMR-6555 (manufactured by Nikon Corporation) in the same manner as described above, and the average value Y of the four sides was calculated.

The dimensional difference before and after peeling was obtained by subtracting the average value Y after peeling from the obtained average value X before peeling and dividing the subtracted value by the average value X before peeling and converting it into ppm. .. The results are shown in Table 1.

(Examples 2 and 3 and Comparative Examples 1 to 5)
A laminate was prepared in the same manner as in Example 1 except that the polymer film and the support were changed to those shown in Table 1, and the dimensional difference before and after peeling was determined.
The results are shown in Table 1.

Further, with respect to Examples 1 to 3 and Comparative Examples 1 to 5, the coefficient of thermal expansion of the polymer film (the coefficient of thermal expansion of the polymer film was determined from the coefficient of thermal expansion of the polymer film and the coefficient of thermal expansion of the support measured as described above. CTE) -The coefficient of thermal expansion (CTE) of the support was calculated. The relationship between the coefficient of thermal expansion (CTE) of the polymer film-the coefficient of thermal expansion (CTE) of the support and the dimensional difference before and after peeling measured as described above is shown in FIGS. 1 and 2. FIG. 1 corresponds to the longitudinal direction and FIG. 2 corresponds to the width direction. Further, in FIGS. 1 and 2, the plots marked with circles correspond to Examples 1 to 3, and the plots marked with triangles correspond to Comparative Examples 1 to 5.

The polymer films and supports in Table 1 are as follows.
≪Polymer film≫
PEN: Polyethylene naphthalate (manufactured by Teijin Film Solution Co., Ltd., Theonex (registered trademark), model number: Q65HA, thickness 125 μm)
PET: Polyethylene terephthalate (manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark), model number: A-1555LS, thickness 188 μm)
PI: Polyimide (manufactured by Toyobo Co., Ltd., XENOMAX (registered trademark), model number: F38LR, thickness 38 μm)
≪Support≫
Alkaline-free glass (Corning, Eagle XG, thickness 1.1 mm)
Soda glass (manufactured by Central Glass Co., Ltd., thickness 1.1 mm)
Aluminum plate (Aluminum plate manufactured by Hitachi Metals Neomaterial Co., Ltd., thickness 0.1 mm and 0.3 mm)
SUS304 steel sheet (SUS304 steel sheet manufactured by Hitachi Metals, Ltd. Neomaterial, thickness 0.1 mm)

As shown in Table 1, FIG. 1 and FIG. 2, in Examples 1 to 3, the CTE difference (absolute value) between the polymer film and the support is 5 ppm or less, and the dimensional difference (absolute value) before and after peeling. Was 620 ppm or less in either the longitudinal direction or the width direction, whichever was larger.
On the other hand, in Comparative Examples 1 to 5, the CTE difference (absolute value) between the polymer film and the support is more than 5 ppm, and the dimensional difference (absolute value) before and after peeling is larger in either the longitudinal direction or the width direction. Was 650 ppm or more.
As described above, in Examples 1 to 3 in which the CTE difference (absolute value) between the polymer film and the support is 5 ppm or less, Comparative Examples 1 to 1 in which the CTE difference (absolute value) between the polymer film and the support is more than 5 ppm. It was shown that the dimensional difference (absolute value) before and after peeling was smaller than that of 5, and the deformation of the polymer film after peeling the support was suppressed.

Claims (5)

A polymer film in which the glass transition temperature determined by differential scanning calorimetry (DSC) is in the range of 50 ° C to 200 ° C, and
A support made of a metal or a metal compound and temporarily fixed to the polymer film,
With
The absolute value of the difference between the longitudinal temperature expansion coefficient of the support in the temperature region A from 30 ° C. to 120 ° C. and the longitudinal temperature expansion coefficient of the polymer film in the temperature region A, and the above. The absolute value of the difference between the temperature expansion coefficient in the width direction of the support in the temperature region A and the temperature expansion coefficient in the width direction of the polymer film in the temperature region A is 5 ppm / ° C. or less, and is flexible. A laminate used in the manufacture of electronic devices. The laminate according to claim 1, wherein at least one of the coefficient of thermal expansion of the support and the coefficient of thermal expansion of the polymer film is 5 ppm / ° C. to 50 ppm / ° C. The laminate according to claim 1 or 2, wherein the coefficient of thermal expansion of the polymer film is equal to or greater than the coefficient of thermal expansion of the support. The laminate according to any one of claims 1 to 3, wherein the polymer film and the support are polyethylene terephthalate and aluminum, or polyethylene naphthalate and a stainless alloy. A manufacturing method for manufacturing a flexible electronic device using the laminate according to any one of claims 1 to 4.
Flexible electrons that temporarily fix the polymer film to the support to form the laminate, print a conductor pattern on the surface on the polymer film side, heat the polymer film, and then peel the polymer film from the support. How to make the device.

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