KR102526049B1 - Laminated substrate and package - Google Patents

Abstract

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 base material, and the first adhesion between the polyimide resin layer and the protective film is F ₁ . , When the second adhesion between the supporting substrate and the protective film is F ₂ , the first adhesion F ₁ is 0.001N/10mm≤F ₁ ≤0.17N/10mm, and the second adhesion F ₂ is 0.05 N/10mm≤F ₂ ≤ (F ₁ (N/10mm)+0.3N/10mm).

Description

Laminated substrate and package {LAMINATED SUBSTRATE AND PACKAGE}

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

solar cells; liquid crystal panels (LCDs); Organic EL panels (OLED); A receiving sensor panel that detects electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, and the like; When an electronic device such as this is manufactured, as described in Patent Literature 1, an aspect of using a polyimide resin layer as a substrate is disclosed. A polyimide resin layer is used in the state of a laminated board provided on a glass substrate, and the laminated board is provided for manufacture of electronic devices. After forming the electronic device, the polyimide resin layer and the glass substrate are separated.

On the other hand, when conveying a some glass substrate, it is conveyed in the form of a glass plate package formed by laminating|stacking several glass plates through the paper containing virgin pulp, for example, as described in patent document 2.

Japanese Unexamined Patent Publication No. 2015-104843 Japanese Publication No. 2016/104450

As described above, since various electronic device members constituting the electronic device are formed on the polyimide resin layer in the laminated substrate, it is preferable that the surface of the polyimide resin layer is free from scratches and foreign matter.

On the other hand, as described in Patent Literature 2, the present inventors use a package 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, and When conveyance of the laminated substrate was attempted, it was found that the surface of the polyimide resin layer in the overlapping laminated substrate was scratched.

In addition, the present inventors have tried to prevent the occurrence of the scratches by bonding a protective film to the polyimide resin layer instead of lamination, and depending on the type of protective film, when the protective film is peeled, the supporting substrate is damaged It has been found that there are cases in which foreign matter is generated on the surface of the polyimide resin layer after peeling of the protective film, and there are cases where foreign matters are generated in the outer peripheral portion of the polyimide resin layer.

Therefore, the present invention is a laminate in which scratches on the surface of the polyimide resin layer are suppressed even when laminated, breakage of the supporting substrate is suppressed when the protective film is peeled off, and foreign matter on the polyimide resin layer is suppressed. It is an object to provide a package on which a substrate and a plurality of laminated substrates are stacked.

As a result of intensive studies, the present inventors have found that the above-described objects can be achieved by the following structures.

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 support base material, and the first adhesion between the polyimide resin layer and the protective film is F ₁ , and assuming that the second adhesion between the supporting substrate and the protective film is F ₂ , the first adhesion F ₁ is 0.001 N/10 mm ≤ F ₁ ≤ 0.17 N/10 mm, and the second adhesion F ₂ is 0.05 N/10 mm. It is to provide a laminated board in which 10 mm≤F ₂ ≤ (F ₁ (N/10 mm)+0.3 N/10 mm).

The size of the protective film is preferably greater than or equal to the size of the supporting substrate.

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

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 preferably 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 substrate and the polyimide resin layer.

A 2nd aspect of this invention provides a package which has a pallet and the laminated board of the above-mentioned 1st aspect which is stacked in multiple numbers on a pallet.

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

The pallet has a bottom plate and a back plate erected on the bottom plate, and the laminated substrate is preferably stacked on the pallet in a tilted state with the supporting base material facing the surface of the back plate.

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

According to the present invention, the occurrence of scratches on the surface of the polyimide resin layer is suppressed even when laminated, the breakage of the supporting base material is suppressed when the protective film is peeled off, and the occurrence of foreign matter on the polyimide resin layer is suppressed. A package on which a substrate and 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 the laminated substrate of the embodiment of the present invention.
5 is a cross-sectional view schematically showing a third example of the laminated substrate of the embodiment of the present invention.
6 is a side view schematically showing an example of a package according to an embodiment of the present invention.
7 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate of the embodiment of the present invention.
8 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate of the embodiment of the present invention.
9 is a cross-sectional view schematically illustrating the generation of buried objects in the laminated substrate of the embodiment of the present invention.
10 is a SEM image showing an example of an embedded object in the laminated substrate of the embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described with reference to 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 made to the following embodiments without departing from the scope of the present invention.

A numerical range expressed using "to" means a range including the numerical values described before and after "to" as a lower limit and an upper limit.

As a characteristic point of the laminated board of this invention, the point which provides the protective film which covers the polyimide resin layer is mentioned. In particular, desired effects are obtained by adjusting the adhesion between the protective film, the polyimide resin layer, and the supporting base material.

The inventors of the present invention, as a cause of scratches on the surface of the polyimide resin layer when using a laminate containing virgin pulp described in Patent Document 2, the adhesion between the laminate and the polyimide resin layer is too low. is observing That is, since the adhesion 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 adhesion between the polyimide resin layer and the protective film is too strong, when the protective film is peeled off, foreign substances derived from components derived from the protective film (for example, materials for the adhesive layer) remain on the polyimide resin layer. .

In view of the above points, the adhesion between the protective film and the polyimide resin layer is adjusted.

In addition, when the adhesive force between the protective film and the supporting base material is too weak, the protective film is peeled off, and foreign matter easily adheres 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 peeling speed will occur between the polyimide resin layer portion and the supporting substrate portion, and the protective film will be attached to the supporting substrate during peeling. A force not to be applied is applied, leading to destruction of the supporting base material.

In view of the above points, the adhesion between the protective film and the supporting substrate is adjusted.

<Laminate board>

[First example of laminated board]

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 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.

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 support substrate 12 made of glass.

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

A protective film 16 is disposed covering the polyimide resin layer 14 on the support substrate 12 . As shown in FIGS. 2 and 3 , the protective film 16 has a substrate 18 and an adhesive layer 19 laminated on the substrate 18 . As shown in FIG. 2 , the adhesive 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 board|substrate. In this case, the adhesive layer 19 of the protective film 16 may peel off 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 reinforcing the polyimide resin layer 14 . In addition, the supporting substrate 12 functions as a transport substrate during transport of the laminated substrate 10 .

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

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

The protective film 16 protects the supporting base material 12 and the polyimide resin layer 14, and in particular, protects the polyimide resin layer 14 from being damaged by blows and scratches caused by external forces. . The protective film 16 is the same size as the supporting base material 12 in the laminated substrate 10 shown in FIG. 1, for example.

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

The first adhesion F ₁ is 0.001 N/10 mm ≤ F ₁ ≤ 0.17 N/10 mm. The second adhesion F ₂ is 0.05 N/10 mm ≤ _{F 2} ≤ (F ₁ (N/10 mm) + 0.3 N/10 mm).

The measurement of the above-mentioned 1st adhesive force F ₁ and 2nd adhesive force F ₂ is performed as follows. First, the protective film 16 cut into a rectangle with a width of 25 mm is bonded to the polyimide resin layer 14 or the supporting substrate 12 . Next, with a load of 16 g per 1 cm 2 applied, it is left to stand for 5 days in an environment of a temperature of 40° C. and a relative humidity of 80%. After that, a 90° peel test is conducted. The pulling speed at the time of peeling is 300 mm/min. The load at the time of peeling the protective film per unit width (10 mm) is computed from the load of the area|region which peeled stably.

As described above, the first adhesion F ₁ is 0.001 N/10 mm ≤ F ₁ ≤ 0.17 N/10 mm. When the first adhesion F ₁ is less than 0.001 N/10 mm, the polyimide resin layer 14 and the protective film 16 are not sufficiently adhered, and the gap between the polyimide resin layer 14 and the protective film 16 is rubbed. This occurs, and the surface 14a of the polyimide resin layer 14 is scratched.

When the first adhesion F ₁ exceeds 0.17 N/10 mm, the adhesion between the polyimide resin layer 14 and the protective film 16 is too strong, and the protective film ( A part of the adhesive layer 19 of 16) remains, leading to generation of foreign matter. In particular, when the adhesive layer is an adhesive layer containing an adhesive, adhesive residue derived from the adhesive occurs. In addition, when a foreign material (particularly, adhesive residue) 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 1st adhesive force F ₁ is too large, such as exceeding 1.5 N/10 mm, the support base material 12 may break.

Especially, as for the 1st adhesive force _F1 , 0.002-0.15 N/10mm is preferable, and 0.003-0.003-0.003-0.15 N/10mm is preferable at the point from which the generation|occurrence|production of the flaw on the surface 14a of the polyimide resin layer 14, and the generation|occurrence|production of a foreign material are suppressed more. 0.145 N/10 mm is more preferable.

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

If the second adhesion F ₂ is less than 0.05 N/10 mm, the adhesion between the protective film 16 and the supporting base material 12 is too weak, and the protective film 16 on the outer edge 12c of the supporting base material 12 is moved during transportation. It peels off, and a large amount of foreign matter adheres to the outer peripheral portion of the polyimide resin layer 14 . The possibility of scratches or the like occurring in the polyimide resin layer 14 due to this foreign matter increases.

When the second adhesive force F ₂ exceeds F ₁ (N/10 mm) + 0.3 N/10 mm, the adhesive force between the protective film 16 and the supporting substrate 12 is too strong, and when the protective film 16 is peeled, poly A difference in peeling speed occurs between the mid resin layer 14 portion and the supporting substrate 12 portion, and unintended force is applied to the supporting substrate 12 at the time of peeling of the protective film 16, and the supporting substrate 12 leads to the destruction of

In the laminated substrate 10, since the second adhesive force F ₂ between the supporting base material 12 and the protective film 16 is within the above-mentioned range, when peeling the protective film 16, it can peel smoothly, and the supporting base material (12) No damage or the like occurs.

Especially, as for the 2nd adhesive force _F2 , 0.06-0.18 N/10mm is preferable at the point from which the generation|occurrence|production of the foreign material on the surface 14a of the polyimide resin layer 14, and the breakage of the support base material 12 are suppressed more. and more preferably 0.07 to 0.17 N/10 mm.

In addition, in the laminated substrate 10, it is preferable that the adhesive force between the supporting substrate 12 and the polyimide resin layer 14 is greater than either of the first adhesive force F ₁ and the second adhesive force F ₂ . As a method of improving the adhesion between the supporting substrate 12 and the polyimide resin layer 14, as described later, a method of modifying the surface of the supporting substrate 12 (eg, 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 A method of providing a layer (for example, a silicone resin layer described later) between (14) to improve the adhesion between them is exemplified.

Further, when a layer such as a silane coupling agent layer and a silicone resin layer is provided between the supporting substrate 12 and the polyimide resin layer 14, the adhesion between the supporting 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 either of the first adhesive force F ₁ and the second adhesive force F ₂ .

[Method of Manufacturing Example 1 of Laminate Substrate]

As a method for manufacturing the laminated substrate 10, which is the first example, a method of laminating the polyimide resin layer 14 on the surface 12a of the supporting substrate 12 is preferable. Among them, before laminating the polyimide resin layer 14 on the surface 12a of the support substrate 12, a known silane coupling agent is applied on the surface 12a of the support substrate 12, and then It is preferable to laminate the polyimide resin layer 14 on the surface 12a of the support substrate 12 to which the silane coupling agent is applied. In this case, a silane coupling agent layer is provided between the supporting substrate 12 and the polyimide resin layer 14 . With the polyimide resin layer 14 formed on the surface 12a of the supporting substrate 12, the protective film 16 is disposed on the surface 12a of the supporting substrate 12 facing the adhesive layer 19, , The polyimide resin layer 14 is covered and the protective film 16 is affixed to the supporting substrate 12 . In this way, the laminated substrate 10 can be manufactured.

[Second example of laminated board]

4 is a plan view schematically showing a second example of the laminated substrate of the embodiment of the present invention. In addition, in the laminated substrate 10 of the second example shown in FIG. 4, the same reference numerals are given to the same components as those of the laminated board 10 of the first example shown in FIGS. 1 and 2, and detailed description thereof is omitted.

Compared with the laminated substrate 10 shown in FIGS. 1 and 2, the laminated substrate 10 of the second example is shown in FIGS. 1 and 2 except that the size of the protective film 16 is larger than that of the supporting substrate 12. It is the same as the laminated substrate 10 shown in .

As in the laminated substrate 10 of the second example, when the size of the protective film 16 is larger than that of the supporting substrate 12, it is easy to hold one end of the protective film 16 when peeling the protective film 16.

[Method of Manufacturing Second Example of Laminate Substrate]

In the laminated substrate 10 of the second example, a protective film 16 larger than the supporting substrate 12 is used, and the protective film 16 is attached to the supporting substrate 12 by covering the polyimide resin layer 14. 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 Board]

5 is a cross-sectional view schematically showing a third example of the laminated substrate of the embodiment of the present invention. In addition, in the laminated substrate 10 of the third example shown in FIG. 5, the same reference numerals are attached to the same components as those of the laminated substrate 10 of the first example shown in FIGS. 1 and 2, and detailed description thereof is omitted.

Compared to the laminated substrate 10 shown in FIGS. 1 and 2 , the laminated substrate 10 of the third example includes the silicone resin layer 13 between the supporting substrate 12 and the polyimide resin layer 14. Except for having, it is the same as the laminated board 10 shown in FIGS. 1 and 2.

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

When heat treatment is applied to the laminated substrate 10, the adhesive force between the supporting substrate 12 and the silicone resin layer 13 is higher than the adhesive force between the silicone resin layer 13 and the polyimide resin layer 14. It is desirable to increase This can be caused by, for example, bonding of the hydroxyl group of the supporting base material 12 and the hydroxyl group of the silicone resin layer 13 by heat treatment.

As a result, when a force is applied in the direction of holding the support substrate 12 and the polyimide resin layer 14 apart, the silicone resin layer 13 and the polyimide resin layer 14 are separated. In this way, the polyimide resin layer 14 can be separated.

In the laminated substrate 10 of the third example, the size of the protective film 16 is not limited. Similar to the laminated substrate 10 shown in FIG. 1, the size of the protective film 16 and the supporting substrate 12 may be the same, and the size of the protective film 16 is supported similarly to the laminated substrate 10 shown in FIG. 4. It may be larger than the substrate 12.

[Manufacturing Method of Third Example of Laminate 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 and 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 base material 12 on the back surface (surface opposite to the surface 13a) of the substrate is preferable.

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), The process of forming the silicone resin layer 13 on the back surface of the paper layer 14 (resin layer formation process) and the back surface of the silicone resin layer 13 (surface opposite to the surface 13a) It has at least a step of laminating (lamination step) and a step of attaching the protective film 16 (joining step). Hereinafter, each process described above will be described in detail.

(resin layer formation process)

The resin layer formation 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 . According to this process, the 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 substrate with a silicone resin layer can be manufactured by 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 into a roll shape again, 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 curable composition described above is applied to the back surface of the polyimide resin layer 14. Next, it is preferable to form a cured layer by subjecting the layer of curable silicone to a curing treatment.

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. law can be heard.

Next, the curable silicone applied to 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 performed appropriately depending on the type of curable silicone used. For example, when using condensation reaction type silicone and addition reaction type silicone, as a hardening process, a heat curing process is preferable.

Conditions for the thermal curing treatment are performed within the range of heat resistance of the polyimide resin layer 14, and, for example, the temperature conditions for thermal curing are preferably 50 to 400°C, and more preferably 100 to 300°C. The heating time is preferably 10 to 300 minutes, and 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 base material 12 on the back surface of the silicone resin layer 13, a method of laminating the supporting base material 12 on the back surface of the silicone resin layer 13 under a normal pressure environment is exemplified. If necessary, after overlapping the support substrate 12 on the back surface of the silicone resin layer 13, you may press the support substrate 12 to the silicone resin layer 13 using a roll or a press. It is preferable because air bubbles mixed between the silicone resin layer 13 and the supporting substrate 12 are relatively easily removed by crimping with a roll or press.

When pressure bonding is carried out by the vacuum lamination method or the vacuum press method, incorporation of air bubbles can be suppressed and good adhesion can be realized, which is preferable. By compressing under vacuum, even when minute air bubbles remain, there is also an advantage that air bubbles are difficult to grow by heat treatment.

When laminating the supporting base material 12, it is preferable to sufficiently wash the surface of the supporting base material 12 in contact with the silicone resin layer 13 and to laminate it in a high-clean environment.

(joining process)

In the bonding step, the protective film 16 is placed on the surface 12a of the supporting base material 12 facing the adhesive layer 19, and the polyimide resin layer 14 is covered, and the protective film 16 is placed on the supporting base material 12. ) attached to In this way, the laminated substrate 10 is obtained.

<Package>

6 is a side view schematically showing an example of a package according to an embodiment of the present invention. In the package 20 shown in FIG. 6 , the same reference numerals are given to the same components as those of the laminated substrate 10 of the first example shown in FIGS. 1 and 2 , 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 substrates 10 are 1200 mm × 1000 mm (G5 size) or larger, it is difficult to pack the laminated boards in a case in a state completely separated from each other, and as will be described later, a plurality of laminated boards 10 are placed on a pallet in a state in which loads are applied to each other. It is preferable to pack the laminated substrate 10 by loading it on (22).

The laminated substrate 10 is rectangular, and the size of the laminated substrate 10 is preferably 850 mm or more on a short side and 1100 mm or more on a long side, more preferably 1200 mm or more on a short side and 1300 mm or more on a long side, still more preferably The short side is 1400 mm or more, and the long side is 1700 mm or more. As an upper limit of the size of the laminated substrate 10, it is preferable that it is 3000 mm x 3000 mm.

The pallet 22 has a bottom plate 24 and a back plate 26, and the back plate 26 is erected on the bottom plate 24 and installed. The surface 24a of the bottom plate 24 and the surface 26a of the back plate 26 are orthogonal. The supporting base material 12 of the laminated substrate 10 is directed toward the surface 26a of the back plate 26, for example, the laminated substrate 10 on the most pallet 22 side is moved, and the supporting base material 12 is placed on the bottom plate 24. ) and the surface 26a of the back plate 26, the multilayer substrate 10 is stacked on the pallet 22 in an inclined state. The angle of angle β formed between 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°.

On the protective film 16 of the laminated substrate 10, the support substrate 12 of the other laminated substrate 10 is contacted and overlapped, and a plurality of laminated substrates 10 are contacted and laminated.

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

The plurality of laminated substrates 10 may be placed on the pallet 22 in direct contact with each other, as long as loads are applied to each other, or, as will be described later, a laminate is provided between the laminated substrates 10 to form a plurality of laminated substrates. You may load the board|substrate 10 on the pallet 22.

Moreover, for the purpose of isolating the back surface 12b of the supporting base material 12 and the surface of the protective film 16 of the adjacent laminated substrate 10, you may put a paper between them. When the laminated substrate 10 is taken from the pallet 22 by reducing 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 by putting the laminated paper Yes, it can be easily taken one by one.

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

The laminated substrate 10 is conveyed in the form of a package 20 in which a plurality of laminated substrates 10 are stacked on a 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 back plate 26 side, and the laminated substrates 10 rub against each other due to vibration during transportation. 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 rub against each other, the polyimide resin layer 14 is scratched and scratched. and furthermore, adhesion of foreign matter is suppressed.

In the laminated substrate 10, since the second adhesion F ₂ between the supporting substrate 12 and the protective film 16 is within the above-mentioned range, even if the package 20 is transported in a general environment, the protective film 16 ) and the supporting base material 12 do not occur, a large amount of foreign matter does not adhere to the outer peripheral portion of the polyimide resin layer 14, and defects do not increase.

The laminated substrates 10 stacked on the pallet 22 are not limited to the laminated substrate 10 of the first example shown in FIG. 1, and the laminated substrates 10 of the second example described above and the laminated substrates of the third example described above. It may be the substrate 10 .

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

The glass packing box is specifically composed of a pedestal on which laminated substrates 10 are arranged and stacked, a bottom plate on which the pedestal is loaded, a front plate, a back plate, and both side plates standing upright on the bottom plate, and a top plate covering the upper part. .

A glass plate packing box is equipped with the attachment member for engaging a front plate and both side plates in the upper front edge and both edge of a bottom plate. In the mounting member, a pair of opposing side plates is provided on the bottom plate, and the front plate and both side plates are sandwiched between the opposing side plates. In addition to the structure described above, the attachment 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 into the groove.

Further, cushioning materials may be attached to each of the bottom receiving plate and the backing plate in order to prevent damage when the laminated board is loaded.

Alternatively, after mounting a plurality of laminated boards on the pedestal, the front side of the storage body including the plurality of laminated boards may be covered with a protective plate made of resin or the like, and angle materials may be placed on both corner portions to bind them with a band. . This band reliably binds the storage body by engaging a fixed metal member provided at an end of a length-adjustable belt member with a toggle clamp or the like. In this way, by binding the storage body using a band, the whole can be reliably fixed with a simple mechanism. In addition, if the guard plate is a member having cushioning properties, the toggle clamp can be more firmly bound after binding the laminated substrate with a band.

Hereinafter, the support 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.

<Support Substrate>

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

As the type 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 oxide type glass, the glass whose content of silicon oxide by oxide conversion is 40-90 mass % is preferable.

More specifically, as a glass plate, the glass plate (brand name "AN100" by AGC Co., Ltd.) containing an alkali-free borosilicate glass is mentioned.

As a manufacturing method of a glass plate, the method of melting glass raw materials and shape|molding molten glass in plate shape is mentioned normally. Such a molding method may be a general one, and examples thereof include a float method, a fusion method, and a slot down-draw method.

The thickness of the supporting substrate 12 may be thicker or thinner than the polyimide resin layer 14 . From the point of the handleability of the laminated substrate 10, it is preferable that the thickness of the support base material 12 is thicker than the polyimide resin layer 14.

Since the supporting substrate 12 is required to function as a reinforcing plate and a transport substrate, it is preferable that it is not flexible. 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, as for the thickness of the support base material 12, 1.0 mm or less is preferable.

<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 the commercial item of a polyimide film, Toyobo Co., Ltd. product "Genomax" and Ube Industries Co., Ltd. product "Upilex 25S" are mentioned.

It is preferable that the surface 14a of the polyimide resin layer 14 is smooth in order to form high-precision wiring and the like constituting the electronic device. 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, still more preferably 10 nm or less. As a lower limit of 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 still 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, and 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 base material 12 is, the smaller the difference is, since warping after heating or cooling can be suppressed. Specifically, the difference in coefficient of thermal expansion between the polyimide resin layer 14 and the supporting substrate 12 is preferably 0 to 90 × 10 ^-6 /°C, and more preferably 0 to 30 × 10 ^-6 /°C.

The area of the polyimide resin layer 14 (the area of the surface 14a) is not particularly limited, but is preferably smaller than the area of the supporting substrate 12 in order to arrange the protective film 16. 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 be formed with an orientation flat (a flat portion formed on the outer periphery of the substrate) 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 including a substrate 18 and an adhesive layer 19 .

The thickness of the protective film 16 is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more in order to reduce the influence of external force. As an upper limit of the thickness of the protective film 16, it is preferable that it is 500 micrometers or less, More preferably, it is 300 micrometers or less, More preferably, it is 100 micrometers or less.

The thickness of the protective film 16 is the total thickness of the substrate 18 and the adhesive layer 19 in the case of a laminated structure including the substrate 18 and the adhesive layer 19 . As an upper limit of the thickness of the protective film 16, since excessive force may be needed when peeling off a protective film when it is too thick, 500 micrometers or less is preferable.

The thickness of the protective film 16 is obtained by measuring the thickness of the protective film 16 at five or more arbitrary positions 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 (eg, polyethylene terephthalate (PET)), a polyolefin resin (eg, polyethylene (PE) and polypropylene), a polyurethane resin. It is preferable to be comprised from resin, such as. Among these, as resin which comprises the base material 18 of the protective film 16, polyolefin is preferable, and polyethylene or polypropylene is more preferable.

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 described above. As the adhesive layer 19, you may use a well-known adhesive layer. Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include (meth)acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives.

Further, the adhesive layer 19 may be composed of resin, and specific examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, butyral resin, A polyurethane resin, a polystyrene elastomer, etc. are mentioned.

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

In addition, depending on the type of the protective film 16, the ease of occurrence of buried matter on the surface 14a of the polyimide resin layer 14 changes. The mechanism will be described in detail below.

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

As shown in FIG. 7 , when foreign matter D exists 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. 8 Likewise, the protective film 16 is difficult to deform, and foreign matter D is buried in the polyimide resin layer 14. As a result, buried substances are formed in the polyimide resin layer 14 . Specifically, as shown 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 buried material.

On the other hand, if the protective film 16 is flexible, as shown in FIG. 9 , the protective film 16 is deformed, foreign matter D adheres to the protective film 16 side, and foreign matter D adheres to the polyimide resin layer 14. is not adhered, and the foreign material D is not filled in the polyimide resin layer 14. Thereby, even if it laminates|stacked with the foreign material D interposed 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 if the base material 18 of the protective film 16 is flexible.

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

In addition, regarding the softness of the protective film 16 described above, Examples 4 to 6 of Examples were evaluated as will be 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. A silicone resin is usually obtained by curing (crosslinking curing) a curable silicone that can be made into a silicone resin by a curing treatment.

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

As a method for producing 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), if necessary. A preferred method is to remove the solvent, form a coating film, and cure the curable silicone in the coating film to form the silicone resin layer 13.

The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, and a metal compound. Specific examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanoid metals, 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 still more preferably 30 μm or less. On the other hand, as for the thickness of the silicone resin layer 13, more than 1 micrometer is preferable and 4 micrometers or more are more preferable. The thickness described above is obtained by measuring the thickness of the silicone resin layer 13 at five or more arbitrary positions with a contact-type film thickness measuring device and arithmetic average of them.

<Use of Laminated Board>

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

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) shutter panels.

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

As described above, after peeling the protective film from the laminated substrate of the present invention, an electronic device comprising a polyimide resin layer and a member for electronic devices is obtained using a laminate comprising the obtained support base material and the polyimide resin layer. are manufactured

As a manufacturing method of an electronic device, for example, a member for electronic devices is formed on the polyimide resin layer in a laminate containing the obtained support base material and the polyimide resin layer, and from the obtained laminate with a member for electronic device, the support base material The method of peeling and obtaining the electronic device which has a polyimide resin layer and the member for electronic devices is mentioned.

Moreover, the said member for electronic devices is a member which comprises at least one part of an electronic device.

<Example>

The present invention will be specifically described below 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 the outer periphery foreign matter, in each case, the location of the defect existing on the surface of the outer periphery 10 mm wide frame region of the polyimide resin layer in advance using an optical inspection device manufactured by Orbotech before providing the protective film. Information and images were acquired. And it was left to stand in the atmosphere of the temperature of 40 degreeC, and the relative humidity of 80% for 5 days in the state which applied the load of 16 g/cm<2> on the protective film of the laminated board obtained in each case. Thereafter, the protective film was peeled off, and positional information and images of defects existing on the surface of a 10 mm wide frame region of the outer periphery of the polyimide resin layer were acquired again using an optical inspection device manufactured by Orbotech.

The presence or absence of foreign matter in the frame region was evaluated by comparing images before and after the provision of the protective film. Since there is a possibility that defects such as adhesive residue or flaws may occur in addition to foreign substances, images representing foreign substances were defined in advance, and the presence or absence of foreign substances was evaluated by referring to images showing foreign substances when comparing images.

As a result of the comparison of the images, if there was a foreign matter in the outer periphery, it was evaluated as "yes", and if there was no foreign matter in the outer periphery, it was evaluated as "no".

(Evaluation of adhesive residue)

In evaluation of adhesive residue, in each case, before providing the protective film, the positional information and image of the defect existing on the surface of the polyimide resin layer were previously acquired using the optical inspection apparatus manufactured by Orbotech. And it was left to stand in the atmosphere of the temperature of 40 degreeC, and the relative humidity of 80% for 5 days in the state which applied the load of 16 g/cm<2> on the protective film of the laminated board obtained in each case. After that, the protective film was peeled off, and positional information and images of defects existing on the surface of the polyimide resin layer were acquired using an optical inspection device manufactured by Orbotech Co., Ltd. again.

The image before and after providing the protective film is compared, and the presence or absence of adhesive residue is evaluated. Since there is a possibility that scratches may occur in addition to the adhesive residue, an image indicating the adhesive residue was defined in advance, and the presence or absence of the adhesive residue was evaluated by referring to the image showing the adhesive residue when comparing the images.

As a result of comparison of the images, it was evaluated as "yes" if there was adhesive residue, and "no" if there was no adhesive residue.

(Evaluation of scratches)

In evaluation of a flaw, in each case, before providing the protective film, the positional information and image of the defect existing on the surface of the polyimide resin layer were previously acquired using the optical inspection apparatus by Orbotech.

And on the protective film of the laminated board obtained in each case, it was left to stand in the atmosphere of the temperature of 40 degreeC, and the relative humidity of 80% for 5 days in the state which piled up 23 glass plates of thickness 2.8mm, and applied the load. After that, the protective film was peeled off, and an image of the surface of the polyimide resin layer was acquired using an optical inspection device manufactured by Orbotech Co., Ltd. again.

Images before and after application of the load were compared to evaluate the presence or absence of scratches. Since there is a possibility that adhesive residue may occur in addition to scratches, an image showing the scratches was defined in advance, and the presence or absence of the scratches was evaluated by referring to the images showing the scratches when comparing the images.

As a result of the comparison of the images, it was evaluated as "yes" if there were any flaws, and "no" if there were no flaws.

(Evaluation of damage to support base material)

When the protective film was peeled off from the laminated substrate obtained in each case, the case where damage to the supporting base material occurred was defined as "Yes", and the case where damage did not occur was defined as "None".

(Evaluation of heat resistance test)

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

A silicon nitride film (SiNx) having a thickness of 200 nm was formed on the laminated substrate used for the pressure-sensitive adhesive residual evaluation using the plasma CVD method. Thereafter, heating was performed at 500°C for 10 minutes in a nitrogen atmosphere. After heating, when the polyimide resin layer did not peel 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 protective film, evaluation of whether or not foreign matter was buried in the polyimide resin layer was performed as follows.

First, in order to intentionally place foreign substances on the polyimide resin layer before preparing the protective film, the polyimide resin layer is left in a room temperature environment under normal pressure, and then defects (foreign substances) are inspected with an optical inspection device manufactured by Orbotech. conducted. Thereafter, a protective film was provided on the polyimide resin layer, and 23 glass plates having a thickness of 2.8 mm were stacked on top of each other, and a load was applied, and the layer was left to stand in an atmosphere at 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 further inspected for defects (foreign matter) on the surface of the polyimide resin layer using an optical inspection device manufactured by Orbotech. By comparing the defect distribution of the optical inspection device manufactured by Orbotech Co., Ltd. before and after bonding the protective film, it is confirmed whether or not the foreign material existing on the polyimide resin layer before bonding remains after peeling the protective film, and then the remaining foreign material Regarding , the surface of the foreign material was observed using an optical microscope and a scanning electron microscope (SEM). It was judged whether it was an embedded foreign material by comparing the image by an optical microscope and the image by a scanning electron microscope.

(Evaluation of 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 confirmed whether adhesive residue or scratches occurred on the surface of the polyimide resin layer. In each case, three laminated substrates for long-term storage tests were prepared. In each case, before providing the protective film, positional information and an image of a defect existing on the surface of the polyimide resin layer were previously acquired 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 to the protective film of the laminated substrate obtained in each case, and the temperature was 40° C. and the relative humidity was 80% for 5 days. left unattended After that, it was taken out in an environment of normal temperature and normal pressure, and was left in a state where a load of 16 g/cm 2 was applied. The protective film is bonded at each period when the sum of the period left in an atmosphere with a temperature of 40 ° C. and a relative humidity of 80% and the period left after being taken out at room temperature and normal pressure is 2 months, 4 months, and 6 months. The load was removed from one sheet of the laminated substrate, the protective film was peeled off, and positional information and images of defects existing on the surface of the polyimide resin layer were acquired again using an optical inspection device manufactured by Orbotech. An image showing adhesive residue or flaws was defined in advance, and when comparing the images, the presence or absence of adhesive residue or flaws was evaluated with reference to images showing adhesive residue or flaws.

The images before and after the protective film was prepared were compared to evaluate the presence or absence of adhesive residue and flaws.

Examples 1 to 16 will be described below.

<Example 1>

(Preparation of curable silicone)

Triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25°C for 20 minutes, then heated to 60°C and reacted for 12 hours. After the obtained reaction crude liquid was cooled to 25°C, the reaction crude liquid was washed 3 times with 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, then heated to 50°C and reacted for 12 hours. After the obtained reaction crude liquid was cooled to 25°C, the reaction crude liquid was washed 3 times with water (300 g).

After toluene was distilled off under reduced pressure from the washed reaction crude liquid to form a slurry, curable silicone 1 as a white organopolysiloxane compound was obtained by drying overnight in a vacuum dryer. Curable silicone 1 was the number of T units: the number of M units = 87:13 (molar ratio).

In addition, M unit means the 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 was mixed with hexane as a solvent, and bismuth (III) 2-ethylhexanoate was added as a metal compound. The amount of solvent was adjusted so that the solid content concentration would be 50% by mass. The addition amount of the metal compound was adjusted so that the metal element was 0.01 part by mass with respect to 100 parts by mass of the resin. A curable composition was obtained by filtering the obtained liquid mixture using a filter having a hole diameter of 0.45 µm.

(Manufacture of laminated board)

The prepared curable composition was applied to a 0.015 mm thick polyimide film (trade name "Genomax" manufactured by Toyobo Co., Ltd.) 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, a 200 × 200 mm, 0.5 mm thick glass plate “AN100” (support substrate) washed with pure water after washing with an aqueous glass cleaner (“PK-LGC213” manufactured by Parker Corporation) was placed on the silicone resin layer, It bonded using the 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. Panaprotect (registered trademark) ETK50B (trade name) having a thickness of 55 μm was used. Protective film 1 had a substrate (thickness of 50 μm, PET film) and an adhesive layer.

<Examples 2 to 16>

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

In Example 2, as the protective film 2, Panac Co., Ltd. Panaprotect (registered trademark) PX50T01A15 (trade name) having a thickness of 65 μm was used. Protective film 2 had a base material (thickness: 50 µm, PET film) and an adhesive layer.

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

In Example 4, as 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. Protective film 5 was a co-extruded film of an LDPE (low density polyethylene) film and an ethylene-vinyl acetate copolymer layer.

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

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

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

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

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

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

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

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

In Example 15, as the protective film 15, a virgin pulp laminate having a thickness of 50 μm 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 board of each case are put together in Table 1 and Table 2, and are shown. The method of measuring each adhesion is as described above.

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

<End of evaluation results>

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

In Examples 1 to 6, since the first adhesion 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 the protective film and the polyimide resin layer are transported in an atmospheric environment, peeling did not occur, and defects were not found to increase at the ends of the polyimide resin layer. Furthermore, in Examples 1 to 6, the second adhesive force F ₂ between the supporting substrate and the protective film is 0.05 N/10 mm≤F ₂ ≤ (F ₁ (N/10 mm)+0.3 N/10 mm), so the protective film peeling At the time of application, smooth peeling was possible, and no damage to the supporting substrate occurred.

Further, for Examples 4 to 6, the protective film was cut out to a size of 100 mm x 100 mm, and folded in half so that the side opposite to the adhesive side faced each other. Next, a load of 16 g/cm 2 was applied to the half-folded glass substrate using a glass substrate. After leaving it to stand for 30 minutes with a load applied, the glass substrate was separated. Then, it was confirmed how much 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 and became 90°. From this, in Example 4, since the restoring force of the protective film is relatively strong and it is difficult to deform following the foreign material, it is estimated that the foreign material was pressed against the polyimide resin layer.

Further, a long-term storage test was conducted for Examples 5 and 6, but no adhesive residue or scratches were observed for any storage period after 2 months, 4 months, or 6 months of long-term storage.

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 board
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: registration
19: adhesion layer
20: pack
22: Palette
24: bottom plate
24a: surface
26: back plate
26a: surface
D: foreign body
β: angle

Claims (11)

A laminated board 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 adhesion between the polyimide resin layer and the protective film is F ₁ and the second adhesion between the supporting substrate and the protective film is F ₂ ,
The first adhesion F ₁ is 0.001N/10mm≤F _1≤0.17N /10mm,
The second adhesion F ₂ is, 0.05N/10mm≤F ₂ ≤(F ₁ (N/10mm)+0.3N/10mm), the laminated substrate. According to claim 1,
The thickness of the protective film is 20㎛ or more, the laminated substrate. According to claim 1 or 2,
The laminated substrate according to claim 1 , 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. According to claim 1 or 2,
The laminated substrate according to claim 1 , wherein an adhesive force between the supporting substrate and the polyimide resin layer is greater than any of the first adhesive force and the second adhesive force. According to claim 1 or 2,
A laminated substrate, wherein a silane coupling agent layer is provided between the support substrate and the polyimide resin layer. According to claim 1 or 2,
A laminated substrate, wherein a silicone resin layer is provided between the support substrate and the polyimide resin layer. A package comprising a pallet and the laminated substrate according to claim 1 or 2 stacked in plurality on the pallet. According to claim 7,
A package wherein a plurality of the laminated substrates are loaded on the pallet in a state in which loads are applied to each other. According to claim 7,
The pallet has a bottom plate and a back plate erected on the bottom plate,
The package according to claim 1, wherein the laminated substrate is stacked on the pallet with the support substrate tilted toward the surface of the back plate. According to claim 7,
The size of the laminated substrate is 850 mm or more on a short side and 1100 mm or more on a long side. delete

Images