KR20200140719A - Laminated substrate and package - Google Patents

Abstract

The present invention relates to a laminated substrate, in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a glass support base material. When F_1 represents first adhesive force between the polyimide resin layer and the protective film, and F_2 represents second adhesive force between the support base material and the protective film, the first adhesive force F_1 satisfies 0.001 N/10 mm <= F_1 <= 0.17 N/10 mm, and the second adhesive force F_2 satisfies 0.05 N/10 mm <= F_2 <= (F_1 (N/10 mm) + 0.3 N/10 mm). Accordingly, the occurrence of scratches on the surface of the polyimide resin layer is suppressed.

Description

Laminated substrate and package {LAMINATED SUBSTRATE AND PACKAGE}

The present invention relates to a laminated substrate and a package.

Solar cells; Liquid crystal panel (LCD); Organic EL panel (OLED); A receiving sensor panel that detects electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, and the like; When manufacturing electronic devices such as, as described in Patent Document 1, an aspect in which a polyimide resin layer is used as a substrate is disclosed. The polyimide resin layer is used in the state of a laminated substrate provided on a glass substrate, and the laminated substrate is provided for manufacture of an electronic device. After forming the electronic device, the polyimide resin layer and the glass substrate are separated.

On the other hand, when transporting a plurality of glass substrates, for example, as described in Patent Document 2, it is transported in the form of a glass plate package formed by laminating a plurality of glass plates through a laminate containing virgin pulp.

Japanese Patent Publication No. 2015-104843 Japan Domestic Publication No. 2016/104450

As described above, since various electronic device members constituting an electronic device are formed on the polyimide resin layer in the laminated substrate, it is preferable that the surface of the polyimide resin layer has no scratches or foreign matter.

On the other hand, as described in Patent Document 2, the present inventors use a package obtained by laminating a plurality of laminated substrates obtained by laminating a plurality of laminated substrates in which a polyimide resin layer is formed on a glass substrate through a laminate containing virgin pulp. When transporting of the laminated substrate of was attempted, it was found that scratches occurred on the surface of the polyimide resin layer in the laminated laminated substrate.

In addition, the present inventors attempted to prevent the occurrence of the above scratches by bonding the protective film to the polyimide resin layer instead of the lamination. Depending on the type of the protective film, the support base material may be damaged when peeling the protective film, After peeling of the protective film, it was found that foreign matters may occur on the surface of the polyimide resin layer or in the outer peripheral portion of the polyimide resin layer.

Therefore, in the present invention, even when laminated, the occurrence of scratches on the surface of the polyimide resin layer is suppressed, damage to the supporting substrate is suppressed when peeling the protective film, and the occurrence of foreign matter on the polyimide resin layer is suppressed. An object of the present invention is to provide a substrate and a package in which a plurality of laminated substrates are stacked.

As a result of intensive examination, the present inventors found that the above-described object can be achieved by the following configuration.

A first aspect of the present invention is a laminated substrate in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a glass supporting substrate, and the first adhesive force between the polyimide resin layer and the protective film is F ₁ and that, when said second urging force of the support substrate and the protection film F _2, F ₁ is a first adhesive force, 0.001N / 10mm≤F ₁ and ≤0.17N / 10mm, the second urging force F ₂ is, 0.05N / It is to provide a laminated substrate of 10mm≦F ₂ ≦(F ₁ (N/10mm)+0.3N/10mm).

It is preferable that the size of the protective film is larger than the size of the supporting substrate.

It is preferable that the thickness of a protective film is 20 micrometers or more.

It is preferable that the protective film has a base material and an adhesion layer laminated on the base material and in contact with the polyimide resin layer, and the base material is made of polyethylene.

It is preferable that the adhesive force between the supporting base material and the polyimide resin layer is greater than any of the first adhesive force and the second adhesive force.

It is preferable that a silane coupling agent layer is provided between the supporting substrate and the polyimide resin layer.

It is preferable that a silicone resin layer is provided between the supporting base material and the polyimide resin layer.

A second aspect of the present invention is to provide a package comprising a pallet and a laminated substrate according to the first aspect, which are plurally stacked on the pallet.

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

It is preferable that the pallet has a bottom plate and a back plate installed on the bottom plate, and the laminated substrate is mounted on the pallet in a tilted state with the supporting substrate facing the surface of the back plate.

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

According to the present invention, even when laminated, the occurrence of scratches on the surface of the polyimide resin layer is suppressed, damage to the supporting substrate is suppressed when peeling the protective film, and the occurrence of foreign matter on the polyimide resin layer is suppressed. A substrate and a package in which a plurality of laminated substrates are stacked can be provided.

1 is a plan view schematically showing a first example of a laminated substrate according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a first example of a laminated substrate according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing a protective film of a first example of a laminated substrate according to an embodiment of the present invention.
4 is a plan view schematically showing a second example of a laminated substrate according to an embodiment of the present invention.
5 is a cross-sectional view schematically showing a third example of a laminated substrate according to an embodiment of the present invention.
6 is a side view schematically showing an example of a package according to the embodiment of the present invention.
Fig. 7 is a cross-sectional view schematically illustrating the occurrence of a buried material in the laminated substrate according to the embodiment of the present invention.
Fig. 8 is a cross-sectional view schematically illustrating the occurrence of a buried material in the laminated substrate according to the embodiment of the present invention.
9 is a cross-sectional view schematically illustrating the occurrence of a buried material in the laminated substrate according to the embodiment of the present invention.
10 is an SEM image showing an example of a buried object in the laminated substrate according to the embodiment of the present invention.

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

The numerical range displayed using "to" means a range including a numerical value described before and after "to" as a lower limit value and an upper limit value.

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

The inventors of the present invention have mentioned that the adhesive force between the paper and the polyimide resin layer is too low as the cause of scratching on the surface of the polyimide resin layer when using the paper containing virgin pulp described in Patent Document 2 Knowing. That is, since the adhesive force between the paper and the polyimide resin layer is weak, rubbing occurs between the paper and the polyimide resin layer, and scratches are generated on the surface of the polyimide resin layer. On the other hand, if the adhesive force between the polyimide resin layer and the protective film is too strong, when the protective film is peeled, foreign matters derived from the components derived from the protective film (for example, the material of the adhesive layer) will remain on the polyimide resin layer. .

In consideration of the above point, the adhesive force between the protective film and the polyimide resin layer is adjusted.

In addition, when the adhesive force between the protective film and the supporting substrate is too weak, the protective film is peeled, and foreign matters are liable to adhere to the outer peripheral portion of the polyimide resin layer. On the other hand, if the adhesive force between the protective film and the supporting substrate is too strong, when peeling the protective film, a difference in the peeling rate occurs between the polyimide resin layer portion and the supporting substrate portion, and the support substrate is intended for peeling the protective film It takes a force that does not do so, leading to destruction of the supporting substrate.

In consideration of the above point, the adhesive force between the protective film and the supporting substrate is adjusted.

<Laminated substrate>

[First Example of Laminated Substrate]

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

In the laminated substrate 10 of the first example, a polyimide resin layer 14 and a protective film 16 covering the polyimide resin layer 14 are laminated on a glass support substrate 12.

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

The protective film 16 covers the polyimide resin layer 14 on the support base 12 and is disposed. As shown in FIGS. 2 and 3, the protective film 16 includes a base 18 and an adhesion layer 19 laminated on the base 18. As shown in FIG. 2, the adhesion layer 19 of the protective film 16 is in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the support substrate 12. The protective film 16 is peeled off when using the polyimide resin layer 14 as a substrate. In this case, the adhesion layer 19 of the protective film 16 may be peeled from the state in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the supporting substrate 12 at the same time. .

The supporting base material 12 is a member that supports the polyimide resin layer 14 and functions as a reinforcing plate for reinforcing the polyimide resin layer 14. In addition, the supporting substrate 12 functions as a conveying substrate during conveyance of the laminated substrate 10.

In the laminated substrate 10, when a force is applied in the direction in which the support substrate 12 and the polyimide resin layer 14 are pulled out, the support substrate 12 and the polyimide resin layer 14 are separated.

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

The protective film 16 protects the support base 12 and the polyimide resin layer 14, and particularly protects the polyimide resin layer 14 from hitting scratches and scratches caused by external forces. . The protective film 16 has the same size as the support base 12 in the laminated substrate 10 shown in FIG. 1, for example.

In the laminated substrate 10, the first adhesion force between the polyimide resin layer 14 and the protective film 16 is referred to as F ₁ , and the second adhesion force between the support substrate 12 and the protective film 16 is referred to as F ₂ .

A first urging force F ₁ is, 0.001N / 10mm≤F is ₁ ≤0.17N / 10mm. A second urging force F _2, is _{0.05N / 10mm≤F 2 ≤ (F 1} (N / 10mm) + 0.3N / 10mm).

The above-described first adhesion force F ₁ and second adhesion force F ₂ are measured as follows. First, the protective film 16 cut out into a rectangle having a width of 25 mm is bonded to the polyimide resin layer 14 or the supporting substrate 12. Then, it is allowed to stand for 5 days in an environment at a temperature of 40°C and a relative humidity of 80% in a state where a load of 16 g per 1 cm 2 is applied. After that, a 90° peeling test is performed. The pulling speed at the time of peeling is set to 300 mm/min. From the load of the stably peeled region, the load when peeling the protective film per unit width (10 mm) is calculated.

As described above, the first urging force F ₁ is, 0.001N / 10mm≤F is ₁ ≤0.17N / 10mm. If the first adhesive force F ₁ is less than 0.001 N/10 mm, the polyimide resin layer 14 and the protective film 16 are not sufficiently adhered to each other, and the polyimide resin layer 14 and the protective film 16 are not in close contact with each other. This occurs, and a scratch is generated on the surface 14a of the polyimide resin layer 14.

When the first adhesive force F ₁ exceeds 0.17 N/10 mm, the adhesive force between the polyimide resin layer 14 and the protective film 16 is too strong, so that the surface 14a of the polyimide resin layer 14 has a protective film ( Part of the adhesion layer 19 of 16) remains, leading to the generation of foreign matter. In particular, when the adhesive layer is an adhesive layer containing an adhesive, residual adhesive derived from the adhesive occurs. In addition, when foreign matter (particularly, residual adhesive) occurs, the heat resistance of the polyimide resin layer 14 may decrease, or defects such as disconnection may occur in an electronic device formed using the polyimide resin layer 14. . Furthermore, when the first adhesive force F _{1 such} that the first adhesive force F ₁ exceeds 1.5 N/10 mm, and the first adhesive force F ₁ is too large, the supporting substrate 12 may be damaged.

Among them, the first adhesion force F ₁ is preferably 0.002 to 0.15 N/10 mm, and 0.003 to from the point that the occurrence of scratches on the surface 14a of the polyimide resin layer 14 and generation of foreign matter are more suppressed. 0.145N/10mm is more preferable.

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

If the second adhesive force F ₂ is less than 0.05 N/10 mm, the adhesive force between the protective film 16 and the support substrate 12 is too weak, and the protective film 16 of the outer edge 12c of the support substrate 12 is transported It peels off, and a large amount of foreign matter adheres to the outer peripheral part of the polyimide resin layer 14. There is a high possibility that a scratch or the like may occur in the polyimide resin layer 14 by this foreign material.

When the second adhesion force F ₂ exceeds F ₁ (N/10mm) + 0.3N/10mm, the adhesion between the protective film 16 and the support substrate 12 is too strong, and when peeling the protective film 16, the polyether A difference in peel rate occurs between the mid resin layer 14 portion and the support substrate 12 portion, and an unintended force is applied to the support substrate 12 when the protective film 16 is peeled off, and the support substrate 12 Leads to destruction of.

In the laminated substrate 10, since the second adhesive force F ₂ between the support substrate 12 and the protective film 16 is in the above-described range, when peeling the protective film 16, it can be smoothly peeled, and the support substrate (12) damage, etc. does not occur.

Among them, the second adhesion force F ₂ is preferably 0.06 to 0.18 N/10 mm from the viewpoint of more suppressing the occurrence of foreign matter on the surface 14a of the polyimide resin layer 14 and the breakage of the supporting substrate 12. And 0.07 to 0.17 N/10 mm is more preferable.

In addition, in the laminated substrate 10, the adhesive force between the support base 12 and the polyimide resin layer 14 is preferably greater than any of the first adhesive force F ₁ and the second adhesive force F ₂ . As a method of improving the adhesion between the support substrate 12 and the polyimide resin layer 14, as described later, 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 substrate 12 and the polyimide resin layer 14), or the support substrate 12 and the polyimide resin layer (14) A method of providing a layer (for example, a silicone resin layer to be described later) improving the adhesion between the two is exemplified.

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, the adhesion between the support substrate 12 and the silane coupling agent layer or the silicone resin layer , And the adhesive force between the polyimide resin layer 14 and the silane coupling agent layer or the silicone resin layer is preferably greater than any of the first adhesive force F ₁ and the second adhesive force F ₂ .

[Manufacturing method of the first example of a laminated substrate]

As a method of manufacturing the laminated substrate 10 that is the first example, a method of laminating the polyimide resin layer 14 on the surface 12a of the support base 12 is preferable. Among them, before laminating the polyimide resin layer 14 on the surface 12a of the supporting substrate 12, a known silane coupling agent is applied on the surface 12a of the supporting substrate 12, and then , It is preferable to laminate the polyimide resin layer 14 on the surface 12a of the support substrate 12 coated with the silane coupling agent. In this case, a silane coupling agent layer is provided between the supporting substrate 12 and the polyimide resin layer 14. In a state where the polyimide resin layer 14 is formed on the surface 12a of the support substrate 12, the protective film 16 is disposed on the surface 12a of the support substrate 12 toward the adhesion layer 19, , The polyimide resin layer 14 is covered, and the protective film 16 is affixed to the support base material 12. Thereby, the laminated substrate 10 can be manufactured.

[Second Example of Laminated Substrate]

4 is a plan view schematically showing a second example of a laminated substrate according to an embodiment of the present invention. In addition, in the laminated substrate 10 of the second example shown in Fig. 4, the same components as those of the laminated substrate 10 of the first example shown in Figs. 1 and 2 are denoted by the same reference numerals, and detailed descriptions thereof are omitted.

The laminated substrate 10 of the second example is compared with the laminated substrate 10 shown in Figs. 1 and 2, except that the size of the protective film 16 is larger than that of the support substrate 12, Figs. 1 and 2 It is the same as the laminated substrate 10 shown in FIG.

Like the laminated substrate 10 of the second example, since the size of the protective film 16 is larger than that of the support substrate 12, it becomes easy to grip one end of the protective film 16 when peeling the protective film 16.

[Manufacturing method of the second example of the laminated substrate]

The laminated substrate 10 of the second example is a protective film 16 that is larger than the support substrate 12, and the protective film 16 is covered with the polyimide resin layer 14 and affixed to the support substrate 12. Except for one point, it can be manufactured by the same method as the laminated substrate 10 of the first example.

[Third Example of Laminated Substrate]

5 is a cross-sectional view schematically showing a third example of a laminated substrate according to an embodiment of the present invention. In addition, in the laminated substrate 10 of the third example shown in Fig. 5, the same components as those of the laminated substrate 10 of the first example shown in Figs. 1 and 2 are denoted by the same reference numerals, and detailed descriptions thereof are omitted.

In the laminated substrate 10 of the third example, compared with the laminated substrate 10 shown in FIGS. 1 and 2, a silicone resin layer 13 is provided between the supporting substrate 12 and the polyimide resin layer 14. It is the same as the laminated substrate 10 shown in Figs. 1 and 2 except that it has.

In the laminated substrate 10 of the third example, the supporting substrate 12, the silicone resin layer 13, and the polyimide resin layer 14 are laminated in this order. The silicone resin layer 13 is provided on the surface 12a of the support base material 12, and the polyimide resin layer 14 is provided on the surface 13a of the silicone resin layer 13. The silicone resin layer 13 and the polyimide resin layer 14 have the same size, but are smaller than the surface 12a of the supporting substrate 12.

In the laminated substrate 10 of the third example, the support base 12 and the silicone resin layer 13 function as a reinforcing plate for reinforcing the polyimide resin layer 14.

When heat treatment is performed on the laminated substrate 10, the adhesive force between the supporting substrate 12 and the silicone resin layer 13 is more than the adhesive force between the silicone resin layer 13 and the polyimide resin layer 14 It is desirable to increase this. This may be caused by the bonding of the hydroxy group of the supporting substrate 12 and the hydroxy group of the silicone resin layer 13 by heat treatment.

As a result, when a force is applied in the direction in which the supporting substrate 12 and the polyimide resin layer 14 are pulled, they are peeled off 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 laminated substrate 10 of the third example, there is no restriction on the size of the protective film 16. Like the laminated substrate 10 shown in FIG. 1, the protective film 16 and the supporting substrate 12 may have the same size, and support the size of the protective film 16 like the laminated substrate 10 shown in FIG. It may be larger than the base material 12.

[Method of manufacturing a third example of a 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, after applying a curable composition containing curable silicone to the back surface of the polyimide resin layer 14, curing the obtained coating film to obtain the silicone resin layer 13, the silicone resin layer 13 A method of manufacturing the laminated substrate 10 by laminating the supporting substrate 12 on the back surface (the surface opposite to the surface 13a) of

More specifically, in the method of manufacturing the laminated substrate 10 of the third example, a layer of curable silicone is formed on the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a), A step of forming a silicone resin layer 13 on the back surface of the formation layer 14 (resin layer formation step), and a supporting substrate 12 on the back surface of the silicone resin layer 13 (the surface opposite to the surface 13a). It has at least a process of laminating (lamination process) and a process (bonding process) of attaching the protective film 16. Hereinafter, each step described above will be described in detail.

(Resin layer formation process)

The resin layer forming step is a step of forming a layer of curable silicone on the back surface of the polyimide resin layer 14 to form the silicone resin layer 13 on the back surface of the polyimide resin layer 14. By this process, a board|substrate with a silicone resin layer provided with the polyimide resin layer 14 and the silicone resin layer 13 in this order is obtained.

The silicon resin layer-equipped substrate can be manufactured in a so-called roll-to-roll method in which the silicone resin layer 13 is formed on the back surface of the polyimide resin layer 14 wound in a roll shape and then wound in a roll shape. The production efficiency is excellent.

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

Specific examples of the method of applying the curable composition to the back surface of the polyimide resin layer 14 include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. The law can be mentioned.

Subsequently, the curable silicone applied 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 an optimal treatment is appropriately performed according to the type of curable silicone to be used. For example, when using a condensation reaction type silicone and an addition reaction type silicone, a thermosetting treatment is preferable as the curing treatment.

The conditions of the thermosetting treatment are carried out within the range of the heat resistance of the polyimide resin layer 14, for example, the temperature conditions for thermosetting are preferably 50 to 400°C, and more preferably 100 to 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 later.

(Lamination process)

The lamination process is a process of laminating the supporting substrate 12 on the surface of the silicone resin layer 13. As a specific example of a method of laminating the supporting substrate 12 on the back surface of the silicone resin layer 13, a method of overlapping the supporting substrate 12 on the back surface of the silicone resin layer 13 in an atmospheric pressure environment is exemplified. If necessary, after overlapping the support substrate 12 on the back surface of the silicone resin layer 13, the support substrate 12 may be press-bonded to the silicone resin layer 13 using a roll or a press. Air bubbles mixed between the silicone resin layer 13 and the supporting substrate 12 are relatively easily removed by compression bonding by a roll or press, which is preferable.

Compression bonding by a vacuum lamination method or a vacuum press method is preferable because mixing of air bubbles is suppressed and good adhesion can be realized. By pressing under vacuum, there is also an advantage that it is difficult to grow bubbles by heat treatment even when microscopic bubbles remain.

When laminating the support substrate 12, it is preferable to sufficiently clean the surface of the support substrate 12 in contact with the silicone resin layer 13 and laminate in an environment with high cleanliness.

(Joining process)

In the bonding process, the protective film 16 is disposed on the surface 12a of the support substrate 12 toward the adhesion layer 19, the polyimide resin layer 14 is covered, and the protective film 16 is attached to the support substrate 12. ). Thereby, the laminated substrate 10 is obtained.

<package>

6 is a side view schematically showing an example of a package according to the embodiment of the present invention. In the package 20 shown in Fig. 6, the same components as those of the laminated substrate 10 of the first example shown in Figs. 1 and 2 are denoted by the same reference numerals, and detailed descriptions thereof are omitted.

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

If the laminated substrate 10 is 1200 mm × 1000 mm (G5 size) or more, it is difficult to pack the laminated substrates completely apart from each other in a case, and as described later, a plurality of laminated substrates 10 are palletized with a load applied to each other. It is preferable to mount on (22) and package the laminated substrate (10).

The laminated substrate 10 is rectangular, and 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, 1300 mm or more on the long side, and more preferably The short side is 1400mm or more and the long side is 1700mm or more. The upper limit of the size of the laminated substrate 10 is preferably 3000 mm×3000 mm.

The pallet 22 has a bottom plate 24 and a back plate 26, and a back plate 26 is erected on the bottom plate 24 and is installed. The surface 24a of the bottom plate 24 and the surface 26a of the back plate 26 are orthogonal. The support base 12 of the laminated substrate 10 faces the surface 26a of the back plate 26, for example, the laminated substrate 10 on the most pallet 22 side, and the support substrate 12 at the bottom plate 24 The laminated substrate 10 is stacked on the pallet 22 in a tilted state over the surface 24a of) and the surface 26a of the back plate 26. The angle of each β formed by the back surface 12b of the support base 12 of the laminated substrate 10 and the surface 24a of the bottom plate 24 is, for example, 45° to 85°.

On the protective film 16 of the laminated substrate 10, the support substrate 12 of the other laminated substrate 10 is brought into contact and overlapped, and a plurality of laminated substrates 10 are laminated in contact with each other.

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

If a plurality of laminated substrates 10 are in a state in which loads are applied to each other, they may be placed in direct contact with each other and placed on the pallet 22, and as will be described later, a laminate is provided between the laminated substrates 10 to provide a plurality of laminated substrates. The substrate 10 may be mounted on the pallet 22.

In addition, for the purpose of separating the rear surface 12b of the supporting substrate 12 and the surface of the protective film 16 of the laminated substrate 10 adjacent to each other, a laminate may be sandwiched. When the laminated substrate 10 is taken from the pallet 22 by reducing the adhesion of the surface of the protective film 16 of the laminated substrate 10 adjacent to the back surface 12b of the support substrate 12 by putting the laminated paper E, you can easily take one by one.

In addition, although the pallet 22 is made into the structure which has the bottom plate 24 and the back plate 26, as long as a plurality of laminated substrates 10 can be stacked and stacked, the structure is not particularly limited.

The laminated substrate 10 is conveyed in the form of a package 20 in which a plurality of laminated substrates 10 are stacked on the pallet 22 in a state in which 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 most back plate 26 side, and the laminated substrates 10 rub against each other due to vibration during transport. By providing the protective film 16 as described above, even if a load is applied to the laminated substrate 10, even if the laminated substrates 10 are rubbed against each other, the polyimide resin layer 14 is damaged and scratches occur. It is suppressed that the adhesion of the thing, and further foreign matters.

In the laminated substrate 10, since the second adhesive force F ₂ between the support substrate 12 and the protective film 16 is within the above-described range, even if the package 20 is transported in a general environment, the protective film 16 ) And the supporting substrate 12 are not separated from each other, a large amount of foreign matter does not adhere to the outer peripheral portion of the polyimide resin layer 14, and the defect does not increase.

The laminated substrate 10 mounted on the pallet 22 is not limited to the laminated substrate 10 of the first example shown in FIG. 1, and the laminated substrate 10 of the second example and the laminated of the third example described above. The substrate 10 may be used.

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

The glass plate packing box is specifically composed of a pedestal for arranging and stacking the laminated substrate 10, a bottom plate on which the pedestal is mounted, a front plate, a rear plate and both side plates erected on the bottom plate, and a ceiling plate covering the top. .

The glass plate packing box is provided with an installation member for fitting the front plate and both side plates to the upper front edge and both side edges of the bottom plate. The mounting member is provided with a pair of opposed side plates on the bottom plate, and a front plate and both side plates are fitted between the opposed side plates. In addition to the above-described configuration, the mounting member may have a structure in which a groove with an upper opening is provided in the bottom plate, and the front plate and both side plates are fitted in the groove.

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

In addition, after mounting a plurality of laminated substrates on the pedestal, the front side of the housing including the plurality of laminated substrates may be covered with a protective plate made of resin or the like, and angle members may be disposed at both corners, and these may be bound with a band. . This band engages the fixed metal member provided at the end of the belt member with an adjustable length to the toggle clamp to reliably bind the storage body. In this way, by binding the storage body using a band, the whole can be reliably fixed with a simple mechanism. In addition, when the protective plate is a member having cushioning properties, after binding the laminated substrate with a band, it is possible to more firmly bind the toggle clamp.

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

<Supporting description>

The glass supporting substrate 12 is a member that supports and reinforces the polyimide resin layer 14, and also functions as a transfer substrate. The supporting base material 12 is comprised of a glass plate, for example.

As the kind of glass, alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high silica glass, and other oxide-based glasses containing silicon oxide as a main component are preferable. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

As the glass plate, more specifically, a glass plate made of alkali-free borosilicate glass (trade name "AN100" by AGC Corporation) is mentioned.

As a manufacturing method of a glass plate, the method of melting|melting a glass raw material and shaping|molding a molten glass into a plate shape is mentioned normally. Such a molding method may be general, and examples thereof include a float method, a fusion method, and a slot downdraw method.

The thickness of the supporting substrate 12 may be thicker or thinner than the polyimide resin layer 14. From the viewpoint of the handleability of the laminated substrate 10, the thickness of the support substrate 12 is preferably thicker than that of the polyimide resin layer 14.

It is preferable that the supporting base material 12 is not flexible in that it is required to function as a reinforcing plate and a transfer substrate. Therefore, the thickness of the supporting substrate 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more. 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 a polyimide resin, and a polyimide film is used, for example. As a specific example of a commercial product of a polyimide film, "Xenomax" by Toyobo Corporation, and "Upilex 25S" by Ube Kosan Corporation are mentioned.

In order to form high-precision wiring and the like constituting the electronic device, it is preferable that the surface 14a of the polyimide resin layer 14 is smooth. Specifically, the surface roughness Ra of the surface 14a 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. As a lower limit of the surface roughness Ra, 0.01 nm or more is mentioned.

The thickness of the polyimide resin layer 14 is preferably 1 µm or more, more preferably 5 µm or more, and even more preferably 10 µm or more, from the viewpoint of handling properties in the manufacturing process. From the viewpoint 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 supporting substrate 12 is preferable because the warpage after heating or cooling can be suppressed. Specifically, the difference in the coefficient of thermal expansion between the polyimide resin layer 14 and the supporting substrate 12 is preferably 0 to 90×10 ^-6 /°C, more preferably 0 to 30×10 ^-6 /°C.

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

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

<protective film>

It is preferable that the protective film 16 is a laminated structure having a base material 18 and an adhesive layer 19 as shown in FIG. 3.

The thickness of the protective film 16 is preferably 20 µm or more, more preferably 30 µm or more, and even more preferably 50 µm or more in order to reduce the influence of external force. 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.

The thickness of the protective film 16 is the total thickness of the base material 18 and the adhesion layer 19 in the case of a laminated structure including the base material 18 and the adhesion layer 19. The upper limit of the thickness of the protective film 16 is preferably 500 µm or less, since excessive force may be required when peeling the protective film if it is too thick.

The thickness of the protective film 16 is obtained by measuring the thickness of the protective film 16 at an arbitrary position of five or more points with a contact-type film thickness measuring device, and arithmetic average of them.

In addition, the base material 18 of the protective film 16 is a polyester resin (e.g., polyethylene terephthalate (PET)), a polyolefin resin (e.g., polyethylene (PE) and polypropylene), a polyurethane resin. It is preferably made of a resin such as. Among these, as the resin constituting the substrate 18 of the protective film 16, polyolefin is preferable, and polyethylene or polypropylene is more preferable.

The adhesion layer 19 is not particularly limited as long as it satisfies the first adhesion force F ₁ and the second adhesion force F ₂ described above. As the adhesive layer 19, a known adhesive layer may be used. Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include a (meth)acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive.

In addition, the adhesion layer 19 may be composed of a resin, and as specific examples of the resin, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, butyral resin, Polyurethane resin, polystyrene elastomer, etc. are mentioned.

In addition, (meth)acrylic is a concept containing acrylic and methacryl.

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

Here, FIGS. 7 to 9 are cross-sectional views schematically explaining the occurrence of buried matter in the laminated substrate according to the embodiment of the present invention. 10 is an SEM image showing an example of a buried object in the laminated substrate according to the embodiment of the present invention. In Figs. 7 to 10, the same components as those of the laminated substrate 10 shown in Figs. 1 and 2 are denoted by the same reference numerals, and detailed descriptions thereof are omitted.

As shown in FIG. 7, when there is a foreign material D between the surface 14a of the polyimide resin layer 14 and the protective film 16, if the protective film 16 is hard, as shown in FIG. Similarly, the protective film 16 is difficult to deform, and the foreign matter D is filled in the polyimide resin layer 14. As a result, a buried material is formed in the polyimide resin layer 14. Specifically, as in the SEM image shown in Fig. 10, the polyimide resin layer 14 is filled with foreign material D, and this foreign material D becomes a buried material.

On the other hand, when the protective film 16 is flexible, the protective film 16 is deformed as shown in FIG. 9, the foreign material D adheres to the protective film 16 side, and the foreign material D is applied to the polyimide resin layer 14. Does not adhere, and the foreign matter D does not fill in the polyimide resin layer 14. Thereby, even if it is laminated with the foreign material D between the surface 14a of the polyimide resin layer 14 and the protective film 16, generation|occurrence|production of the defect of the polyimide resin layer 14 is suppressed. From this, it is preferable that the base material 18 of the protective film 16 is flexible.

In addition, the softness of the base material 18 of the protective film 16 is determined by a relative relationship between the size of the foreign material D or the hardness of the foreign material D.

In addition, about the flexibility of the protective film 16 described above, Examples 4 to 6 of Examples were evaluated as described later.

<Silicone resin layer>

The silicone resin layer 13 mainly contains a silicone resin. The structure of the silicone resin is not particularly limited. The silicone resin is usually obtained by curing (crosslinking curing) a curable silicone that can become a silicone resin by curing treatment.

Specific examples of the curable silicone include condensation-reactive silicone, addition-reactive silicone, ultraviolet-curable silicone, and electron beam-curable silicone, depending on the curing mechanism. 5,000 to 60,000 are preferable and, as for the weight average molecular weight of curable silicone, 5,000 to 30,000 are more preferable.

As a manufacturing method of the silicone resin layer 13, a curable composition containing curable silicone made of the above-described silicone resin is applied to the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a), and if necessary. Accordingly, a method of removing the solvent to form a coating film and curing the curable silicone in the coating film to form the silicone resin layer 13 is preferred.

In addition to the curable silicone, the curable composition may contain a solvent, a platinum catalyst (when an addition reaction type silicone is used 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 metal, 4d transition metal, lanthanoid metal, bismuth, aluminum, and tin. The content of the metal compound is appropriately adjusted.

The thickness of the silicone resin layer 13 is preferably 100 µm or less, more preferably 50 µm or less, and even more preferably 30 µm or less. On the other hand, the thickness of the silicone resin layer 13 is preferably more than 1 µm, more preferably 4 µm or more. The above-described thickness is obtained by measuring the thickness of the silicone resin layer 13 at an arbitrary position of five or more points with a contact-type film thickness measuring device, and arithmetic average of them.

<Use of laminated substrate>

Examples of the use of the laminated substrate 10 include display devices, reception sensor panels, solar cells, thin-film secondary batteries, and integrated circuits described later. In a state in which the protective film 16 has been peeled off, the polyimide resin layer may be exposed to a high temperature condition of, for example, 450° C. or higher for 20 minutes or longer.

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

Specific examples of the reception sensor panel include an electromagnetic wave reception sensor panel, an X-ray reception sensor panel, an ultraviolet ray reception sensor panel, a visible ray reception sensor panel, and an infrared ray reception sensor panel. When used for a reception sensor panel, the polyimide resin layer may be reinforced with a reinforcing sheet such as resin.

As described above, after peeling the protective film from the laminated substrate of the present invention, an electronic device including a polyimide resin layer and a member for an electronic device is prepared using a laminate comprising the obtained supporting substrate and a polyimide resin layer. Is manufactured.

As a method for manufacturing an electronic device, for example, a member for an electronic device is formed on a polyimide resin layer in a laminate comprising the obtained support substrate and a polyimide resin layer, and from the obtained laminate provided with the member for electronic devices, a supporting substrate A method of peeling off and obtaining an electronic device having a polyimide resin layer and a member for electronic devices is mentioned.

In addition, the member for electronic devices is a member constituting at least a part of the electronic device.

<Example>

Hereinafter, the present invention will be specifically described by examples and the like, but the present invention is not limited by these examples. Examples 1 to 6 described later are examples, and examples 7 to 16 are comparative examples.

<Evaluation>

(Evaluation of foreign matter on the outer periphery)

In the evaluation of foreign matter on the outer periphery, in each example, before preparing the protective film, the position of the defect existing on the surface of the frame area of the outer periphery of the polyimide resin layer 10 mm wide using an optical inspection device manufactured by Orbotech. Information and images were acquired. Then, on the protective film of the laminated substrate obtained in each example, a load of 16 g/cm 2 was applied and left in an atmosphere at a temperature of 40°C and a relative humidity of 80% for 5 days. Then, the protective film was peeled off, and the positional information and image of the defect existing on the surface of the frame area|region 10 mm wide of the outer peripheral part of the polyimide resin layer were acquired again using the optical inspection apparatus manufactured by Orbotech.

The images before and after providing the protective film were compared, and the presence or absence of foreign matter in the frame area was evaluated. In addition to the foreign matter, since there is a possibility that defects such as residual adhesive or scratches may occur, an image representing the foreign matter was defined in advance, and the presence or absence of the foreign matter referred to the image representing the foreign matter was evaluated when comparing the images.

As a result of the comparison of the images, if there is a foreign object on the outer periphery, it is said to be "yes", and if there is no foreign object on the outer periphery, it is said to be "no".

(Evaluation of residual adhesive)

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

The images before and after providing the protective film are compared, and the presence or absence of residual adhesive is evaluated. In addition to residual pressure-sensitive adhesive, there is a possibility that scratches and the like may occur, so an image indicating residual pressure-sensitive adhesive was defined in advance, and when comparing images, the presence or absence of residual pressure-sensitive adhesive was evaluated with reference to an image indicating residual pressure-sensitive adhesive.

As a result of the comparison of the images, if there was an adhesive residue, it was said to be "yes", and if there was no adhesive residue, it was said to be "no".

(Evaluation of scratch)

In the evaluation of a flaw, in each example, before providing a protective film, positional information and an image of the flaw existing on the surface of the polyimide resin layer were obtained in advance using an optical inspection device manufactured by Orbotech.

Then, 23 sheets of 2.8 mm-thick glass plates were stacked on the protective film of the laminated substrate obtained in each example, and a load was applied, and left in an atmosphere at a temperature of 40°C and a relative humidity of 80% for 5 days. Thereafter, the protective film was peeled off, and the surface of the polyimide resin layer was again obtained by using an optical inspection device manufactured by Orbotech Co., Ltd. to obtain an image of the surface of the polyimide resin layer.

The images before and after applying the load were compared to evaluate the presence or absence of scratches. In addition to the scratches, since there is a possibility that adhesive residue or the like may occur, an image showing a scratch was defined in advance, and the presence or absence of a scratch was evaluated with reference to the image showing the scratch when comparing the images.

As a result of the comparison of the images, if there was a flaw, it was said to be "yes", and if there was no flaw, it was said to be "no".

(Evaluation of support substrate damage)

When the protective film was peeled from the laminated substrate obtained in each example, the case where the damage of the supporting substrate occurred was referred to as "yes", and the case where the damage did not occur was referred to as "nothing".

(Evaluation of heat resistance test)

Heat resistance evaluation of the laminated substrate after peeling of the protective film was performed as follows.

A 200 nm thick silicon nitride film (SiNx) was formed on the laminated substrate used for the adhesive residual evaluation by the plasma CVD method. Then, it heated at 500 degreeC for 10 minutes in nitrogen atmosphere. After heating, when the polyimide resin layer did not peel off from the supporting substrate, heat resistance was evaluated as "○", and when there was peeling, heat resistance was evaluated as "x".

(Evaluation of buried foreign matter)

Depending on the type of the protective film, evaluation of whether or not a foreign substance was embedded in the polyimide resin layer was performed as follows.

First, before preparing the protective film, in order to intentionally put a foreign material on the polyimide resin layer, after leaving the polyimide resin layer in an ambient pressure room temperature environment, inspection of defects (foreign matter) with an optical inspection device manufactured by Orbotech Implemented. Thereafter, a protective film was provided on the polyimide resin layer, 23 sheets of 2.8 mm-thick glass plates were stacked and loaded, and left in an atmosphere at a temperature of 40°C and a relative humidity of 80% for 5 days. Next, the protective film was peeled, and the surface of the polyimide resin layer was again inspected for defects (foreign substances) on the surface of the polyimide resin layer using an optical inspection device manufactured by Orbotech. By comparing the distribution of defects of the optical inspection device manufactured by Orbotech before and after bonding the protective film, after confirming whether or not the foreign material present on the polyimide resin layer before bonding remains after peeling the protective film, the remaining foreign material Regarding, the surface of the foreign material was observed using an optical microscope and a scanning electron microscope (SEM). By comparing the image with the optical microscope and the image with the scanning electron microscope, it was judged whether it was a buried foreign object.

(Evaluation on long-term storage)

When the protective film was bonded and stored in a state in which a load was applied to the bonded surface, it was checked whether or not residual pressure-sensitive adhesive or scratches occurred on the surface of the polyimide resin layer. In each example, three laminated substrates for a long-term storage test were prepared. In each example, before providing the protective film, positional information and an image of the defect existing on the surface of the polyimide resin layer were obtained in advance using an optical inspection device manufactured by Orbotech. Then, a protective film was provided on the polyimide resin layer, and a load of 16 g/cm 2 was applied on the protective film of the laminated substrate obtained in each example, in an atmosphere of a temperature of 40°C and a relative humidity of 80% for 5 days. Left unattended. Thereafter, it was taken out in an environment of room temperature and pressure, and left to stand in a state to which a load of 16 g/cm 2 was applied. The protective film is bonded at each time when the sum of the period left in an atmosphere of 40°C and 80% relative humidity and the period left after being taken out at room temperature and pressure is 2 months, 4 months, and 6 months. The load was removed from the obtained laminated substrate, the protective film was peeled off, and the positional information and images of the defects existing on the surface of the polyimide resin layer were obtained again using an optical inspection device manufactured by Orbotech. An image showing residual pressure-sensitive adhesive or flaws was defined in advance, and the presence or absence of residual pressure-sensitive adhesive or flaws was evaluated with reference to an image showing residual pressure-sensitive adhesive or flaws when comparing images.

Images before and after providing the protective film were compared to evaluate the presence or absence of residual pressure-sensitive adhesive and scratches.

Hereinafter, Examples 1 to 16 will be described.

<Example 1>

(Preparation of curable silicone)

To a 1 L flask, triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added, and the mixture was stirred at 25°C for 20 minutes, and then heated to 60°C for 12 hours. After cooling the obtained reaction crude liquid to 25 degreeC, the reaction crude liquid was washed 3 times using water (300 g).

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

Toluene was distilled off under reduced pressure from the washed reaction crude liquid, made into a slurry state, and dried overnight in a vacuum dryer to obtain curable silicone 1 as a white organopolysiloxane compound. In the curable silicone 1, the number of T units: the number of M units = 87:13 (molar ratio).

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

(Preparation of curable composition)

Curable silicone 1 and hexane were mixed as a solvent, and bismuth (III) 2-ethylhexanoate was further added as a metal compound. The amount of the solvent was adjusted so that the solid content concentration was 50% by mass. In addition, the amount of the metal compound added was adjusted so that the metal element was 0.01 parts by mass with respect to 100 parts by mass of the resin. The obtained liquid mixture was filtered using a filter having a pore diameter of 0.45 µm to obtain a curable composition.

(Production of laminated substrate)

The prepared curable composition was applied to a polyimide film having a thickness of 0.015 mm (trade name "Xenomax" manufactured by Toyobo Corporation), 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 was 10 µm.

Next, after washing with an aqueous glass cleaner ("PK-LGC213" manufactured by Parker Corporation), a 200 x 200 mm, 0.5 mm thick glass plate "AN100" (supporting substrate) washed with pure water was placed on the silicone resin layer, It bonded using a bonding apparatus, and produced the laminated body.

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.

The protective film 1 was bonded to the polyimide film side of the obtained laminate to obtain a laminated substrate. As the used protective film 1, Panak Co., Ltd. Pana Protect (registered trademark) ETK50B (trade name) having a thickness of 55 µm was used. The protective film 1 had a base material (thickness 50 µm, PET film) and an adhesive layer.

<Examples 2 to 16>

Except having changed the kind of protective film, according to the procedure similar to Example 1, the laminated board|substrates of Examples 2-16 were obtained.

In addition, in Example 2, Panak Co., Ltd. Panaprotect (registered trademark) PX50T01A15 (brand name) having a thickness of 65 µm was used as the protective film 2. The protective film 2 had a base material (50 µm in thickness, PET film) and an adhesive layer.

In Example 3, as the protective film 3, Fujimori Kogyo Co., Ltd. Mastag (registered trademark) PC-751 (brand name) having a thickness of 55 µm was used. Protective film 3 had a base material (thickness 50 µm, PET film) and an adhesive layer.

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

In Example 5, as the protective film 5, Sunei Kaken PAC-3-70 (trade name) having a thickness of 70 µm was used. The protective film 5 was a coextrusion film of an LDPE (low density polyethylene) film and an ethylene-vinyl acetate copolymer layer.

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

In Example 7, Panak Co., Ltd. Panaprotect (registered trademark) ST50 (brand name) having a thickness of 57 µm was used as the protective film 7. The protective film 7 had a base material (thickness 50 µm, PET film) and an adhesive layer.

In Example 8, as the protective film 8, Panak Co., Ltd. Panaprotect (registered trademark) GC50 (brand name) having a thickness of 80 µm was used. The protective film 8 had a base material (thickness 50 µm, PET film) and an adhesive layer.

In Example 9, as the protective film 9, Panak Co., Ltd. Pana Protect (registered trademark) GS50 (brand name) having a thickness of 63 µm was used. The protective film 9 had a base material (50 µm in thickness, PET film) and an adhesive layer.

In Example 10, as the protective film 10, Panak Co., Ltd. Panaprotect (registered trademark) GN50 (brand name) having a thickness of 60 µm was used. The protective film 10 had a base material (50 µm in thickness, PET film) and an adhesive layer.

In Example 11, as the protective film 11, Sunei Kaken JA16F (brand name) having a thickness of 60 µm was used. The protective film 11 had a base material (LDPE film) and an adhesive layer.

In Example 12, as the protective film 12, Sunei Kaken Y16F (trade name) having a thickness of 60 µm was used. The protective film 12 had a base material (LDPE film) and an adhesive layer.

In Example 13, as the protective film 13, Sunei Kaken P27 (brand name) of 74 µm in thickness was used. The protective film 13 had a base material (PE film) and an adhesive layer.

In Example 14, as the protective film 14, Sunei Kaken B35 (trade name) having a thickness of 50 µm was used. The protective film 14 had a base material (PE film) and an adhesive layer.

In Example 15, as the protective film 15, a 50 µm thick virgin pulp laminate was used. The protective film 15 did not have an adhesive layer.

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

The 1st adhesive force and the 2nd adhesive force in the laminated substrate of each example are put together in Table 1 and Table 2, and are shown. The measuring method of each adhesive force is as described above.

"Adhesive" in Tables 1 and 2 represents the kind of the adhesive in the adhesive layer in the protective film, "acrylic" means that the adhesive is an acrylic adhesive, and "silicone" means that the adhesive is a silicone-based adhesive.

<End of evaluation result>

As shown in Table 1 and Table 2 above, in Examples 1 to 6 satisfying predetermined 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 0.001 N/10 mm or more and 0.17 N/10 mm or less, even if transported in an air environment, the protective film and the polyimide resin layer No peeling occurred, and no increase in defects was observed at the end of the polyimide resin layer. Further, in Examples 1 to 6, since the second adhesion F ₂ between the supporting substrate and the protective film is 0.05N/10mm ≤ F ₂ ≤ (F ₁ (N/10mm) + 0.3N/10mm), the protective film is peeled off At the time, smooth peeling was possible, and no damage to the supporting substrate occurred.

In addition, for Examples 4 to 6, the protective film was cut out to a size of 100 mm×100 mm, and it was half-folded so that the side opposite to the adhesive surface faced. Next, a load of 16 g/cm 2 was applied to the half-folded one using a glass substrate. After allowing to stand for 30 minutes in a state where a load was applied, the glass substrate was separated. And, it was confirmed to what extent the protective film was restored. In Examples 5 and 6, the bent state (0°) was maintained, but in Example 4, the protective film was restored to some extent to be 90°. From this, in Example 4, the restoring force of the protective film is relatively strong, and since it is difficult to follow and deform the protective film, it is estimated that the foreign material is pressed against the polyimide resin layer.

In addition, for Examples 5 and 6, a long-term storage test was performed, but no residual adhesive or scratch was observed in any storage period after 2 months, 4 months, and 6 months after long-term storage.

This application is based on Japanese Patent Application No. 2019-106053 for which it applied on June 6, 2019, The content is taken in here as a reference.

10: laminated substrate
12: supporting substrate
12a: surface
12b: back side
12c: outer edge
13: silicone resin layer
13a: surface
14: polyimide resin layer
14a: surface
16: protective film
18: description
19: adhesion layer
20: package
22: pallet
24: bottom plate
24a: surface
26: backplate
26a: surface
D: foreign body
β: angle

Claims (11)

It is a laminated substrate in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a glass supporting substrate,
When the first adhesive force between the polyimide resin layer and the protective film is F ₁ , and the second adhesive force between the supporting substrate and the protective film is F ₂ ,
Wherein a 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). The method of claim 1,
The size of the protective film is greater than or equal to the size of the support substrate. The method according to claim 1 or 2,
The thickness of the protective film is 20㎛ or more, the laminated substrate. The method according to any one of claims 1 to 3,
The protective film has a substrate and an adhesive layer laminated on the substrate and in contact with the polyimide resin layer, and the substrate is made of polyethylene. The method according to any one of claims 1 to 4,
The laminated substrate, wherein the adhesive force between the support substrate and the polyimide resin layer is greater than any of the first adhesive force and the second adhesive force. The method according to any one of claims 1 to 5,
A laminated substrate in which a silane coupling agent layer is provided between the supporting substrate and the polyimide resin layer. The method according to any one of claims 1 to 5,
A laminated substrate in which a silicone resin layer is provided between the supporting substrate and the polyimide resin layer. A package comprising a pallet and the laminated substrate according to any one of claims 1 to 7, which are stacked in plural on the pallet. The method of claim 8,
A package, wherein the plurality of laminated substrates are stacked on the pallet in a state in which loads are applied to each other. The method according to claim 8 or 9,
The pallet has a bottom plate and a back plate erected on the bottom plate,
The laminated substrate is a package in which the supporting substrate is placed on the pallet in a tilted state toward the surface of the back plate. The method according to any one of claims 8 to 10,
The size of the laminated substrate is a package having a short side of 850 mm or more and a long side of 1100 mm or more.

Images