TWI803752B - Laminated substrates and packages - Google Patents

Abstract

The present invention relates to a laminated substrate, which is laminated with a polyimide resin layer and a protective film covering the polyimide resin layer on a support substrate made of glass, and the polyimide resin When the first adhesive force between the layer and the above-mentioned protective film is _F1 , and the second adhesive force between the above-mentioned support substrate and the above-mentioned protective film is _F2 , the above-mentioned first adhesive force _F1 is 0.001 N/10 mm≦F ₁ ≦0.17 N/10 mm, the above-mentioned second adhesion force F ₂ is 0.05 N/10 mm≦F ₂ ≦(F ₁ (N/10 mm)+0.3 N/10 mm).

Description

Laminated substrates and packages

The present invention relates to a laminated substrate and a packing body.

Manufacture such as solar cells; liquid crystal panels (LCD, Liquid Crystal Display); organic EL panels (OLED, Organic Light-Emitting Diode); receiving sensor panels for sensing electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc.; and other electronics For the device, as described in Patent Document 1, there is disclosed an aspect in which a polyimide resin layer is used as a substrate. The polyimide resin layer is used in the state of a build-up substrate provided on a glass substrate, and the build-up substrate is provided for manufacturing electronic devices. After the electronic device is formed, the polyimide resin layer is separated from the glass substrate.

On the other hand, when conveying a plurality of glass substrates, for example, as described in Patent Document 2, it is conveyed in the form of a glass plate package in which a plurality of glass plates are laminated with a base paper containing virgin pulp interposed therebetween.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-104843

[Patent Document 2] Japanese Domestic Publication No. 2016/104450

As described above, in order to form various components for electronic devices constituting electronic devices on the polyimide resin layer in the buildup substrate, it is desirable that the surface of the polyimide resin layer has no damage or foreign matter.

On the other hand, the inventors of the present invention found that although as described in Patent Document 2, they tried to use a base paper containing virgin pulp, and laminated a plurality of laminated substrates on a glass substrate to form a polyimide resin layer. The package transports a plurality of laminated substrates, but the surface of the polyimide resin layer in the laminated laminated substrates is damaged.

Also, the inventors of the present invention found that instead of the backing paper, a protective film was attached to the polyimide resin layer to prevent the above-mentioned damage, but depending on the type of protective film, when the protective film was peeled off, the supporting substrate was damaged. When the protective film is peeled off, foreign matter is generated on the surface of the polyimide resin layer, or when foreign matter is generated on the outer peripheral portion of the polyimide resin layer.

Therefore, the object of the present invention is to provide a kind of lamination that also suppresses damage to the surface of the polyimide resin layer, when peeling off the protective film, suppresses the damage of the supporting substrate, and furthermore, suppresses foreign matter on the polyimide resin layer. The produced laminated substrate, and a package loaded with a plurality of laminated substrates.

As a result of intensive studies by the inventors of the present invention, it was found that the above object can be achieved by the following configuration.

The first aspect of the present invention provides a laminated substrate, which is laminated on a support substrate made of glass with a polyimide resin layer and a protective film covering the polyimide resin layer, and the polyimide When the first adhesive force between the imide resin layer and the protective film is F ₁ , and the second adhesive force between the support substrate and the protective film is F ₂ , the first adhesive force F ₁ is 0.001N/10mm≦F ₁ ≦ 0.17N/10mm, the second adhesion force F ₂ is 0.05N/10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm).

Preferably, the size of the protective film is equal to or larger than the size of the supporting substrate.

Preferably, the thickness of the protective film is 20 μm or more.

Preferably, the protective film has a base material and an adhesive layer laminated on the base material and in contact with the polyimide resin layer, and the base material is made of polyethylene.

Preferably, the adhesive force between the support base material and the polyimide resin layer is larger than either the first adhesive force or the second adhesive force.

Preferably, a silane coupling agent layer is provided between the support substrate and the polyimide resin layer.

Preferably, a silicone resin layer is provided between the support substrate and the polyimide resin layer.

The 2nd aspect of this invention provides the packing body which has a pallet, and the laminated board|substrate of the said 1st aspect which mounted several sheets on the pallet.

It is preferable that a plurality of laminated substrates are loaded on the pallet in a state where loads are applied to each other.

Preferably, the pallet has a base plate and a back plate standing upright on the base plate, and the laminated substrates are placed on the pallet in a state in which the surface of the supporting base material is inclined toward the back plate.

Preferably, the size of the laminated substrate is 850 mm or more on the short side and 1100 mm or more on the long side.

According to the present invention, there is provided a laminated substrate that suppresses damage to the surface of the polyimide resin during lamination, suppresses damage to the support substrate when the protective film is peeled off, and suppresses generation of foreign matter on the polyimide resin layer, and a carrier A package with a plurality of laminated substrates.

10:Laminated substrate

12: Support substrate

12a: Surface

12b: back

12c: Outer edge

13: Silicone resin layer

13a: Surface

14: polyimide resin layer

14a: surface

16: Protective film

18: Substrate

19: Adhesive layer

20: Bale body

22: pallet

24: Bottom plate

24a: surface

26: Backplane

26a: surface

D: Foreign matter

β: angle

Fig. 1 is a plan view schematically showing a first example of a build-up substrate according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view schematically showing a first example of a build-up substrate according to an embodiment of the present invention.

Fig. 3 is a cross-sectional view schematically showing the protective film of the first example of the laminated substrate according to the embodiment of the present invention.

Fig. 4 is a plan view schematically showing a second example of the laminated substrate according to the embodiment of the present invention.

Fig. 5 is a cross-sectional view schematically showing a third example of a build-up substrate according to an embodiment of the present invention.

Fig. 6 is a side view schematically showing an example of a packing body according to an embodiment of the present invention.

Fig. 7 is a cross-sectional view schematically illustrating generation of buried objects in a build-up substrate according to an embodiment of the present invention.

Fig. 8 is a cross-sectional view schematically illustrating generation of buried objects in a build-up substrate according to an embodiment of the present invention.

Fig. 9 is a cross-sectional view schematically illustrating generation of buried objects in a build-up substrate according to an embodiment of the present invention.

FIG. 10 is a SEM (Scanning Electron Microscope: Scanning Electron Microscope) image showing an example of buried objects in a build-up substrate according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. In addition, various changes and substitutions may be added to the following embodiments without departing from the scope of the present invention.

The numerical range indicated by "~" means that the numerical value recorded before and after "~" is taken as the lower limit The range included in the value and the upper limit.

As a characteristic point of the laminated substrate of the present invention, the point of providing a protective film covering the polyimide resin layer can be mentioned. In particular, the desired effect can be obtained by adjusting the adhesion between the protective film, the polyimide resin layer and the supporting substrate.

The inventors of the present invention have found that when using the base paper described in Patent Document 2, the damage caused on the surface of the polyimide resin layer can be, for example, the tightness between the base paper and the polyimide resin layer. Focus too low. That is, because the adhesion between the backing paper and the polyimide resin layer is weak, friction occurs between the backing paper and the polyimide resin layer, and damage occurs on the surface of the polyimide resin layer. On the other hand, if the adhesion between the polyimide resin layer and the protective film is too strong, when the protective film is peeled off, foreign matter originating from the components of the protective film (for example, the material of the adhesive layer) remains on the polyimide resin. layer.

Considering the above points, adjust the adhesion between the protective film and the polyimide resin layer.

Furthermore, if the adhesive force between the protective film and the supporting substrate is too weak, the protective film will be easily peeled off, and foreign matter will adhere to the outer peripheral portion of the polyimide resin layer. On the other hand, if the adhesion between the protective film and the supporting substrate is too strong, when the protective film is peeled off, there will be a difference in peeling speed between the polyimide resin layer part and the supporting substrate part, and when the protective film is peeled off, the The support substrate exerts undesired force, resulting in the destruction of the support substrate.

Considering the above points, adjust the adhesion between the protective film and the supporting substrate.

<Laminated substrate>

[The first example of laminated substrate]

Fig. 1 is a plan view schematically showing a first example of a laminated substrate according to an embodiment of the present invention, Fig. 2 is a cross-sectional view schematically showing a first example of a build-up substrate according to an embodiment of the present invention. Fig. 3 is a cross-sectional view schematically showing the protective film of the first example of the laminated substrate according to the embodiment of the present invention.

The laminated substrate 10 of the first example is one in which a polyimide resin layer 14 and a protective film 16 covering the polyimide resin layer 14 are laminated on a support substrate 12 made of glass.

As shown in FIG. 2 , on the surface 12 a of the support substrate 12 , a polyimide resin layer 14 is provided. As shown in FIG. 1 , the area of the polyimide resin layer 14 is smaller than the surface 12 a of the support substrate 12 , and is not provided on the entire area of the surface 12 a of the support substrate 12 . The polyimide resin layer 14 is not provided on the outer edge portion 12c of the surface 12a of the support base material 12, that is, the forehead portion of the support base material 12.

The protective film 16 is disposed so as to cover the polyimide resin layer 14 on the support base 12 . As shown in FIGS. 2 and 3 , the protective film 16 has a base material 18 and an adhesive layer 19 laminated on the base material 18 . As shown in FIG. 2 , the adhesive layer 19 of the protective film 16 is in contact with the surface 14 a of the polyimide resin layer 14 and the surface 12 a of the support substrate 12 . The protective film 16 is peeled off when the polyimide resin layer 14 is used as a substrate. In this case, the adhesive layer 19 of the protective film 16 may peel off from the state which contact|connected the surface 14a of the polyimide resin layer 14 and the surface 12a of the support base material 12 simultaneously.

The supporting base material 12 is a member supporting the polyimide resin layer 14 and functions as a reinforcing plate for reinforcing the polyimide resin layer 14 . In addition, the support base 12 also functions as a transfer substrate when the build-up substrate 10 is transferred.

In the laminated substrate 10, when a force is applied in a direction in which the supporting base material 12 and the polyimide resin layer 14 are separated, the supporting base material 12 and the polyimide resin layer 14 are separated.

The polyimide resin layer 14 is a substrate for manufacturing electronic devices. On the surface 14a of the polyimide resin layer 14, electronic components such as transistors, coils, and resistors constituting the electronic device, and signal lines are formed.

The protective film 16 protects the support base material 12 and the polyimide resin layer 14, and particularly protects the polyimide resin layer 14 so as not to be scratched or damaged due to force received from the outside. The protective film 16 has the same size as the supporting base material 12 in the build-up substrate 10 shown in FIG. 1 , for example.

In the laminated substrate 10, when the first adhesive force between the polyimide resin layer 14 and the protective film 16 is _F1 , and the second adhesive force between the support base material 12 and the protective film 16 is _F2 ,

The first adhesion force F ₁ is 0.001N/10mm≦F ₁ ≦0.17N/10mm. The second adhesion force F ₂ is 0.05 N/10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm).

The measurement of the said 1st adhesive force _F1 and the 2nd adhesive force _F2 was performed as follows. First, the protective film 16 cut into short strips with a width of 25 mm was bonded to the polyimide resin layer 14 or the support substrate 12 . Next, it was left to stand for 5 days in an environment with a temperature of 40°C and a relative humidity of 80% under the state of applying a load of 16 g per 1 cm ² . Thereafter, a 90° C. peel test was implemented. The lifting speed of peeling is set at 300mm/min. Calculate the load when peeling the protective film per unit width (10 mm) from the load in the area where the peeling is stable.

As described above, the first adhesion force F ₁ is 0.001N/10mm≦F ₁ ≦0.17N/10mm. When the first adhesion force _F1 is less than 0.001N/10mm, the polyimide resin layer 14 and the protective film 16 are not sufficiently adhered, and friction occurs between the polyimide resin layer 14 and the protective film 16, and the The surface 14a of the imide resin layer 14 is damaged.

If the first adhesive force _F1 exceeds 0.17N/10mm, the adhesive force between the polyimide resin layer 14 and the protective film 16 is too strong, and a part of the adhesive layer 19 of the protective film 16 remains on the polyimide resin layer 14 surface 14a, resulting in foreign matter. In particular, when the adhesive layer is an adhesive layer containing an adhesive, residues of the adhesive derived from the adhesive are generated. In addition, if foreign matters (especially adhesive residues) are generated, the heat resistance of the polyimide resin layer 14 is lowered, or a disconnection may occur in an electronic device formed using the polyimide resin layer 14 . Furthermore, if the first adhesive force F ₁ exceeds 1.5 N/10mm, when the first adhesive force F ₁ is too large, the supporting base material 12 may be damaged.

Among them, based on the point of further suppressing the damage and generation of foreign matter on the surface 14a of the polyimide resin layer 14, the first adhesion force _F1 is preferably 0.002-0.15N/10mm, more preferably 0.003-0.145N/10mm.

As described above, the second adhesion force F ₂ is 0.05 N/10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm). The upper limit of the second adhesive force F ₂ is greater than the first adhesive force F ₁ .

When the second adhesive force _F2 is less than 0.05N/10mm, the adhesive force between the protective film 16 and the support substrate 12 is too weak, and the protective film 16 on the outer edge 12c of the support substrate 12 is rolled up during transportation, resulting in a large amount of foreign matter Attached to the outer peripheral portion of the polyimide resin layer 14 . The possibility of damage or the like occurring in the polyimide resin layer 14 increases due to the foreign matter.

If the second adhesion force _F2 exceeds _F1 (N/10mm)+0.3N/10mm, then the adhesion force between the protective film 16 and the support substrate 12 is too strong, and when the protective film 16 is peeled off, the polyimide resin layer 14 There is a difference in peeling speed between the portion and the portion of the supporting substrate 12 , and an undesired force is applied to the supporting substrate 12 when the protective film 16 is peeled off, resulting in damage to the supporting substrate 12 .

In the laminated substrate 10, since the second adhesive force _F2 between the supporting base material 12 and the protective film 16 is within the above range, the protective film 16 can be peeled off smoothly without damage to the supporting base material 12 or the like.

Among them, based on further suppressing the generation of foreign matter on the surface 14a of the polyimide resin layer 14 and the damage of the support substrate 12, the second adhesion force _F2 is preferably 0.06-0.18N/10mm, more preferably 0.07-0.17 N/10mm.

In addition, in the laminated substrate 10, it is preferable that the adhesive force between the support base material 12 and the polyimide resin layer 14 is larger than any one of the above-mentioned first adhesive force _F1 and second adhesive force _F2 . As a method of improving the adhesion between the support substrate 12 and the polyimide resin layer 14, as described later, it is a method of modifying the surface of the support substrate 12 (for example, a method of modifying with a silane coupling agent). That is, a method of providing a silane coupling agent layer (a layer formed using a silane coupling agent) between the support base 12 and the polyimide resin layer 14, or a method of providing a layer between the support base 12 and the polyimide resin Between the layers 14, a method of providing a layer (for example, a silicone resin layer described later) to improve the adhesion between the two layers.

In addition, when a layer such as a silane coupling agent layer and a silicone resin layer is provided between the support substrate 12 and the polyimide resin layer 14, it is preferable that the support substrate 12 and the silane coupling agent layer or silicone resin The adhesive force of the layers, and the adhesive force between the polyimide resin layer 14 and the silane coupling agent layer or the silicone resin layer are larger than any of the above-mentioned first adhesive force _F1 and second adhesive force _F2 .

[Manufacturing method of the first example of laminated substrate]

As a method of manufacturing the laminated substrate 10 of the first example, a method of laminating the polyimide resin layer 14 on the surface 12 a of the support substrate 12 is preferable. Among them, it is preferable to coat a well-known silane coupling agent on the surface 12a of the support substrate 12 before laminating the polyimide resin layer 14 on the surface 12a of the support substrate 12, and then, coat the silane coupling agent on the surface 12a coated with the silane coupling agent. On the surface 12a of the support substrate 12 of the mixture, a polyimide resin layer 14 is laminated. In this case, a silane coupling agent layer is provided between the support substrate 12 and the polyimide resin layer 14 . In the state where the polyimide resin layer 14 is formed on the surface 12a of the support substrate 12, the adhesive layer 19 is arranged and kept facing the surface 12a of the support substrate 12. The protective film 16 is to attach the protective film 16 covering the polyimide resin layer 14 to the support substrate 12 . Thereby, the build-up substrate 10 can be manufactured.

[Second example of laminated substrate]

Fig. 4 is a plan view schematically showing a second example of the laminated substrate according to the embodiment of the present invention. In the build-up substrate 10 of the second example shown in FIG. 4, the same components as those of the build-up substrate 10 of the first example shown in FIG. 1 and FIG.

Compared with the build-up substrate 10 shown in FIGS. 1 and 2, the build-up substrate 10 of the second example is the same as the build-up substrate 10 shown in FIGS.

Like the build-up substrate 10 of the second example, by making the size of the protective film 16 larger than that of the supporting substrate 12, one end of the protective film 16 can be easily held when the protective film 16 is peeled off.

[Manufacturing method of the second example of laminated substrate]

The build-up substrate 10 of the second example can be the same as that of the first example, except that the protective film 16 is larger than the supporting base material 12, and the protective film 16 is attached to the supporting base material 12 so as to cover the polyimide resin layer 14. The laminated substrate 10 is manufactured in the same manner.

[The third example of laminated substrate]

Fig. 5 is a cross-sectional view schematically showing a third example of a build-up substrate according to an embodiment of the present invention. In the build-up substrate 10 of the third example shown in FIG. 5, the same components as those of the build-up substrate 10 of the first example shown in FIGS.

Compared with the build-up substrate 10 shown in FIGS. 1 and 2 , the build-up substrate 10 of the third example is the same as that shown in FIG. 1 and FIG. Figure 2 The build-up substrate 10 shown is the same.

In the build-up substrate 10 of the third example, a support base material 12, a silicone resin layer 13, and a polyimide resin layer 14 are laminated in this order. A silicone resin layer 13 is provided on the surface 12 a of the support substrate 12 , and a polyimide resin layer 14 is provided on the surface 13 a of the silicone resin layer 13 . Although the size of the silicone resin layer 13 is the same as that of the polyimide resin layer 14 , it is smaller than the surface 12 a of the support substrate 12 .

In the build-up substrate 10 of the third example, the supporting base material 12 and the silicone resin layer 13 function as a reinforcing plate for reinforcing the polyimide resin layer 14 .

When heat-processing the laminated substrate 10, it is preferable to make the adhesive force between the support base material 12 and the silicone resin layer 13 larger than the adhesive force between the silicone resin layer 13 and the polyimide resin layer 14. This can be produced by, for example, bonding the hydroxyl groups of the support substrate 12 to the hydroxyl groups of the silicone resin layer 13 by heat treatment.

As a result, when a force is applied in a direction in which the supporting substrate 12 and the polyimide resin layer 14 are peeled off, peeling occurs between the silicone resin layer 13 and the polyimide resin layer 14 . Thereby, the polyimide resin layer 14 can be separated.

In addition, in the build-up substrate 10 of the third example, the size of the protective film 16 is not limited. Like the laminated substrate 10 shown in FIG. 1 , the size of the protective film 16 and the supporting substrate 12 can be the same, or the same as the laminated substrate 10 shown in FIG. 4 , the size of the protective film 16 can be larger than that of the supporting substrate 12. .

[Manufacturing method of the third example of laminated substrate]

The method of manufacturing the laminated substrate 10 of the third example is preferably a method of forming the silicone resin layer 13 on the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a). Specifically, it is preferable to The following method: apply a curable composition containing curable silicone on the back surface of the polyimide resin layer 14, and perform curing treatment on the obtained coating film to obtain the silicone resin layer 13, and then coat the silicone resin layer 13 On the back side (the side opposite to the front surface 13 a ), the support substrate 12 is laminated to manufacture the laminated substrate 10 .

More specifically, the method of manufacturing the laminated substrate 10 of the third example has at least the following steps: forming a curable silicone layer on the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a), The step of forming the silicone resin layer 13 on the back of the imide resin layer 14 (resin layer forming step); the step of laminating the supporting base material 12 on the back of the silicone resin layer 13 (the side opposite to the surface 13a) (lamination step) ; and the step of sticking the protective film 16 (bonding step). Hereinafter, each of the above-mentioned steps will be described in detail.

(Resin layer forming step)

The resin layer forming step is a step of forming a curable silicone layer on the back of the polyimide resin layer 14 , and forming the silicone resin layer 13 on the back of the polyimide resin layer 14 . Through this step, a substrate with a silicone resin layer provided with the polyimide resin layer 14 and the silicone resin layer 13 in sequence is obtained.

The substrate with the silicone resin layer can be manufactured by the so-called roll-to-roll method in which the silicone resin layer 13 is formed on the back of the polyimide resin layer 14 wound into a roll, and then wound into a roll again, thereby improving production efficiency. excellent.

In this step, in order to form a curable silicone layer on the back of the polyimide resin layer 14 , the above-mentioned curable composition is coated on the back of the polyimide resin layer 14 . Next, it is preferable to form a cured layer by performing a curing process on the curable silicone layer.

Specific examples of the method of coating the curable composition on the back surface of the polyimide resin layer 14 include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, net Lithographic printing method and gravure printing coating method.

Next, the curable silicone coated on the back surface of the polyimide resin layer 14 is cured to form the silicone resin layer 13 .

The curing method for forming the silicone resin layer 13 is not particularly limited, and the optimum treatment is appropriately performed according to the type of curable silicone used. For example, when using a condensation reaction type silicone and an addition reaction type silicone are appropriate, as the hardening treatment, heat hardening treatment is preferable.

The conditions of thermosetting treatment are carried out within the range of heat resistance of the polyimide resin layer 14, for example, the temperature condition of thermosetting is preferably 50~400°C, more preferably 100~300°C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes.

The silicone resin layer 13 will be described below.

(lamination step)

The lamination step is a step of laminating the supporting substrate 12 on the surface of the silicone resin layer 13 . As a specific example of the method of laminating the support base material 12 on the back surface of the silicone resin layer 13, a method of laminating the support base material 12 on the back surface of the silicone resin layer 13 under a normal pressure environment may be mentioned. Optionally, after the support base material 12 is overlapped on the back surface of the silicone resin layer 13, the support base material 12 can be pressure-bonded to the silicone resin layer 13 using a roller or a pressing member. It is preferable to relatively easily remove air bubbles mixed between the silicone resin layer 13 and the support substrate 12 by pressing with a roller or a pressing member.

It is preferable to press-bond by a vacuum lamination method or a vacuum pressing method because it can suppress the mixing of air bubbles and achieve good adhesion. By performing crimping under vacuum, there is also an advantage that even when minute air bubbles remain, air bubbles are less likely to grow due to heat treatment.

When laminating the supporting substrate 12, it is preferable to fully clean the supporting substrate in contact with the silicone resin layer 13 The surface of the material 12 is laminated in an environment with a high degree of cleanliness.

(fitting step)

In the attaching step, the protective film 16 is arranged so that the adhesive layer 19 faces the surface 12 a of the supporting substrate 12 , and the protective film 16 is attached to the supporting substrate 12 by covering the polyimide resin layer 14 . Thereby, the build-up substrate 10 is obtained.

<pack body>

Fig. 6 is a side view schematically showing an example of a packing body according to an embodiment of the present invention. In the package body 20 shown in FIG. 6 , the same components as those in the first example of the build-up substrate 10 shown in FIGS. 1 and 2 are assigned the same reference numerals, and detailed description thereof will be omitted.

The package 20 has the plurality of laminated substrates 10 shown in FIG. 1 above, and a pallet 22 on which the plurality of laminated substrates 10 are stacked.

When the laminated substrate 10 is more than 1200mm×1000mm (G5 size), it is difficult to pack the laminated substrates in a box in a state where the laminated substrates are completely separated from each other. It is preferable to apply a plurality of laminated substrates 10 to each other as described later. The state of the load is loaded on the pallet 22, and the laminated substrate 10 is packed.

The laminated substrate 10 is quadrangular. The size of the laminated substrate 10 is preferably 850 mm or more on the short side and 1100 mm or more on the long side, more preferably 1200 mm or more on the short side and 1300 mm or more on the long side, and more preferably 1400 mm or more on the short side and 1400 mm or more on the long side. Above 1700mm. The upper limit of the size of the laminate substrate 10 is preferably 3000 mm×3000 mm.

The supporting board 22 has a bottom board 24 and a back board 26 , and the back board 26 is erected on the bottom board 24 . Base plate 24 table Face 24a is orthogonal to surface 26a of back plate 26 . With the supporting base material 12 of the laminated substrate 10 facing the surface 26a of the back plate 26, the supporting base material 12 is mounted on the surface 24a of the bottom plate 24 and the surface 26a of the back plate 26, and for example, the laminated substrate on the side closest to the supporting plate 22 10 is laminated on the pallet 22 in a state where the laminated substrate 10 is tilted. The angle β formed by the back surface 12b of the support substrate 12 of the laminated substrate 10 and the surface 24a of the bottom plate 24 is, for example, 45° to 85°.

The support substrate 12 of other laminated substrates 10 is contacted and superimposed on the protective film 16 of the laminated substrate 10, and a plurality of laminated substrates 10 are laminated in contact.

The pallet 22 is made of resin such as polypropylene resin, but is not particularly limited.

If the plurality of laminated substrates 10 are in a state where loads are applied to each other, they can be placed in direct contact with each other and loaded on the pallet 22. Also, as will be described later, a backing paper can be provided between the laminated substrates 10, and the plurality of laminated substrates can be placed. The build-up substrate 10 is placed on the pallet 22 .

Also, for the purpose of separating the back surface 12b of the support base 12 from the surface of the protective film 16 of the adjacent build-up substrate 10, a backing paper is placed between them. By putting the backing paper, the adhesion between the back surface 12b of the support base material 12 and the surface of the protective film 16 of the adjacent laminated substrate 10 is reduced, so that when the laminated substrate 10 is taken from the pallet 22, it is easy to Take piece by piece.

In addition, the pallet 22 is configured to have a bottom plate 24 and a back plate 26, but its configuration is not particularly limited as long as a plurality of laminated substrates 10 can be stacked and loaded.

The build-up substrate 10 is conveyed in a form in which a plurality of build-up substrates 10 are loaded on the package body 20 of the pallet 22 in a state where loads are applied to each other. At this time, among the plurality of laminated substrates 10, the largest load is applied to the laminated substrate 10 on the side closest to the back plate 26, and the laminated substrates 10 rub against each other due to the vibration during transportation. As described above, by providing the protective film 16, even if a load is applied to the laminated substrate 10, even if the laminated substrates 10 are rubbed against each other, scratches and scratches on the polyimide resin layer 14 are suppressed. Damage, and even foreign body attachment.

In the laminated substrate 10, since the second adhesion force F2 between the support base material 12 and the protective film 16 is within the above-mentioned range, even if the packaging body 20 is transported in a general environment, the protective film 16 and the support base will not be produced. The peeling of the material 12 prevents a large amount of foreign matter from adhering to the outer peripheral portion of the polyimide resin layer 14, and defects do not increase.

The build-up substrate 10 mounted on the pallet 22 is not limited to the build-up substrate 10 of the first example shown in FIG.

In addition, the laminated substrate 10 can be packaged using, for example, a glass plate packing box (see FIGS. 1 to 17 ) described in Japanese Patent No. 4251290 .

Specifically, the glass plate packing box is composed of a stand on which the laminated substrate 10 is placed, a bottom plate on which the stand is placed, a front plate, a rear plate, and side plates erected on the bottom plate, and a top plate covering the upper part.

The glass plate packing box is provided with installation components for embedding the front plate and the two side plates on the upper front edge and side edges of the bottom plate. The mounting member is provided with a pair of facing side panels on the bottom panel, and the front panel and two side panels are embedded between the facing side panels. In addition to the above configuration, the mounting member may also be provided with a groove opening on the bottom plate, and the front plate and the side plates are embedded in the groove.

In addition, in order to prevent damage when the laminated substrate is placed, cushioning materials may be attached to the base plate and the back plate respectively.

In addition, after placing the plurality of laminated substrates on the stand, cover the front side of the storage body containing the plurality of laminated substrates with a protective plate made of resin, arrange triangular members at the two corners, and attach these with a tape. bundled. The belt combines the fixed metal parts at the end of the adjustable length belt member with the Securely bind the storage body by snapping it with the elbow clip, etc. In this way, by binding the storage body with a belt, the whole can be fixed firmly with a simple mechanism. In addition, if the protective plate is used as a cushioning member, after the laminated substrates are bound with tapes, the elbow clips can be further firmly bound.

Hereinafter, the supporting base material 12, the polyimide resin layer 14, the silicone resin layer 13, and the protective film 16 constituting the build-up substrate 10 will be described in detail.

<Support substrate>

The support substrate 12 made of glass supports and reinforces the polyimide resin layer 14 and functions as a transfer substrate. The supporting substrate 12 is formed of, for example, a glass plate.

As the type of glass, alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high-silica glass, and oxide-based glass mainly composed of other silicon oxides are preferable. The oxide-based glass is preferably glass having a silicon oxide content of 40 to 90% by mass in terms of oxides.

More specifically, the glass may, for example, be a glass plate made of alkali-free borosilicate glass (manufactured by AGC Co., Ltd., brand name "AN100").

As a manufacturing method of a glass plate, the method of melting a glass raw material normally, and forming a molten glass into a plate shape is mentioned, for example. Such a forming method may be a general one, and examples thereof include a float method, a fusion method, and an orifice downdraw method.

The supporting substrate 12 may be thicker or thinner than the polyimide resin layer 14 . Based on the rationality of the laminated substrate 10 , it is preferable to make the thickness of the supporting base material 12 thicker than that of the polyimide resin layer 14 .

Since the supporting base material 12 is required to function as a reinforcing plate and transporting the substrate, it is preferably non-flexible. Therefore, the thickness of the supporting substrate 12 is preferably more than 0.3mm, more preferably 0.5mm above. On the other hand, the thickness of the supporting substrate 12 is preferably 1.0 mm or less.

<Polyimide resin layer>

The polyimide resin layer 14 contains polyimide resin, and uses, for example, a polyimide film. Specific examples of commercially available polyimide films include "XENOMAX" manufactured by Toyobo Co., Ltd. and "UPILEX 25S" manufactured by Ube Industries, Ltd.

The surface 14a of the polyimide resin layer 14 is smooth in order to form high-definition wiring and the like constituting an electronic device. Specifically, the surface roughness Ra of the surface 14 a of the polyimide resin layer 14 is preferably 50 nm or less, more preferably 30 nm or less, and still more preferably 10 nm or less. The lower limit of the surface roughness Ra is, for example, 0.01 nm or more.

The thickness of the polyimide resin layer 14 is preferably at least 1 μm, more preferably at least 5 μm, and still more preferably at least 10 μm, from the viewpoint of the operability of the manufacturing steps. In terms of flexibility, the thickness of the polyimide resin layer 14 is preferably 1 mm or less, more preferably 0.2 mm or less.

The smaller the difference between the coefficient of thermal expansion of the polyimide resin layer 14 and the coefficient of thermal expansion of the support substrate 12 is, it is preferable because it can suppress warping after heating or cooling. Specifically, the difference in thermal expansion coefficient between the polyimide resin layer 14 and the support substrate 12 is preferably 0~90×10 ^-6 /°C, more preferably 0~30×10 ^-6 /°C.

The area of the polyimide resin layer 14 (the area of the surface 14 a ) is not particularly limited, but it is preferably smaller than the area of the support substrate 12 in order to arrange the protective film 16 . On the other hand, based on the productivity of electronic devices, the area of the polyimide resin layer 14 is preferably more than 300 cm ² .

The shape of the polyimide resin layer 14 is not particularly limited, and may be rectangular or circular. It is also possible to form an orientation flat (a flat portion formed on the outer periphery of the substrate) on the polyimide resin layer 14, and a notch (at least one V-shaped notch formed on the outer periphery of the substrate).

<protective film>

As shown in FIG. 3 , the protective film 16 preferably has a laminated structure of a substrate 18 and an adhesive layer 19 .

In order to reduce the influence of force received from the outside, the thickness of the protective film 16 is preferably at least 20 μm, more preferably at least 30 μm, and still more preferably at least 50 μm. The upper limit of the thickness of the protective film 16 is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less.

In the case of having a laminated structure of the base material 18 and the adhesive layer 19 , the thickness of the protective film 16 is the total thickness of the base material 18 and the adhesive layer 19 . The upper limit of the thickness of the protective film 16 is preferably 500 μm or less because excessive force may be required to peel the protective film if it is too thick.

Thickness of the protective film 16 Measure the thickness of the protective film 16 at more than 5 arbitrary positions with a contact-type film thickness measuring device, and calculate the arithmetic mean of these.

Also, the substrate 18 of the protective film 16 is preferably made of polyester resin (for example, polyethylene terephthalate (PET)), polyolefin resin (for example, polyethylene (PE) and polypropylene, etc.), polyurethane resin And other resin composition. Among them, the resin constituting the base material 18 of the protective film 16 is preferably polyolefin, more preferably polyethylene or polypropylene.

The adhesive layer 19 is not particularly limited as long as it satisfies the first adhesive force F ₁ and the second adhesive force F ₂ . As the adhesive layer 19, a well-known adhesive layer can also be used. Specific examples of the adhesive constituting the adhesive layer include (meth)acrylic adhesives, silicone adhesives, and urethane adhesives.

In addition, the adhesive layer 19 may also be made of resin, and specific examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, etc. Grease, (meth)acrylic resin, butyral resin, polyurethane resin, polystyrene elastomer, etc.

In addition, (meth)acrylic acid includes the concept of acrylic acid and methacrylic acid.

In addition, depending on the type of the protective film 16, the degree of difficulty in generating buried objects on the surface 14a of the polyimide resin layer 14 changes. Hereinafter, the mechanism thereof will be described in detail.

Here, FIGS. 7 to 9 are cross-sectional views schematically illustrating generation of embedded objects in a build-up substrate according to an embodiment of the present invention. In addition, FIG. 10 is a SEM image showing an example of the buried object of the build-up substrate according to the embodiment of the present invention. In addition, in FIGS. 7 to 10 , the same components as those of the build-up substrate 10 shown in FIGS. 1 and 2 are given the same reference numerals, and detailed description thereof will be omitted.

As shown in FIG. 7, when there is a foreign matter D between the surface 14a of the polyimide resin layer 14 and the protective film 16, if the protective film 16 is relatively hard, then as shown in FIG. 8, the protective film 16 is not easily deformed, resulting in The foreign matter D is buried in the polyimide resin layer 14 . As a result, buried objects are generated in the polyimide resin layer 14 . Specifically, in the SEM image shown in FIG. 10 , the foreign matter D is embedded in the polyimide resin layer 14 , and this foreign matter D becomes an embedded matter.

On the other hand, if the protective film 16 is soft, the protective film 16 is deformed as shown in FIG. It is buried in the polyimide resin layer 14 . Thereby, even if the foreign matter D exists between the surface 14a of the polyimide resin layer 14, and the protective film 16, and is laminated|stacked, generation|occurence|production of a defect in the polyimide resin layer 14 is suppressed. Therefore, the base material 18 of the protective film 16 is preferably soft.

In addition, the softness of the base material 18 of the protective film 16 is determined according to the relative relationship between the size of the foreign matter D and the hardness of the foreign matter D.

In addition, about the softness of the said protective film 16, Examples 4-6 of an Example were evaluated as mentioned later.

<Silicone resin layer>

The silicone resin layer 13 mainly contains silicone resin. The structure of the silicone resin is not particularly limited. Silicone resins are generally obtained by hardening silicone hardening (cross-linking hardening) that can be cured into silicone resins by hardening treatment.

Specific examples of curable silicones include condensation reaction silicones, addition reaction silicones, ultraviolet curable silicones, and electron beam curable silicones, depending on their curing mechanism. The weight average molecular weight of the curable silicone is preferably from 5,000 to 60,000, more preferably from 5,000 to 30,000.

As a method of manufacturing the silicone resin layer 13, the method of coating the back surface (the surface opposite to the surface 14a) of the polyimide resin layer 14 with a hardening agent including curable silicone that becomes the above-mentioned silicone resin is preferably used. If necessary, the solvent is removed to form a coating film, and the curable silicone in the coating film is cured to form the silicone resin layer 13 .

The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (in the case of using an additional reactive silicone as the curable silicone), a leveling agent, a metal compound, and the like. Specific examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanide metals, bismuth, aluminum, and tin. Properly adjust the content of metal compounds.

The thickness of the silicone resin layer 13 is preferably at most 100 μm, more preferably at most 50 μm, and even more preferably at most 30 μm. On the other hand, the thickness of the silicone resin layer 13 is preferably over 1 μm, more preferably over 4 μm. The above-mentioned thickness is the thickness of the silicone resin layer 13 at 5 or more arbitrary positions measured with a contact-type film thickness measuring device, and the arithmetic average of these is performed.

<Applications of laminated substrates>

Examples of applications of the laminated substrate 10 include a display device, a sensor panel, a solar cell, a thin-film secondary battery, and an integrated circuit, which will be described later. There is also a case where the polyimide resin layer is exposed to a high temperature condition of 450° C. or higher for 20 minutes or longer in the air atmosphere with the protective film 16 peeled off.

Specific examples of display devices include LCD, OLED, electronic paper, plasma display panels, field emission panels, quantum dot LED panels, micro LED display panels, and MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems) shutter panels .

Specific examples of the receiving sensor panel include an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible light receiving sensor panel, and an infrared receiving sensor panel. In the case of receiving a sensor panel, the polyimide resin layer may be reinforced with a reinforcing sheet of resin or the like.

As described above, after the protective film is peeled off from the laminated substrate of the present invention, an electronic device including the polyimide resin layer and the electronic device member is manufactured using the obtained laminate including the support base material and the polyimide resin layer.

As a method of manufacturing an electronic device, for example, a method of forming an electronic device member on the polyimide resin layer in the obtained laminate comprising a support base material and a polyimide resin layer, placing the support base The material was peeled off from the obtained laminate with the member for electronic device, and an electronic device having the polyimide resin layer and the member for electronic device was obtained.

In addition, the above-mentioned member for an electronic device is a member constituting at least a part of the electronic device.

[Example]

Hereinafter, although an Example etc. demonstrate this invention more concretely, this invention is not limited by these examples. Examples 1 to 6 described later are examples, and examples 7 to 16 are comparative examples.

<assessment>

(Assessment of Foreign Objects in the Peripheral Area)

In the evaluation of foreign matter in the outer periphery, in each case, before the protective film was installed, the optical inspection device manufactured by Orbotech was used to obtain the position information and map of the defects existing on the surface of the edge area of the outer peripheral part of the polyimide resin layer with a width of 10 mm. picture. Then, a load of 16 g/cm ² was applied to the protective film of the laminated substrate obtained in each example, and left to stand in an atmosphere of a temperature of 40° C. and a relative humidity of 80% for 5 days. Thereafter, the protective film was peeled off, and the optical inspection device manufactured by Orbotech was used again to obtain positional information and images of defects existing on the surface of the edge region with a width of 10 mm in the outer peripheral portion of the polyimide resin layer.

Compare the images before and after setting the protective film, and evaluate whether there are foreign objects in the edge area. In addition to foreign matter, defects such as adhesive residue or damage may also occur, so the image showing foreign matter is defined in advance, and when comparing images, the presence or absence of foreign matter is evaluated with reference to the image showing foreign matter.

As a result of image comparison, if there is a foreign object in the outer peripheral portion, it is set as “Yes”, and if there is no foreign object in the outer peripheral portion, it is set as “No”.

(Assessment of Adhesive Residue)

In the evaluation of adhesive residue, in each case, before installing the protective film, the optical inspection device manufactured by Orbotech was used to obtain the position information and image of the defect existing on the surface of the polyimide resin layer in advance. Then, a load of 16 g/cm ² was applied to the protective film of the laminated substrate obtained in each example, and left for 5 days in an atmosphere at a temperature of 40° C. and a relative humidity of 80%. Thereafter, the protective film was peeled off, and the optical inspection device manufactured by Orbotech was used again to obtain positional information and images of defects existing on the surface of the polyimide resin layer.

Compare the images before and after installing the protective film to evaluate whether there is any adhesive residue. In addition to adhesive residue, there may also be damage, so the image showing adhesive residue is defined in advance, and when comparing images, refer to the image showing adhesive residue to evaluate whether there is adhesive residue.

As a result of the image comparison, if any adhesive remains, it is set as "Yes", and if no adhesive remains, it is set as "No".

(Assessment of damage)

In the assessment of damage, in each example, before installing the protective film, the optical inspection device manufactured by Orbotech was used to acquire the positional information and images of defects existing on the surface of the polyimide resin layer in advance.

In addition, 23 glass plates with a thickness of 2.8mm were stacked on the protective film of the laminated substrate obtained in each example and placed under a load for 5 days in an atmosphere at a temperature of 40°C and a relative humidity of 80%. Thereafter, the protective film was peeled off, and an image of the surface of the polyimide resin layer was obtained by using the optical inspection device manufactured by Orbotech again.

Compare the images before and after applying the load to evaluate whether there is damage. In addition to damage, adhesive residue may also occur, so the image showing damage is defined in advance, and when comparing images, the image showing damage is used to evaluate whether there is damage.

As a result of the image comparison, if there is damage, it is set to "Yes", and if there is no damage, it is set to "None".

(Supports the assessment of base material damage)

When the protective film was peeled from the laminated substrate obtained in each example, the case where the support substrate was damaged was set as "present", and the case where no damage occurred was set as "absence".

(Evaluation of heat resistance test)

The heat resistance evaluation of the laminated substrate after peeling off the protective film was carried out as follows.

A silicon nitride film (SiNx) with a film thickness of 200nm was formed on the laminated substrate for adhesive residue evaluation using plasma CVD (Chemical Vapor Deposition: Chemical Vapor Deposition) method. Thereafter, heating was performed at 500° C. for 10 minutes in a nitrogen atmosphere. After heating, when the polyimide resin layer was not peeled off from the supporting substrate, the heat resistance was evaluated as "◯", and when peeling occurred, the heat resistance was evaluated as "×".

(Assessment of Embedded Foreign Objects)

Depending on the type of protective film, the evaluation of whether foreign matter is embedded in the polyimide resin layer is carried out as follows.

First, before installing the protective film, in order to deliberately place foreign matter on the polyimide resin layer, the polyimide resin layer is placed in a normal pressure and normal temperature environment, and the optical inspection device manufactured by Orbotech Co., Ltd. is used to perform defect inspection. (foreign matter) inspection. Thereafter, a protective film was placed on the polyimide resin layer, and 23 glass plates with a thickness of 2.8mm were stacked to apply a load, and placed in an atmosphere with a temperature of 40°C and a relative humidity of 80% for 5 days. Next, the protective film was peeled off, and the surface of the polyimide resin layer was inspected for defects (foreign matter) on the surface of the polyimide resin layer using an optical inspection device manufactured by Orbotech again. By comparing the defect distribution of the optical inspection device made by Orbotech before and after the protective film is attached, it is confirmed whether the foreign matter existing on the polyimide resin layer before lamination remains after the protective film is peeled off, and the foreign matter remaining after that, Using an optical microscope and scanning Type electron microscope (SEM) to observe the surface of foreign matter. By comparing the image of the optical microscope and the image of the scanning electron microscope, it is judged whether it is a buried foreign object.

(Assessment about long-term storage)

In the case of storing with a protective film attached and a load applied to the bonding surface, it is carried out to confirm whether there is adhesive residue or damage on the surface of the polyimide resin layer. In each example, three laminated substrates for long-term storage tests were prepared. In each example, before installing the protective film, the optical inspection device manufactured by Orbotech Co., Ltd. was used to acquire positional information and images of defects existing on the surface of the polyimide resin layer in advance. Next, a protective film was provided on the polyimide resin layer, and a load of 16 g/ ^cm2 was applied to the protective film of the laminated substrate obtained in each example, in an atmosphere with a temperature of 40°C and a relative humidity of 80%. Leave it for 5 days. Thereafter, it was taken out in an environment of normal temperature and normal pressure, and left in a state where a load of 16 g/cm ² was applied. The sum of the period of being placed in an atmosphere with a temperature of 40°C and a relative humidity of 80%, and the period of taking it out and placing it under normal temperature and normal pressure is 2 months, 4 months, and 6 months. Remove the load from one laminated substrate of the protective film, peel off the protective film, and use the optical inspection device made by Orbotech again to obtain position information and images of defects existing on the surface of the polyimide resin layer. Predefine images showing adhesive residue or damage, and when comparing images, evaluate whether there is adhesive residue or damage with reference to the image showing adhesive residue or damage.

Compare the images before and after setting the protective film to evaluate whether there is adhesive residue or damage.

Hereinafter, examples 1 to 16 will be described.

<Example 1>

(Preparation of curable silicone)

In a 1L flask, add triethoxymethylsilane (179g), toluene (300g), acetic acid (5 g), after stirring the mixture at 25° C. for 20 minutes, it was further heated to 60° C. and reacted for 12 hours. After cooling the obtained reaction crude liquid to 25 degreeC, the reaction crude liquid was washed 3 times with water (300g).

Trimethylsilyl chloride (70 g) was added to the crude reaction solution after washing, and the mixture was stirred at 25° C. for 20 minutes, and then heated to 50° C. to react for 12 hours. After cooling the obtained reaction crude liquid to 25 degreeC, the reaction crude liquid was washed 3 times with water (300g).

Toluene was distilled off from the reaction crude liquid after washing under reduced pressure, and after being made into a slurry state, it was dried in a vacuum dryer overnight, thereby obtaining curable silicone 1, which is a white organopolysiloxane compound. The number of T units of curable silicone 1: the number of M units=87:13 (molar ratio).

In addition, the M unit means a monofunctional organosilyloxy unit represented by (R) ₃ SiO _1/2 . The T unit refers to a trifunctional organosilyloxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group).

(Preparation of curable composition)

Curable silicone 1 was mixed with hexane as a solvent, and bismuth (III) 2-ethylhexanoate was added as a metal compound. The amount of the solvent was adjusted so that the solid content concentration was 50% by mass. Moreover, the addition amount of a metal compound was adjusted so that a metal element may become 0.01 mass part with respect to 100 mass parts of resin. A curable composition was obtained by filtering the resulting mixed solution with a filter having a pore size of 0.45 μm.

(Manufacturing of laminated substrates)

The prepared curable composition was coated on a polyimide film with a thickness of 0.015mm (manufactured by Toyobo Co., Ltd., trade name "XENOMAX"), and heated at 140°C for 10 minutes using a hot plate to form a silicone resin layer . The thickness of the silicone resin layer is 10 μm.

Next, a 200×200 mm, 0.05 mm thick glass plate “AN100” (support substrate) washed with an aqueous glass cleaner (manufactured by Parkercorp Co., Ltd., “PK-LGC213”) and then washed with pure water was placed on the The silicone resin layer is bonded using a bonding device to produce a laminate.

Next, the obtained laminate was heated at 500° C. for 30 minutes in a nitrogen atmosphere. Thereafter, air blowing was performed to remove fine dust from the surface of the polyimide film.

A protective film was bonded to the polyimide film side of the obtained laminate to obtain a laminate substrate. As the protective film used, Panac Co., Ltd. Panaprotect (registered trademark) ETK50B (trade name) having a thickness of 55 μm was used. The protective film has a substrate (thickness 50 μm, PET film) and an adhesive layer.

<Example 2~16>

The laminated substrates of Examples 2 to 16 were obtained according to the same procedure as Example 1 except that the type of protective film was changed.

In addition, in Example 2, Panac Co., Ltd. Panaprotect (registered trademark) PX50T01A15 (trade name) having a thickness of 65 μm was used as the protective film. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 3, as the protective film, Mastac (registered trademark) PC-751 (trade name) of Fujimori Shangyo Co., Ltd. with a thickness of 55 μm was used. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 4, as a protective film, a film having a base material (PET film) and an adhesive layer having a thickness of 65 μm was used.

In Example 5, as the protective film, Sun-A.Kaken Co., Ltd. with a thickness of 70 μm Division PAC-3-70 (trade name). The protective film is a coextruded film of LDPE (low density polyethylene) film and ethylene-vinyl acetate copolymer layer.

In Example 6, Futamura (Futamura) Chemical Co., Ltd. FSA (registered trademark) 010M (trade name) having a thickness of 30 μm was used as the protective film. The protective film is a self-adhesive protective film using biaxially stretched polypropylene (OPP) as the substrate (thickness: 30 μm).

In Example 7, Panac Co., Ltd. Panaprotect (registered trademark) ST50 (trade name) having a thickness of 57 μm was used as the protective film. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 8, Panac Co., Ltd. Panaprotect (registered trademark) GC50 (trade name) having a thickness of 80 μm was used as the protective film. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 9, Panac Co., Ltd. Panaprotect (registered trademark) GS50 (trade name) having a thickness of 63 μm was used as the protective film. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 10, Panac Co., Ltd. Panaprotect (registered trademark) GN50 (trade name) having a thickness of 60 μm was used as the protective film. The protective film has a substrate (thickness: 50 μm, PET film) and an adhesive layer.

In Example 11, Sun-A. Kaken Co., Ltd. JA16F (trade name) having a thickness of 60 μm was used as the protective film. The protective film has a substrate (LDPE film) and an adhesive layer.

In Example 12, as the protective film, Sun-A. Kaken Co., Ltd. Y16F (trade name) having a thickness of 60 μm was used. The protective film has a substrate (LDPE film) and an adhesive layer.

In Example 13, as the protective film, Sun-A. Kaken Co., Ltd. P27 (trade name) having a thickness of 74 μm was used. The protective film has a substrate (PE film) and an adhesive layer.

In Example 14, Sun-A. Kaken Co., Ltd. B35 (trade name) having a thickness of 50 μm was used as the protective film. The protective film has a substrate (PE film) and an adhesive layer.

In Example 15, as a protective film, a raw pulp backing paper with a thickness of 50 μm was used. The protective film does not have an adhesive layer.

In Example 16, a PET film having a thickness of 50 μm was used as the protective film. The protective film does not have an adhesive layer.

Table 1 and Table 2 summarize the first adhesive force and the second adhesive force of the laminated substrates of each example. The measurement method of each adhesive force is as above.

The "adhesive" column in Table 1 and Table 2 indicates the type of adhesive in the adhesive layer in the protective film, "acrylic" means that the adhesive is an acrylic adhesive, and "silicone" means the adhesive It is a silicone adhesive.

<Summary of Evaluation Results>

As shown in Table 1 and Table 2 above, in Examples 1 to 6 satisfying the specific requirements, desired effects were obtained.

In addition, in Examples 1 to 6, since the first adhesive force between the protective film and the polyimide resin layer is 0.001N/10mm or more and 0.17N/10mm or less, even if it is transported in an atmospheric environment, it will not produce protection. The peeling of the film and the polyimide resin layer was not confirmed, and the increase in edge defects of the polyimide resin layer was not confirmed. Furthermore, since in Examples 1 to 6, the second adhesion force F ₂ between the support substrate and the protective film is 0.05N/10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm), the protective film When peeling, it can be peeled off smoothly without causing damage to the supporting substrate.

In addition, in Examples 4 to 6, the protective film was cut into a size of 100mm×100mm, and folded in half so that the side opposite to the adhesive surface faced. Next, using a glass substrate, a load of 16 g/cm ² was applied to the double fold. And after leaving it for 30 minutes with the load applied, the glass substrate was removed. And, to what extent the protective film recovered was confirmed. In Examples 5 and 6, the bent state (0°) was maintained, but in Example 4, the protective film recovered to a certain extent to 90°. Therefore, in Example 4, the restoration force of the protective film is relatively strong, and it is not easy to follow the foreign matter and deform, so it is speculated that it can push the foreign matter to the polyimide resin layer.

In addition, in Examples 5 and 6, the long-term storage test was carried out, but no adhesive residue or damage was found in any of the storage periods after long-term storage for 2 months, 4 months, and 6 months.

This application is based on Japanese Patent Application No. 2019-106053 filed on June 6, 2019, the contents of which are incorporated herein by reference.

10:Laminated substrate

12: Support substrate

12a: Surface

12c: Outer edge

14: polyimide resin layer

14a: surface

16: Protective film

18: Substrate

19: Adhesive layer

Claims (10)

A laminated substrate, which is laminated on a support substrate made of glass, with a polyimide resin layer and a protective film covering the polyimide resin layer, and the polyimide resin layer and the protective film are laminated. When the first adhesive force of the film is _F1 , and the second adhesive force between the above-mentioned support substrate and the above-mentioned protective film is _F2 , the above-mentioned first adhesive force _F1 is 0.001N/10mm≦ _F1 ≦0.17N/ 10 mm, the above-mentioned second adhesion force F ₂ is 0.05N/10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm). The laminated substrate according to claim 1, wherein the thickness of the protective film is 20 μm or more. The laminated substrate according to claim 1 or 2, wherein the protective film has a base material and an adhesive layer laminated on the base material and in contact with the polyimide resin layer, and the base material is made of polyethylene. The laminated substrate according to claim 1 or 2, wherein the adhesion between the support substrate and the polyimide resin layer is greater than any of the first adhesion and the second adhesion. The laminated substrate according to claim 1 or 2, wherein a silane coupling agent layer is provided between the above-mentioned support substrate and the above-mentioned polyimide resin layer. The laminated substrate according to claim 1 or 2, wherein a silicone resin layer is provided between the above-mentioned support substrate and the above-mentioned polyimide resin layer. A package comprising a pallet, and a plurality of laminated substrates according to any one of claims 1 to 6 mounted on the pallet. The package according to claim 7, wherein the plurality of laminated substrates are loaded on the pallet in a state where loads are applied to each other. The packing body according to claim 7 or 8, wherein the pallet has a bottom plate and a back plate erected on the bottom plate, and the laminated substrate is loaded on the pallet. The packaged body according to claim 7 or 8, wherein the size of the above-mentioned laminated substrate is 850 mm or more on the short side and 1100 mm or more on the long side.

Images