TW201609377A - Manufacturing method of electronic device, manufacturing method of glass lamination body - Google Patents

Abstract

The present invention relates to a manufacturing method of electronic device, which comprises: step (1) to form the polyimide resin layer on the temporarily supporting layer, wherein the side surface of polyimide resin layer opposite to the temporarily supporting layer is processed by Silane coupling agent; step (2) to allocate a glass substrate with thickness below 0.2mm on the aforementioned polyimide resin layer, so as to obtain the glass lamination body; step (3) to allocate the member for electronic devices on the surface of aforementioned glass substrate, so as to obtain the glass lamination body with the member attached thereto; and step (4) to remove the aforementioned temporarily supporting body from the aforementioned glass lamination body with the member attached thereto, thereby obtaining the electronic device comprising the aforementioned polyimide resin layer, the glass substrate, and the member for the aforementioned electronic device.

Description

Method for manufacturing electronic device, method for manufacturing glass laminate

The present invention relates to a method of manufacturing an electronic device and a method of manufacturing a glass laminate.

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL panels (OLEDs) have been thinned and lightened, and the thinning of glass substrates used in such devices has progressed. If the strength of the glass substrate is insufficient due to the thinning, the glass substrate is rationally lowered in the manufacturing process of the device.

Therefore, a technique of arranging a resin layer or the like on a glass substrate to reinforce the glass substrate has been disclosed (for example, Patent Document 1). However, recently, the size of the thinned glass substrate has been further expanded, and it has been difficult to form a resin layer excellent in properties on such a glass substrate. For example, when a composition for forming a resin layer is applied to a glass substrate, the glass substrate is bent, and it is difficult to form a coating film having a uniform thickness.

On the other hand, as one of the methods of forming a resin layer on a glass substrate, a transfer method has been proposed (Patent Document 2). More specifically, in the column of the example of Patent Document 2, it is disclosed that the uncured curable resin composition layer and the glass substrate are sequentially formed on the surface of the releasable auxiliary substrate which exhibits easy peelability. The pre-hardened laminate, and thereafter, the uncured curable resin composition layer in the laminate before curing is cured to obtain a cured laminate having a resin layer, and further, a glass substrate is obtained from the cured laminate A glass substrate with a resin layer attached to the resin layer in contact with the surface.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Special Table 2002-542971

[Patent Document 2] International Publication No. 2013/054792

In recent years, the polyimide film has attracted attention in terms of excellent heat resistance.

In the transfer method described in Patent Document 2, the inventors of the present invention used a composition containing a polyamido acid corresponding to a precursor of a polyimide resin as a curable resin composition, and attempted to manufacture the above-mentioned resin. A layer of glass substrate. More specifically, a composition containing polyamic acid is applied onto the releasable auxiliary substrate to form an uncured curable resin composition layer, a glass substrate is laminated thereon, and heat treatment is performed, and as a result, obtained Foaming occurs at the interface between the resin layer (polyimine resin layer) and the glass substrate. It is presumed that the foaming system is caused by the volatilization of water generated during the so-called hydrazine imidization. Therefore, the surface of the glass substrate where the foaming occurs is embossed, and the flatness of the surface of the glass substrate is impaired. When the flatness of the surface of the glass substrate is deteriorated, the positional displacement is likely to occur when the various electronic device members are placed on the surface of the glass substrate, and as a result, the productivity of the electronic device is inferior.

Moreover, when foaming occurs at the interface between the resin layer (polyimine resin layer) and the glass substrate, the adhesion between the resin layer and the glass substrate is also impaired.

The present invention has been made in view of the above problems, and an object thereof is to provide a method of manufacturing an electronic device which can easily manufacture a member including an electronic device, a glass substrate, and a polyimide layer for reinforcing the glass substrate. In the electronic device, foaming between the glass substrate and the polyimide resin layer is suppressed in the obtained electronic device, and the adhesion between the two is excellent.

Further, another object of the present invention is to provide a method for producing a glass laminate which can be preferably used in the manufacture of the above electronic device and which includes a temporary support, a polyimide resin layer, and a glass substrate.

The inventors of the present invention have diligently studied in order to solve the above problems, and as a result, have completed the present invention.

That is, a first aspect of the present invention provides a method for producing an electronic device comprising the step (1) of forming a polysiloxane-based treatment agent on a surface of a temporary support opposite to the temporary support side. a bismuth imine resin layer; the step (2), wherein a glass substrate having a thickness of 0.2 mm or less is disposed on the polyimide film layer to obtain a glass laminate; and the step (3) is disposed on the surface of the glass substrate a member for an electronic device to obtain a glass laminate with a member; and a step (4) for removing the temporary support from the glass laminate with the member, thereby obtaining a layer comprising a polyimide film, a glass substrate, and an electron Electronic device for components of the device.

In a first aspect, preferably, the step (1) comprises: a step (A) of applying a composition comprising polyamic acid to a temporary support to form a coating film comprising polyamic acid; a step (B) of applying a decane coupling agent to the surface of the coating film; and a step (C) of subjecting the coating film to heat treatment to obtain a surface opposite to the side of the temporary support by a decane coupling agent. Polyimine resin layer.

In the first aspect, preferably, the step (1) comprises: a step (D) of forming a polyimine resin layer on the temporary support; and a step (E) of the polyimine resin A decane coupling agent was applied to the surface of the layer to obtain a polyimide resin layer treated with a decane coupling agent on the surface opposite to the side of the temporary support.

In the first aspect, the step (2) is preferably the following step (2′), wherein the step (2′) is to form a glass substrate having a size smaller than that of the polyimine resin layer. The polyimine resin layer is laminated on the polyimide film layer so as not to be in contact with the glass substrate, and further comprises the following step (5) between the steps (2) and (3), In the step (5), the polyimide layer and the temporary support in the glass laminate are cut along the outer periphery of the glass substrate.

According to a second aspect of the present invention, there is provided a method for producing a glass laminate comprising a temporary support and a polyimide layer treated with a decane coupling agent on a surface opposite to the side of the temporary support. And a glass substrate for arranging a member for an electronic device on a surface of the glass substrate, and thereafter removing the temporary support to obtain an electronic device including a polyimide layer, a glass substrate, and a member for an electronic device, and The method for producing a glass laminate includes the step (1) of forming a polyimine resin layer treated with a decane coupling agent on a surface of the temporary support opposite to the side of the temporary support; and the step (2) A glass substrate having a thickness of 0.2 mm or less is disposed on the polyimide film layer to obtain a glass laminate.

In a second aspect, preferably, the step (1) comprises: a step (A) of applying a composition comprising polyamic acid to a temporary support to form a coating film comprising polyamic acid; a step (B) of applying a decane coupling agent to the surface of the coating film; and a step (C) of subjecting the coating film to heat treatment to obtain a surface opposite to the side of the temporary support by a decane coupling agent. Polyimine resin layer.

In the second aspect, preferably, the step (1) comprises: a step (D) of forming a polyimine resin layer on the temporary support; and a step (E) of the polyimine resin A decane coupling agent was applied to the surface of the layer to obtain a polyimide resin layer treated with a decane coupling agent on the surface opposite to the side of the temporary support.

In the second aspect, the step (2) is preferably the following step (2′), wherein the step (2′) is to form a glass substrate having a size smaller than that of the polyimine resin layer. The polyimine resin layer is laminated on the polyimide film layer so as not to remain in contact with the glass substrate, and further includes the following step (5) after the step (2), the step (5) The polyimide layer and the temporary support in the glass laminate are cut along the outer periphery of the glass substrate.

According to the present invention, a method of manufacturing an electronic device can be provided, which can be easily manufactured And an electronic device comprising a member for an electronic device, a glass substrate, and a polyimide layer for reinforcing the glass substrate, and the generated between the glass substrate and the polyimide resin layer in the obtained electronic device The bubbles are suppressed, and the adhesion between the two is excellent.

Moreover, according to the present invention, it is also possible to provide a method for producing a glass laminate which can be preferably used for the manufacture of the above electronic device and which includes a temporary support, a polyimide resin layer, and a glass substrate.

10‧‧‧ temporary support

12‧‧‧ Polyimine resin layer

12a‧‧‧ surface

12b‧‧‧ Peripheral area

14‧‧‧ glass substrate

14a‧‧‧1st main face

14b‧‧‧2nd main face

16‧‧‧Members for electronic devices

100‧‧‧glass laminate

110‧‧‧Glass laminate with components

120‧‧‧Electronic devices

200‧‧‧glass laminate

300‧‧‧After cutting the laminated body

Fig. 1 is a flow chart showing the manufacturing procedure of the first embodiment of the method of manufacturing an electronic device of the present invention.

2(A) to 2(D) are schematic cross-sectional views showing a first embodiment of a method of manufacturing an electronic device according to the present invention in order of steps.

Fig. 3 is a flow chart showing the manufacturing procedure of the second embodiment of the method of manufacturing the electronic device of the present invention.

4(A) to 4(E) are schematic cross-sectional views showing a second embodiment of a method of manufacturing an electronic device according to the present invention in order of steps.

Fig. 5(A) is a plan view of the glass laminate obtained in the step (2'). Fig. 5 (B) is an enlarged cross-sectional view showing the vicinity of the peripheral portion of the polyimide film layer. Fig. 5(C) is an enlarged cross-sectional view showing a state in which a glass substrate is laminated on the polyimide film of Fig. 5(B).

In the following, the embodiments of the present invention are described with reference to the drawings, but the present invention is not limited to the embodiments described below, and various changes and substitutions may be made in the following embodiments without departing from the scope of the invention.

One of the features of the electronic device and the method for producing a glass laminate according to the present invention is that a polyimine resin layer having a surface treated with a decane coupling agent is disposed on a temporary support and transferred to a glass substrate. on.

As described above, a certain layer is provided on the surface of the thinned glass substrate. When a surface is provided with various materials, it is difficult to form a uniform coating film. Even if a coating film is formed, if a glass substrate is to be conveyed in order to carry out subsequent processing (for example, drying treatment), the glass substrate is also bent, and the thickness of the coating film is formed. The unevenness is generated, and the layer (for example, the resin layer) provided on the surface of the glass substrate is broken. Further, when various materials are directly applied to the surface of the glass substrate, the surface of the glass substrate opposite to the side on which the material is applied is usually in contact with the member for supporting the glass substrate. When the above-mentioned members are in contact with each other, the surface properties such as damage to the surface of the glass substrate are deteriorated, which may cause adverse effects in the subsequent manufacture of the member for an electronic device. Moreover, in many cases, it is fixed to the vacuum adsorption stage when it is applied on a glass substrate. However, if the thickness of the glass substrate is thin, it is easy to cause liquid migration and uneven drying of the coating film due to the temperature difference between the adsorption hole and the contact portion. .

On the other hand, in the present invention, since the polyimide film is temporarily provided on the temporary support and transferred to the glass substrate, the number of times of operation on the glass substrate is reduced, and damage to the surface of the glass substrate can be reduced. Further, since the polyimide layer is formed on the temporary support, it is easier to control the thickness of the polyimide layer. Further, since the surface of the polyimide resin layer is treated with a decane coupling agent, it is excellent in adhesion to a glass substrate. Therefore, the member for an electronic device can be formed on the glass substrate in the glass laminate as follows, and thereafter, the temporary support is easily removed by using the interface between the temporary support and the polyimide resin layer as a release surface.

Thus, according to the present invention, a specific electronic device can be easily manufactured. Moreover, the glass laminate of the present invention can be preferably used for easily manufacturing an electronic device including a polyimide film layer and a glass substrate which function as a reinforcing layer of a thin glass substrate.

[First Embodiment]

Fig. 1 is a flow chart showing the manufacturing procedure of the first embodiment of the method of manufacturing an electronic device of the present invention. As shown in FIG. 1, the method of manufacturing an electronic device includes a polyimine resin layer forming step S102 (corresponding to the step (1)), in which a specific polyimide resin layer is disposed on a temporary support; a glass substrate Laminating step S104 (corresponding to step (2)), which is tied to the poly a glass substrate is disposed on the yttrium imide resin layer; a member forming step S106 (corresponding to step (3)) for arranging the member for electronic device on the glass substrate; and a separating step S108 (step (4)), which is separated Obtain an electronic device.

2(A) to 2(D) are schematic cross-sectional views showing the respective manufacturing steps of the first embodiment of the method of manufacturing the electronic device of the present invention.

Hereinafter, the materials used in the respective steps and the order thereof will be described in detail with reference to FIGS. 1 and 2 (A) to (D). First, the polyimine resin layer forming step S102 will be described in detail.

<Step (1): Polyimine resin layer forming step S102>

The step (1) is a step of forming a polyimine resin layer treated with a decane coupling agent on the surface of the temporary support on the side opposite to the temporary support side. As shown in Fig. 2(A), by carrying out this step, a laminate of the polyimine resin layer 12 having the surface 12a treated with a decane coupling agent on the temporary support 10 is obtained.

Hereinafter, the members and materials used in this step will be described in detail first, and the order of the steps will be described in detail later.

(temporary support)

The temporary support 10 is a substrate which supports the polyimide resin layer before the step (4), and is separated from the polyimide resin layer 12 in the step (4). That is, the temporary support 10 is adhered to the polyimide layer 12 in a peelable manner.

The temporary support 10 is not particularly limited as long as it can be peeled off from the polyimide resin layer 12, and a known substrate can be used. For example, as the temporary support, a metal plate such as a glass plate, a plastic plate (for example, a polymethoxyl plate), a SUS plate, or the like can be used.

Further, as described below, when a leveling agent (surface conditioning agent) is used in the production of the polyimide resin layer 12 (in other words, when a leveling agent is contained in the polyimide layer), The effect of the leveling agent, regardless of the type of material of the temporary support, temporarily Both the support 10 and the polyimide resin layer 12 are easily peeled off.

The thickness of the temporary support 10 is not particularly limited, and may be thicker than the laminated polyimide layer 12 or thinner than the laminated polyimide layer 12. The thickness of the temporary support 10 is preferably from 0.3 to 3.0 mm, more preferably from 0.5 to 1.0 mm, in terms of the current manufacturing apparatus and the operability.

Further, if necessary, the surface of the temporary support 10 may be treated with a polyfluorene-based release agent (for example, a polyoxygenated oil such as dimethyl polyoxyalkylene) or another release agent. The releasability of the polyimide film layer 12. Specific examples of the release treatment as described above include a method in which the polyfluorene-based release agent is brought into contact with the surface of the temporary support 10 and subjected to a baking treatment (for example, at about 350 ° C).

(polyimine resin layer)

The polyimide phase resin layer 12 is a layer disposed on the temporary support 10, and the surface 12a (surface opposite to the side of the temporary support 10) is treated with a decane coupling agent. The polyimide film 12 is transferred onto the glass substrate 14 by contacting the glass substrate 14 with the surface 12a in the glass substrate lamination step S104 as follows.

The thickness of the polyimide layer 12 is not particularly limited, and it is preferable in the case of the step (4) that the blade is easily invaded between the temporary support 10 and the polyimide resin layer 12 to cause a peeling starting point. The thickness is 1 μm or more, and more preferably 2 μm or more, and still more preferably 4 μm or more in terms of peelability. In addition, the upper limit is not particularly limited, and is preferably 100 μm or less, and more preferably 50 μm or less in terms of film formation.

Further, the above thickness means an average thickness, and is obtained by measuring the thickness of any five points of the polyimide film 12 and arithmetically averaging them.

The polyimine resin layer 12 is a layer containing a polyimide resin, and the structure of the polyimide resin is not particularly limited, and a known polyimide resin can be used. In terms of heat resistance and handleability, a repeating unit containing a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the following formula (1) is preferred. Furthermore, the polyimine resin contains the formula (1) The repeating unit is shown as a main component (preferably 95 mol% or more with respect to all repeating units), but may also contain other repeating units (for example, the following formula (2-1) or (2-2)) The repeating unit indicated).

Further, the residue (X) of the tetracarboxylic acid means a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and a residue (A) of a diamine, which means removal of an amine group from a diamine. The resulting diamine residue.

In the formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and A represents a diamine residue obtained by removing an amine group from a diamine.

In the formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxyl group from a tetracarboxylic acid, and preferably contains at least 1 selected from the group consisting of groups represented by the following formulas (X1) to (X4). Kind of base. In particular, in terms of more excellent heat resistance of the polyimide resin layer 12, more preferably 50 mol% or more (preferably 80 to 100 mol%) of the total number of X is selected from the following formula (X1) At least one of the groups consisting of the groups represented by ~(X4). Further, it is preferable that substantially all of the total number of X (100 mol%) includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4). Further, A represents a diamine residue obtained by removing an amine group from a diamine, and preferably contains at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8). In particular, in terms of more excellent heat resistance of the polyimide resin layer 12, more preferably 50 mol% or more (preferably 80 to 100 mol%) of the total number of A is selected from the following formula (A1) At least one of the groups consisting of the bases represented by ~(A8). Further, it is preferable that substantially all of the total number of A (100 mol%) includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

In addition, in terms of more excellent heat resistance of the polyimide resin layer 12, it is preferable that 80 to 100 mol% of the total number of Xs is selected from the group represented by the following formulas (X1) to (X4). At least one of the groups of the group, and 80 to 100 mol% of the total number of A includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8), More preferably, substantially all of the total number of X (100 mol%) includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4), and the essence of the total number of A All of the above (100 mol%) contains at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

In the case where the heat resistance of the polyimide resin layer 12 is more excellent, X is preferably a group represented by the formula (X1) and a group represented by the formula (X4), and more preferably a formula (X1). The basis of the representation.

In addition, as for A, the base represented by the formula (A1) and the group represented by the formula (A6) are more preferable, and the formula (A1) is more preferable. The basis of the representation.

As the polyimine resin containing a preferred combination of the groups represented by the formulae (X1) to (X4) and the groups represented by the formulae (A1) to (A8), X is preferably a formula (X1). The polyimine resin 1 having the group represented by the formula (A1) and the group represented by the formula (X4), and A being a group represented by the formula (A6) Resin 2. In the case of the polyimide resin 1, the heat resistance is more excellent. Moreover, in the case of the polyimine resin 2, it is preferable in terms of colorless transparency.

The number of repetitions (n) of the repeating unit represented by the above formula (1) in the polyimine resin is not particularly limited, and is preferably an integer of 2 or more, in terms of heat resistance and coating film of the polyimide layer 12 . In terms of film formability, it is preferably from 10 to 10,000, more preferably from 15 to 1,000.

The polyimine resin may further contain, as a tetracarboxylic acid residue (X), one or more selected from the group consisting of the groups exemplified below in the range of non-deterioration heat resistance. Further, two or more kinds of the groups exemplified below may be included.

[Chemical 3]

In addition, the polyimine resin may contain one or more kinds of diamines (A) selected from the group consisting of the groups exemplified below in the range of non-destructive heat resistance. Further, two or more kinds of the groups exemplified below may be included.

[Chemical 4]

The content of the polyimine resin in the polyimide layer 12 is not particularly limited, and the heat resistance of the polyimide layer 12 is more excellent, preferably 50% with respect to the total mass of the resin layer. 100% by mass, more preferably 75 to 100% by mass, still more preferably 90 to 100% by mass.

The polyimine resin layer 12 may contain other components than the above-mentioned polyimine resin (for example, a filler which does not impair heat resistance), if necessary.

Examples of the filler that does not inhibit heat resistance include a fibrous filler or a plate, Examples of the non-fibrous filler such as a scaly shape, a granular shape, an indefinite shape, and a crushed product, and specific examples thereof include metal fibers such as glass fibers, PAN-based or pitch-based carbon fibers, stainless steel fibers, aluminum fibers, or brass fibers. , gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, cerium oxide fiber, titanium oxide fiber, cerium carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker , cerium nitride whiskers, mica, talc, kaolin, cerium oxide, calcium carbonate, glass beads, glass flakes, glass microspheres, clay, molybdenum disulfide, ash, titanium oxide, zinc oxide, calcium polyphosphate, Graphite, metal powder, metal flakes, metal strips, metal oxides, carbon powder, black lead, carbon flakes, scaly carbon, carbon nanotubes, and the like. Specific examples of the metal type of the metal powder, the metal foil, and the metal strip include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin, and the like.

Further, in terms of facilitating the control of the adhesion by chemical bonding of the decane coupling agent to the side chain carboxylic acid, the polyimine resin layer 12 is preferably composed of polyglycine ( It is formed by a layer which is a hardening resin of a polyimine resin by thermal hardening. That is, the polyimide film 12 is preferably a layer formed by heat-treating a layer containing polyamic acid, and more preferably a layer formed by heat hardening. A curable resin (polyproline) comprising a polyimine resin having a repeating unit of a residue (X) of a tetracarboxylic acid represented by the above formula (1) and a residue (A) of a diamine The layer is subjected to a heat treatment. Further, the heat treatment can be carried out stepwise by changing the temperature.

Further, the surface 12a of the polyimide layer 12 (the surface opposite to the side of the temporary support 10) is treated with a decane coupling agent. In other words, a layer of a decane coupling agent is disposed on the surface of the polyimide resin layer 12. Further, the treatment with the decane coupling agent may be carried out on the entire surface 12a of the polyimide resin layer 12, or a part thereof may be carried out.

The type of the decane coupling agent to be used is not particularly limited, and it is preferably a reactive group which can react with the polyamic acid used in forming the polyimide layer. If the decane coupling agent has the reactive group, the decane coupling agent is reacted with the polyimine via the reactive group. The resin layer 12 forms a bond and forms a bond with the glass substrate 14 via the stanol group contained in the decane coupling agent, and the adhesion between the two is further improved.

The reactive group is not particularly limited as long as it can react with a functional group in polyamic acid, and examples thereof include a carboxylic acid group or a secondary amine group (-NH-) in polyglycine. Specific examples of the reaction group include a primary amino group, a secondary amino group, a hydroxyl group, a carboxylic acid group, and an epoxy group.

Preferred examples of the decane coupling agent include compounds represented by the following formula (3).

Formula (3) XL-Si(Y) ₃

X represents a reactive group, L represents a single bond or a divalent linking group, and Y each independently represents a hydroxyl group or a hydrolyzable group.

The definition of the reactive group is as described above.

Examples of the divalent linking group include -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an extended aryl group, and a heterocyclic group ( Heteroaryl group), and the combination of these groups.

The hydrolyzable group means a group which can form a stanol group, or a group which can form a siloxane condensate, and specifically, a halogen group, an alkoxy group, a decyloxy group, an isocyanate group, etc. are mentioned. Among them, an alkoxy group (preferably having a carbon number of 1 to 2) is preferable.

(order of steps)

The order of the step (1) is not particularly limited as long as it can form a polyimine resin layer treated with a decane coupling agent on the side opposite to the side of the temporary support on the temporary support, and a known method can be employed.

Among them, in terms of being more excellent in adhesion between the polyimide film and the glass substrate, the following two aspects are preferable, and the aspect X is more preferable.

(Section X) has the following steps: Step (A), which is applied to a temporary support to coat a composition comprising polyamic acid to form a coating film comprising polyamic acid; and step (B) , Providing a decane coupling agent to the surface of the coating film; and a step (C) of heat-treating the coating film to obtain a polyimide resin treated with a decane coupling agent on the opposite side of the temporary support side. Floor

(Stage Y) has the following steps: step (D), which forms a polyimide layer on the temporary support; and step (E), which is imparted to the surface of the polyimide layer a decane coupling agent to obtain a polyimine resin layer treated with a decane coupling agent on the opposite side of the temporary support side

The difference between the aspect X and the aspect Y is that the period of the decane coupling agent is different. The aspect X is as follows: a decane coupling agent is applied to a coating film containing polyamic acid, and then a heat treatment (closed-loop treatment (醯imination treatment)) is applied to harden the coating film to obtain a surface decane. A coupling agent treated polyimine resin layer. On the other hand, the aspect Y is as follows: after temporarily preparing a polyimide resin layer, a decane coupling agent is imparted to the polyimide film layer to obtain a polyimide resin having a surface treated with a decane coupling agent. Floor.

When comparing the above two aspects, the pattern X makes the interface between the layer of the decane coupling agent and the coating film containing the poly-proline acid easy to be mixed, and the adhesion between the two is excellent, and as a result, the polyimide layer and the polyimide layer are The adhesion of the glass substrate is more excellent. Further, in the case where the decane coupling agent has a reactive group capable of reacting with poly-proline, the adhesion between the polyimine resin layer and the glass substrate is particularly excellent in the aspect X.

Hereinafter, the order of the above-described aspects X and Y will be described in detail.

(state X)

In the aspect X, first, the step (A) is carried out by coating a composition containing polylysine on a temporary support to form a coating film containing polylysine.

Hereinafter, the material (polylysine, etc.) used in this step will be described in detail first.

The polyamic acid is a curable resin which is a polyimine resin by thermal curing, and is preferably a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, more preferably a tetracarboxylic acid. At least a portion of the acid dianhydride comprises a compound selected from the group consisting of the following formulas (Y1) to (Y4) At least one of the tetracarboxylic dianhydrides in the group, and at least a part of the diamines contains at least one diamine selected from the group consisting of compounds represented by the following formulas (B1) to (B8) class.

Further, poly-proline is usually represented by a structural formula containing a repeating unit represented by the following formula (2-1) and/or formula (2-2). Further, in the formula (2-1) and/or the formula (2-2), X and A are as defined above.

The reaction conditions of the tetracarboxylic dianhydride and the diamine are not particularly limited, and in terms of efficiently synthesizing the polyamic acid, it is preferably -30 to 70 ° C (preferably -20 to 40 ° C). The reaction is carried out.

The mixing ratio of the tetracarboxylic dianhydride to the diamine is not particularly limited, and is preferably 0.66 to 1.5 mol, more preferably 0.9 to 1.1 mol, and more preferably 1 mol of the diamine. Preferably, 0.97~1.03 mole of tetracarboxylic dianhydride is reacted.

When reacting a tetracarboxylic dianhydride with a diamine, an organic solvent can be used as needed. The type of the organic solvent to be used is not particularly limited, and for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N, can be used. N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, hexamethylphosphoniumamine, tetramethylene hydrazine, dimethyl hydrazine, m. Phenol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, two Alkane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone or the like may be used in combination of two or more kinds.

In the above reaction, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride selected from the group consisting of the compounds represented by the above formulas (Y1) to (Y4) may be used as needed.

Further, at the time of the above reaction, other diamines other than the diamines selected from the group consisting of the compounds represented by the above formulas (B1) to (B8) may be used as needed.

In the composition containing polylysine, a component other than polyamic acid may be contained as needed.

For example, a solvent may be contained in the composition. As the solvent, in particular, in terms of solubility of polyamic acid, an organic solvent is preferred. The organic solvent to be used may, for example, be an organic solvent used in the reaction of the above polyamic acid.

In addition, when the organic solvent is contained in the composition, the content of the organic solvent is not particularly limited as long as the thickness of the coating film can be adjusted and the coating property is good, and generally relative to the total composition. The mass is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass.

Further, a dehydrating agent or a dehydration ring-closing catalyst for promoting the dehydration ring closure of polyamic acid may be used as needed. As the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used.

Further, a leveling agent may be contained in the composition as needed. The leveling agent is a compound which reduces the surface tension of the coating material and improves the wetting of the object to be coated. As the leveling agent, a general leveling agent can be used, and examples thereof include a fluorine-based leveling agent (for example, a fluorine-based surfactant), an acrylic leveling agent, and a polyfluorene-based leveling agent (for example, a polyfluorene-based interface). One or two or more of these may be used as the active agent or the like.

The method of applying the composition on the surface of the temporary support is not particularly limited, and a known method can be used. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, a gravure coating method, and the like can be given.

The thickness of the coating film obtained by the above treatment is not particularly limited, and is appropriately adjusted so as to obtain the above-mentioned preferred thickness of the polyimide film.

After the above coating, a drying treatment may be carried out in order to remove a volatile component (for example, a solvent) contained in the coating film as needed. The method of the drying treatment is not particularly limited as long as it is a method in which the ring closure reaction of the polyamic acid (the ruthenium imidization reaction) is not carried out. For example, it can be enumerated A method of heat treatment, a method of performing air drying treatment, or the like.

The conditions of the heat treatment vary depending on the structure of the polyamic acid to be used, and the heating temperature is usually preferably from 40 to 200 ° C, and from 40 to 150 ° C in terms of suppressing foaming of the resin layer. It is particularly preferred to carry out the heating at a boiling point of the solvent within the above range of the heating temperature. The heating time is appropriately selected according to the structure of the polyamic acid to be used, and further, it is preferably 5 to 60 minutes, more preferably 10 to 10, in terms of depolymerization of polyglycine. 30 minutes.

The heating environment is not particularly limited, and is, for example, carried out in the atmosphere, under vacuum or under an inert gas. When it is carried out under vacuum, even if it is heated at a relatively low temperature, the volatile component can be removed in a shorter period of time, and the depolymerization of polyglycine can be further controlled, which is preferable.

Furthermore, the drying treatment can also be carried out stepwise under different temperature conditions.

Then, the step (B) is carried out: a decane coupling agent is imparted to the surface of the coating film containing the polyamic acid obtained in the above step (A).

The method of imparting the decane coupling agent is not particularly limited, and a known method can be employed. For example, a method of applying a composition containing a decane coupling agent to the surface of a coating film (coating method), or a method of immersing the above-mentioned coating film-attached support in a composition containing a decane coupling agent (impregnation) method). Among them, in terms of easily adjusting the amount of the decane coupling agent to be applied, a coating method is preferred. In the coating method, the method of applying the composition containing the decane coupling agent is not particularly limited, and a method of applying the composition containing the polyaminic acid described above can be mentioned.

The above decane coupling agent is contained in the composition containing a decane coupling agent.

Further, the composition containing a decane coupling agent may optionally contain a solvent. The type of the solvent may, for example, be a solvent which may be contained in the above-mentioned composition containing polyamic acid.

Furthermore, after the above-mentioned decane coupling agent is added, it is also possible to remove the coating film as needed. Drying treatment is carried out by containing a volatile component (for example, a solvent). The method of the drying treatment is not particularly limited as long as it is a method in which the ring closure reaction of the polyamic acid (the ruthenium imidization reaction) does not proceed rapidly. For example, a method of performing heat treatment or a method of performing air-drying treatment may be mentioned. The conditions of the heat treatment include the conditions (heating temperature, heating time, and environment) which can be subjected to the heat treatment performed in the above step (A).

Then, the step (C) is carried out: a coating film containing a polydecyl acid having a decane coupling agent is subjected to heat treatment on the surface obtained in the step (B), and a polyimide resin having a surface treated with a decane coupling agent is obtained. Floor. In the present step (C), a so-called ring closure reaction (oxime imidization reaction) is carried out.

The heating temperature in the step (C) is not particularly limited, but is preferably from 250 to 500 ° C, and is more preferably in the case where the residual solvent ratio is low and the ruthenium iodide ratio is further increased to make the effect of the present invention more excellent. 300~450 °C.

The heating time is not particularly limited, and the optimum time is appropriately selected depending on the structure of the polyamic acid to be used, and the residual solvent ratio is lowered and the sulfiliation rate is further increased to further improve the effect of the present invention. It is preferably 15 to 120 minutes, more preferably 30 to 60 minutes.

The heating environment is not particularly limited, and is, for example, carried out in the atmosphere, under vacuum or under an inert gas.

Furthermore, the heat treatment can also be carried out stepwise at different temperatures.

The polyimine resin layer containing the polyimide resin is formed by the above step (C).

The ruthenium imidization ratio of the polyimide resin is not particularly limited, and is preferably 99.0% or more, and more preferably 99.5% or more, in terms of further excellent heat resistance of the polyimide film.

The method for measuring the imidization rate of hydrazine is to set the polyaminic acid to be heated at 350 ° C for 2 hours under a nitrogen atmosphere, and to set the imidization ratio of 100% according to the IR spectrum of poly-proline. peak derived from the carbonyl (PEI): a peak strength of about 1780cm ^-1 to the peak intensity of the phase change before and after heat treatment (e.g., benzene ring derived peak: about 1500cm ^-1) and the intensity ratio is obtained.

(state Y)

In the aspect Y, first, the step (D) is carried out: a polyimine resin layer is formed on the temporary support.

The method of forming the polyimide layer of the polyimide resin is not particularly limited, and a known method can be employed. For example, a method of forming a coating film by applying the composition containing polyamic acid to a temporary support to form a coating film, followed by heat treatment to obtain a polyimide film layer (method 1); or containing a poly The composition of the quinone imine resin layer is applied to a temporary support, and if necessary, a drying treatment is carried out to obtain a method of the polyimine resin layer (method 2). Among them, in the aspect of adjusting the thickness of the polyimide film layer more easily, the above method 1 is preferred. Further, the method 1 corresponds to the steps of the steps (A) and (C) in the above-described aspect X, and the order and conditions of the respective steps are the same as those in the above steps (A) and (C).

Then, the step (E) is carried out: a decane coupling agent is imparted to the surface of the polyimine resin layer obtained in the step (D) to obtain a polyimine resin layer having a surface treated with a decane coupling agent.

The method of imparting the decane coupling agent is not particularly limited, and examples thereof include the same procedures as in the step (B) of the above-described aspect X.

<Step (2): Glass Substrate Lamination Step S104>

The step (2) is a step of disposing a glass substrate having a thickness of 0.2 mm or less on the polyimide film obtained in the above step (1) to obtain a glass laminate. As shown in Fig. 2(B), by performing this step, the glass substrate 14 is placed on the surface 12a of the polydecylene resin layer 12 treated with the decane coupling agent, and the temporary support 10 and the polyfluorene are obtained in this order. The imide resin layer 12 and the glass laminate 100 of the glass substrate 14. Further, the polyimide resin layer 12 and the glass substrate 14 are in close contact with each other via a decane coupling agent.

Hereinafter, the members and materials used in this step will be described in detail first, and the order of the steps will be described in detail later.

(glass substrate)

In the glass substrate 14, the first main surface 14a is in contact with the polyimide film 12, and the electronic device member is provided on the second main surface 14b on the side opposite to the polyimide layer 12 side. That is, the glass substrate 14 is used to form a substrate of the following electronic device.

The type of the glass substrate 14 can be a general one, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 14 is excellent in chemical resistance and moisture permeability resistance, and has a low heat shrinkage rate. As an index of the heat shrinkage rate, the linear expansion coefficient prescribed in JIS R 3102 (1995 Revision) can be used.

When the linear expansion coefficient of the glass substrate 14 is large, in many cases, the following member forming step is accompanied by heat treatment, and thus various problems are likely to occur. For example, when a TFT (thin film transistor) is formed on the glass substrate 14, if the glass substrate 14 in which the TFT is formed under heating is cooled, the positional shift of the TFT is excessive due to thermal contraction of the glass substrate 14. After that.

The glass substrate 14 is obtained by melting a glass raw material and shaping the molten glass into a plate shape. Such a molding method may be a general one, and for example, a floating method, a melting method, a flow down method, a rich method, a Luber method, or the like may be used. Further, in particular, the glass substrate 14 having a small thickness can be formed by heating a glass which is temporarily formed into a plate shape to a temperature at which it can be formed, and stretching it by stretching or the like (re-drawing method). And get.

The type of the glass of the glass substrate 14 is not particularly limited, and is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda lime glass, a high cerium oxide glass, or another oxide-based glass containing cerium oxide as a main component. The oxide-based glass is preferably a glass having a cerium oxide content of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 14, a glass suitable for the type of the member for an electronic device or a manufacturing step thereof is used. For example, a glass substrate for a liquid crystal panel contains a glass (alkali-free glass) which does not substantially contain an alkali metal component (but usually contains an alkaline earth metal component) because the elution of an alkali metal component is likely to affect the liquid crystal. Thus, the glass system of the glass substrate 14 It is appropriately selected depending on the type of the device to be applied and its manufacturing steps.

The thickness of the glass substrate 14 is 0.2 mm or less, and is preferably 0.15 mm or less, and more preferably 0.10 mm or less from the viewpoint of thickness reduction and/or weight reduction of the glass substrate 14. When it is 0.2 mm or less, the glass substrate 14 can be provided with good flexibility. When it is 0.15 mm or less, the glass substrate 14 can be wound up in a roll shape.

Moreover, the thickness of the glass substrate 14 is preferably 0.03 mm or more for the reason that the operation of the glass substrate 14 and the glass substrate 14 is easy.

Furthermore, the glass substrate 14 may also include two or more layers. In this case, the materials forming the layers may be the same material or different materials. Moreover, in this case, "the thickness of the glass substrate 14" means the total thickness of all the layers.

(order of steps)

The method of laminating the glass substrate 14 on the surface of the polyimide film 12 (the surface of the polyimide layer 12 opposite to the side of the temporary support 10) is not particularly limited, and a known method can be employed. .

For example, a method in which the glass substrate 14 is superposed on the surface of the polyimide film 12 under a normal pressure environment can be mentioned. Further, the glass substrate 14 may be laminated on the surface of the polyimide resin layer 12 as needed, and then the glass substrate 14 may be pressure-bonded to the polyimide film 12 using a roll or a press. It is preferable to remove the bubbles mixed between the layers of the polyimide film 12 and the glass substrate 14 relatively easily by pressure bonding using a roll or a press machine.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum press method, it is preferable to suppress the incorporation of air bubbles or to ensure good adhesion. By the pressure bonding under vacuum, even when fine bubbles remain, there are cases where bubbles do not grow by heating, and the deformation defects of the glass substrate 14 are not easily caused. Moreover, by crimping under vacuum heating, bubbles are less likely to remain.

In the case of laminating the glass substrate 14, it is preferable that the surface of the glass substrate 14 which is in contact with the polyimide resin layer 12 is sufficiently cleaned and laminated in an environment having high cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 14, which is preferable.

Further, after the laminated glass substrate 14, a pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 14 to the polyimide resin layer 12 is improved, and the positional shift of the electronic device member is less likely to occur in the following step (4), and the electrons are not generated. The productivity of the device is improved.

The conditions of the pre-annealing treatment are appropriately selected according to the kind of the polyimide resin layer 12 to be used, and the peeling strength between the glass substrate 14 and the polyimide layer 12 is more appropriate. Preferably, the heat treatment is carried out at 200 ° C or higher (preferably 200 to 400 ° C) for 5 minutes or longer (preferably 5 to 30 minutes).

(glass laminate)

The glass laminate 100 of the present invention obtained by the above-described steps can be used for various purposes, and examples thereof include the use of a panel for a display device, a PV, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed thereon. . Further, in this application, the glass laminate 100 is often exposed to high temperature conditions (for example, 400 ° C or higher) (for example, 1 hour or longer).

Here, the panel for a display device includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

This glass laminate 100 is used in the step (4). In other words, the glass laminate 100 is used to form a member for an electronic device such as a liquid crystal display device on the surface of the second main surface 14b of the glass substrate 14. Thereafter, the glass laminate in which the member for electronic device is formed is separated into the temporary support 10 and the electronic device, and the temporary support 10 does not become a part constituting the electronic device.

Further, in the glass laminate 100, the polyimide resin layer 12 is fixed to the glass substrate 14, and the temporary support 10 is detachably adhered to the polyimide resin layer 12. In the present invention, the fixing is in close contact with the peelable strength (i.e., the stress required for peeling), and the fixing means that the peeling strength is large with respect to the adhesion. That is, the polyimide layer 12 and The peel strength at the interface of the glass substrate 14 is greater than the peel strength at the interface between the polyimide film 12 and the temporary support 10. In other words, the term "peelable" means that the peeling can be performed without peeling off the surface of the fixed surface.

More specifically, the interface between the glass substrate 14 and the polyimide resin layer 12 has a peel strength (x), and a peeling direction exceeding the peel strength (x) is applied to the interface between the glass substrate 14 and the polyimide layer 12 The stress is peeled off at the interface between the glass substrate 14 and the polyimide film layer 12. The interface between the polyimide resin layer 12 and the temporary support 10 has a peel strength (y), and when the interface between the polyimide layer 12 and the temporary support 10 is applied with a stress exceeding the peel strength (y), Then, the interface between the polyimide film 12 and the temporary support 10 is peeled off.

In the glass laminate 100 (also referred to as the glass laminate having the member described below), the peel strength (x) is higher than the peel strength (y). Therefore, when the stress in the direction in which the temporary support 10 and the glass substrate 14 are peeled off is applied to the glass laminate 100, the glass laminate 100 of the present invention is peeled off at the interface between the temporary support 10 and the polyimide resin layer 12. Further, it is separated into a temporary support 10 and a laminate including the polyimide layer 12 and the glass substrate 14.

Further, the adhesion between the polyimide resin layer 12 and the glass substrate 14 can be improved by the above-described decane coupling agent.

<Step (3): Member Formation Step S106>

The step (3) is a step of disposing a member for an electronic device on the surface of the glass substrate in the glass laminate obtained in the step (2) to obtain a glass laminate having a member. As shown in Fig. 2(C), by performing this step, the member for electronic device 16 is placed on the second surface 14b of the glass substrate (on the surface opposite to the polyimide layer 12). The glass laminate 110 having the temporary support 10, the polyimide phase resin layer 12, the glass substrate 14, and the electronic device member 16 is attached.

Hereinafter, the electronic device member 16 used in this step will be described in detail first, and the order of the steps will be described in detail later.

(Mechanical components (functional components))

The electronic device member 16 is formed on the glass substrate 14 in the glass laminate 100 to constitute at least a part of the electronic device. More specifically, the electronic device member 16 is a member for use in a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, for a display device) Member, member for solar cell, member for thin film secondary battery, circuit for electronic component).

For example, as a member for a solar cell, a transparent electrode such as a tin oxide of a positive electrode, a ruthenium layer represented by a p layer/i layer/n layer, a metal of a negative electrode, or the like may be mentioned as the ruthenium type, and a compound type may also be mentioned. Various components such as dye-sensitized type and quantum dot type.

In addition, examples of the lithium ion type include a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a collector layer, and a resin as a sealing layer. Further, various members corresponding to a nickel hydrogen type, a polymer type, a ceramic electrolyte type, and the like may be mentioned.

In addition, as a circuit for an electronic component, a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor) includes a metal of a conductive portion and yttrium oxide or nitridation of an insulating portion. In addition, various members such as various sensors such as a pressure sensor and an acceleration sensor, or a rigid printed circuit board, a flexible printed circuit board, a rigid flexible printed circuit board, and the like may be used.

(order of steps)

The method for producing the glass laminate 110 having the member is not particularly limited, and the second main surface 14b of the glass substrate 14 of the glass laminate 100 can be formed by a conventionally known method depending on the type of the constituent member of the electronic device member. A member 16 for an electronic device is formed on the surface.

In addition, the electronic device member 16 may not be all of the members (hereinafter referred to as "all members") which are finally formed on the second main surface 14b of the glass substrate 14, and may be one of all members. Points (hereinafter referred to as "partial components"). The glass substrate with the partial members obtained by peeling off the temporary support 10 may be formed into a glass substrate (corresponding to the following electronic device) with all the members in the subsequent step.

Further, a laminate having all the members may be assembled, and thereafter, the temporary support 10 is peeled off from the laminate having all the members, and an electronic device is manufactured. Further, the electronic device may be assembled by using two laminated bodies with all the members attached thereto, and thereafter, the two temporary members 10 are peeled off from the laminated body with all the members, and an electronic device having two glass substrates is manufactured.

For example, in the case of manufacturing an OLED, the surface of the glass substrate 14 of the glass laminate 100 on the opposite side to the side of the polyimide layer 12 (corresponding to the second main surface 14b of the glass substrate 14) is formed. In the organic EL structure, various layers are formed or processed by forming a transparent electrode, and further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like on the surface on which the transparent electrode is formed to form a back surface. The electrode is sealed using a sealing plate. Specific examples of the formation or treatment of the layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, in the case of manufacturing a TFT-LCD, there are various steps such as a TFT forming step on the second main surface 14b of the glass substrate 14 of the glass laminate 100, using a resist liquid on CVD ( A metal film and a metal oxide film formed by a general film formation method such as a chemical vapor deposition method and a sputtering method form a pattern to form a thin film transistor (TFT); a CF forming step is performed on another a second color filter (CF) is formed on the second main surface 14b of the glass substrate 14 of the glass laminate 100 by using a resist liquid; and a bonding step is performed in the TFT forming step. The laminate having the TFT is laminated with the CF-attached laminate obtained in the CF forming step.

In the TFT forming step or the CF forming step, a TFT or CF is formed on the second main surface 14b of the glass substrate 14 by using a known photolithography technique or an etching technique. At this time, a resist liquid is used as a coating liquid for pattern formation.

Furthermore, the second main surface of the glass substrate 14 may be formed as needed before forming the TFT or CF. 14b is cleaned. As the cleaning method, a well-known dry cleaning or wet cleaning can be used.

In the bonding step, the thin film transistor forming surface of the laminated body with the TFT is opposed to the color filter forming surface of the laminated body with CF, and a sealing agent (for example, an ultraviolet curing type sealing agent for cell formation) is used. ) to make a fit. Thereafter, a liquid crystal material is injected into a cell formed of a laminate having a TFT and a laminate having CF. As a method of injecting a liquid crystal material, for example, a pressure reduction injection method or a dropping injection method is available.

<Step (4): Separation step S108>

The step (4) is a step of obtaining an electronic device including a polyimide film, a glass substrate, and a member for an electronic device by removing the temporary support from the glass laminate with the member obtained in the step (3). As shown in Fig. 2(D), there is a step of using the interface of the temporary support 10 and the polyimide resin layer 12 as a peeling surface from the glass laminate 110 with the member obtained in the above step (3). The temporary support 10 is separated and removed, whereby the electronic device 120 including the polyimide layer 12, the glass substrate 14, and the member 16 for electronic devices is obtained.

When the electronic device member 16 on the glass substrate 14 at the time of peeling is a part of all the constituent members required, the remaining constituent members may be formed on the glass substrate 14 after the separation.

The method of separating the temporary support 10 from the electronic device 120 is not particularly limited. Specifically, for example, a sharp cutter can be inserted into the interface between the temporary support 10 and the polyimide resin layer 12 to provide a peeling opening, and thereafter, a mixed fluid of water and compressed air is blown and peeled off. Preferably, the temporary support 10 of the glass laminate 110 having the member is placed on the pressure plate so that the side of the electronic device member 16 is on the lower side, and the electronic device member 16 is vacuum-adsorbed to the pressure. On the disk, in this state, the cutter is first introduced into the interface of the temporary support 10-polyimine resin layer 12. Then, the side of the temporary support 10 is adsorbed by a plurality of vacuum suction pads, and the vacuum suction pad is gradually raised from the vicinity of the portion where the cutter is inserted. If so, an air layer can be formed at the interface between the temporary support 10 and the polyimide resin layer 12, and the air layer diffuses to the entire interface, and the temporary support 10 is accommodated. Easy to peel off.

Further, when the temporary support 10 is separated from the electronic device 120, it is preferable to peel off the peeling aid while blowing the interface between the temporary support 10 and the polyimide resin layer 12. The term "peeling aid" means a solvent such as the above water. Examples of the release aid to be used include water or an organic solvent (for example, ethanol) or a mixture thereof or the like.

Further, when the temporary support 10 is separated from the glass laminate 110 to which the member is attached, it is possible to further suppress the electrostatic adsorption of the fragments of the polyimide resin layer 12 to the temporary support by controlling the blowing or humidity by the ionizer. Body 10.

The above-described manufacturing method of the electronic device 120 is suitable for manufacturing a small display device used by a mobile terminal such as a mobile phone or a PDA. The display device is mainly LCD or OLED, and as LCD, including TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, FE (Field Effect) type, TFT type, MIM (Metal-Insulator-Metal, metal-insulator-metal) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, and the like. It can be applied basically in the case of a display device of either a passive drive type or an active drive type.

The electronic device 120 manufactured by the above-mentioned method includes a panel for a display device having a member for a glass substrate and a display device, a solar cell having a member for a glass substrate and a solar cell, and a glass substrate and a thin film secondary battery. A thin film secondary battery of a member, an electronic component having a glass substrate and a member for an electronic device, and the like. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

[Second Embodiment]

Fig. 3 is a flow chart showing the manufacturing procedure of the second embodiment of the method of manufacturing the electronic device of the present invention. As shown in FIG. 3, the method of manufacturing an electronic device includes a polyimine resin layer forming step S102 (corresponding to step (1)), which is disposed on a temporary support. a polyimide substrate layer; a glass substrate lamination step S110 (corresponding to the step (2')), which is a glass substrate having a size smaller than that of the polyimine resin layer, and a polyimine resin The layer is laminated on the polyimide layer to leave a peripheral region not in contact with the glass substrate; and the cutting step S112 (corresponding to the step (5)) is carried out along the periphery of the glass substrate to The amine resin layer and the temporary support are cut; the member forming step S106 (corresponding to the step (3)) is to arrange the member for the electronic device on the glass substrate; and the separating step S108 (step (4)) is obtained by separating Electronic device.

4(A) to 4(E) are schematic cross-sectional views showing the respective manufacturing steps of the second embodiment of the method of manufacturing the electronic device of the present invention.

The steps shown in FIG. 3 are the same as the steps shown in FIG. 1 except for the steps of the glass substrate lamination step S110 and the cutting step S112, and the same steps are denoted by the same reference numerals, and the description thereof is omitted. The glass substrate lamination step S110 and the cutting step S112 will be described.

<Step (2'): Glass Substrate Lamination Step S110>

The step (2') is to laminate a glass substrate having a size smaller than that of the polyimine resin layer to form a polyimide layer on the polyimide layer to leave a peripheral region not in contact with the glass substrate. The step of obtaining a glass laminate on the imide resin layer. As shown in FIG. 4(A), the polyimine resin layer 12 is placed on the temporary support 10 in the polyimine resin layer forming step S102, and next, as shown in FIG. 4(B), In step S110, a glass substrate 14 having a size smaller than that of the polyimine resin layer 12 is disposed on the polyimide layer 12 . The glass substrate 14 is laminated on the polyimide film layer so as to leave a peripheral region which is not in contact with the glass substrate 14 on the polyimide film layer 12. In other words, the glass substrate 14 is laminated on the polyimide film 12 in such a manner that the polyimide film 12 is exposed on the outer periphery of the glass substrate 14.

More specifically, as shown in FIG. 5(A), the glass substrate 14 is laminated on the polyamid resin layer 12 so as to leave the peripheral region 12b not in contact with the glass substrate 14. On the amine resin layer 12. In other words, the glass substrate 14 is laminated on the polyimide film 12 in such a manner that all the outer edges of the glass substrate 14 are not in contact with the outer periphery of the polyimide layer 12 .

In general, on the exposed surface of the polyimide resin layer 12, a convex portion is likely to be generated in the vicinity of the peripheral portion due to the influence of the surface tension (see FIG. 5(B)). When the glass substrate 14 is laminated, when the convex portion is in contact with the convex portion, the central portion of the glass substrate 14 is bent so as to be damaged, thereby impairing the flatness of the glass substrate 14 (see FIG. 5(C)). When the flatness of the glass substrate 14 is impaired, the position of the electronic device member disposed on the glass substrate 14 is shifted, and the like, and the yield of the electronic device is lowered.

Therefore, by using the glass substrate 14 having a shape smaller than that of the polyimine resin layer 12, the glass substrate 14 can be brought into contact with the polyimide film 12 without coming into contact with the convex portion. As a result, the glass substrate 14 is suppressed from being bent, and the yield of the electronic device is suppressed from being lowered.

In this aspect, the outer shape of the polyimide film 12 is larger than the outer shape of the glass substrate 14. The ratio (area A / total area B) of the area A of the region of the polyimide film 12 in contact with the glass substrate 14 to the total area B of the polyimide resin layer 12 is preferably 0.98 or less, more preferably 0.95. the following. If it is in the above range, the glass substrate 14 is further suppressed from being bent. The lower limit is not particularly limited, and is preferably 0.75 or more, and more preferably 0.80 or more in terms of productivity and the like.

Moreover, the length from the outer periphery of the glass substrate 14 to the outer periphery of the polyimide resin layer 12 is preferably 10 mm or more, and more preferably 15 mm or more. When it is in the above range, the thickness unevenness of the polyimide film 12 is further suppressed. The upper limit is not particularly limited, and is preferably 100 mm or less in terms of productivity and the like.

Further, as a method of laminating the glass substrate 14, the method of the step (2) of the first embodiment described above can be mentioned.

By performing this step, the glass laminate 200 including the temporary support 10, the polyimide resin layer 12, and the glass substrate 14 is obtained.

<Step (5): Cutting off step S112>

The step (5) is a step of cutting the polyimine resin layer and the temporary support in the glass laminate obtained in the above step (2') along the outer periphery of the glass substrate. In other words, the outer peripheral portion of each of the temporary support and the polyimide resin layer in the glass laminate is cut, and the temporary support, the polyimide resin layer, and the glass substrate are each outer periphery. The edge is aligned all week. More specifically, as shown in FIG. 4(C), the temporary support 10 and the polyimide layer 12 are cut along the outer periphery of the glass substrate 14 by this step S112, and the layered body 300 after cutting is obtained ( The laminate after the cutting process is performed).

The method of cutting the temporary support 10 and the polyimide resin layer 12 is not particularly limited, and a known method (cutting by a cutter, cutting by a laser, or the like) can be employed. For example, the method described in paragraphs 0079 to 0095 of JP-A-2013-82182 can be cited.

After the above step (5), by performing the above step (3), as shown in FIG. 4(D), the electronic device member 16 is placed on the glass substrate 14, and the glass laminate 110 with the member is formed. Further, by performing the above step (4), as shown in FIG. 4(E), the temporary support 10 is removed from the glass laminate 110 having the member, and the polyimide substrate 12 and the glass substrate 14 are obtained. The electronic device 120 of the member 16 for electronic devices.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

In the following examples and comparative examples, a glass plate containing an alkali-free borosilicate glass (150 mm in length, 150 mm in width, 0.1 mm in plate thickness, and linear expansion coefficient 38 × 10 ^-7 /° C., Asahi Glass Co., Ltd.) was used as the glass substrate. The product name "AN100" is manufactured. In addition, as the temporary support, the same glass plate containing the alkali-free borosilicate glass (200 mm in length, 200 mm in width, 0.5 mm in thickness, and linear expansion coefficient of 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd.) was used. AN100").

(Manufacture of polyaminic acid solution (A))

P-phenylenediamine (10.8 g, 0.1 mol) was dissolved in 1-methyl-2-pyrrolidone (226.0 g) and stirred at room temperature. 3,3',4,4'-biphenyltetracarboxylic dianhydride (29.4 g, 0.1 mol) was added thereto over 1 minute, and stirred at room temperature for 2 hours, and obtained to have the above formula (2-1) And/or a polyamic acid solution (A) having a solid content of a polyamine of a repeating unit represented by the formula (2-2) of 20% by mass. The viscosity of the solution was measured and found to be 3000 cps at 20 °C.

The viscosity was obtained by measuring the rotational viscosity at 20 ° C using a DVL-BII type digital viscometer (B type viscometer) manufactured by Toki Seiki Co., Ltd.

Further, X in the repeating unit represented by the formula (2-1) and/or the formula (2-2) contained in the polyamic acid is a group represented by the formula (X1), and A is a formula (A1). The basis of the representation.

(Manufacture of decane coupling agent solution (B))

After adding a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxydecane, trade name KBM903) to isopropyl alcohol (IPA), the solution was stirred for about 1 hour using a rotary mixer. And make solution B. Further, the content of the decane coupling agent was added so as to be 0.1% by mass based on the total mass of the isopropyl alcohol.

<Example 1>

The solution A was applied onto the temporarily supported support by a die coater, and then dried at 90 ° C for 10 minutes, and further dried at 150 ° C for 10 minutes, and on a temporary support. A coating film containing polylysine is formed.

Next, the solution B was applied onto the surface of the coating film by a die coater, and then dried at 120 ° C for 10 minutes to obtain a coating film to which a decane coupling agent was applied.

Next, the coating film was subjected to heat treatment at 350 ° C for 1 hour under nitrogen gas to carry out a ring closure reaction of polyglycine, thereby obtaining a polyimine resin layer having a surface treated with a decane coupling agent.

Next, a glass substrate having a size smaller than that of the polyimine resin layer is left on the polyimide layer to leave a peripheral region not in contact with the glass substrate. In the formula, the substrates are aligned with each other at the center position to laminate, thereby obtaining the glass laminate S1. Further, in the glass laminate S1, the peel strength (x) at the interface between the glass substrate and the polyimide layer is higher than the peel strength (y) at the interface between the polyimide film layer and the temporary support.

Then, the glass substrate of the glass laminate S1 is fixed to the pressure plate on which the positioning fixture is mounted, and is overlapped with one of the outer edges of the glass substrate from the upper surface of the pressure plate, and is the second of the temporary support. After the cutting line is drawn by the diamond grinding wheel cutter on the main surface (the main surface opposite to the polyimine resin layer side), the outer side of the cutting line of the temporary support body is clamped by the clamping jig and cut. Similarly, the outer side of the temporary support which overlaps the remaining three sides of the outer periphery of the glass substrate is cut, and then the chamfer is ground by grinding the temporary support by the grindstone having a curved surface, thereby obtaining the cutting process. The glass laminate SA.

Next, the glass laminate SA is subjected to heat treatment performed at the time of disposing the electronic device member on the glass substrate, that is, heat treatment at 450 ° C for 1 hour. After the heat treatment, the mixture was cooled to room temperature. As a result, no separation of the glass substrate and the temporary support, or foaming or whitening of the polyimide resin layer was observed in the glass laminate SA.

Then, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the temporary support and the polyimide resin layer at one of the four corners of the glass laminate SA to form a peeled cut portion, and the vacuum adsorption pad is adsorbed to Each of the glass substrate and the temporary support is not the surface of the peeling surface, and the water is blown toward the interface between the temporary support and the polyimide film layer, and an external force is applied in a direction in which the glass substrate and the temporary support are separated from each other, and temporary support is provided. The body is separated from the glass laminate SA without damage. Here, the inserting of the cutter is performed while the electrostatic fluid is blown from the ionizer (manufactured by Keyence Corporation) to the interface.

Further, the polyimide layer is separated from the temporary support together with the glass substrate. From the above results, it was confirmed that the peel strength (x) at the interface between the glass substrate and the polyimide film layer was higher than the peel strength (y) at the interface between the polyimide film layer and the temporary support.

<Example 2>

The solution A was applied onto the temporarily supported support by a die coater, and then dried at 90 ° C for 10 minutes, and further dried at 150 ° C for 10 minutes, and on a temporary support. A coating film containing polylysine is formed.

Next, the coating film was subjected to heat treatment at 350 ° C for 1 hour under nitrogen to carry out a ring closure reaction of polyglycine, thereby obtaining a polyimine resin layer.

Next, the solution B was applied onto the surface of the polyimide resin layer by a die coater, followed by drying at 120 ° C for 10 minutes to obtain a polyimide film having a surface treated with a decane coupling agent. .

Next, a glass substrate having a size smaller than that of the polyimine resin layer is left in the polyimide layer to leave a peripheral region not in contact with the glass substrate, and the center positions of the substrates are opposite to each other. The layers are laminated to obtain the glass laminate S2. Further, in the glass laminate S2, the peel strength (x) at the interface between the glass substrate and the polyimide film layer is higher than the peel strength (y) at the interface between the polyimide film layer and the temporary support.

Then, the glass substrate of the glass laminate S2 is fixed on the pressure plate on which the positioning fixture is mounted, and the second surface of the temporary support body is overlapped from the upper surface of the glass substrate from the upper surface of the pressure plate. After the cutting line is drawn by the diamond grinding wheel cutter on the main surface, the outer side of the cutting line of the temporary support body is clamped by the clamping jig and cut. Similarly, the outer side of the temporary support which overlaps the remaining three sides of the outer periphery of the glass substrate is also cut, and then the chamfer is ground by grinding the temporary support by the grindstone having the curved surface, thereby obtaining the cut. The treated glass laminate SB.

Then, the glass laminate SB is subjected to a heat treatment performed at a time when the electronic device member is placed on the glass substrate, that is, a heat treatment at 450 ° C for one hour. After the heat treatment, the film was cooled to room temperature. As a result, no separation of the glass substrate and the temporary support, or foaming or whitening of the polyimide film layer was observed in the glass laminate SB.

Thereafter, the temporary support was removed in the same manner as in Example 1 except that the glass laminate SB was used instead of the glass laminate SA.

From the above results, it was confirmed that the peel strength (x) at the interface between the glass substrate and the polyimide film layer was higher than the peel strength (y) at the interface between the polyimide film layer and the temporary support.

As shown in the above-described first and second embodiments, according to the method of the present invention, it is possible to produce a glass laminate including a glass substrate having excellent surface flatness without causing foaming between the polyimide film and the glass substrate. In addition, after the heat treatment at 450 ° C for one hour as a condition for manufacturing a member for an electronic device, the glass laminate can be peeled off at the interface between the temporary support and the polyimide resin layer, and the polyfluorene can be contained. The laminate of the imide resin layer and the glass substrate is separated from the temporary support. From these results, it was confirmed that the polyimide and the glass substrate were excellent in adhesion. Further, it is clear that even after the electronic device is fabricated on the glass substrate by a specific heat treatment, the temporary support can be separated from the glass laminate with the member attached thereto.

(Adhesion evaluation)

In Examples 1 and 2, the adhesion of the polyimide film to the glass substrate was evaluated by comparing the presence or absence of the ridge defect (adhesion defect of the polyimide film) when the temporary support was peeled off. In addition, the "bumping defect" means a defect in which one portion of the polyimide film layer is stretched by the temporary support and the polyimide film layer is partially peeled off from the glass substrate when the temporary support is peeled off.

As a method of evaluation of adhesion, five glass laminates were prepared in each of Examples 1 and 2, and the temporary support was peeled off from each sample, and the bump defect was observed. In addition, as a method of observing the ridge defect, it is visually confirmed whether or not there is a defect having a size of 1 mmφ or more under a fluorescent lamp, and the case of the defect is "x", and the case of no defect is "○".

None of the five samples of Example 1 had "bumping defects". On the other hand, with respect to two of the five samples of Example 2, although the temporary support was peeled off, a bulging defect was also found.

From these results, it was confirmed that the aspect of the first embodiment (corresponding to the above-described aspect X) is inferior to the aspect of the second embodiment (corresponding to the above-described aspect Y), and the adhesion between the glass substrate and the polyimide film layer. More excellent.

Further, it was confirmed that the desired effect can be obtained when the temporary support subjected to the release treatment obtained by the following procedure is used as the temporary support used in Examples 1 and 2.

(release treatment)

The dimethylpolysiloxane was brought into contact with the surface of the glass plate containing the alkali-free borosilicate glass, and subjected to a heat-sealing treatment at 350 °C.

<Comparative Example 1>

The solution A was applied onto the temporarily supported support by a die coater, and then dried at 90 ° C for 10 minutes, and further dried at 150 ° C for 10 minutes, and on a temporary support. A coating film containing polylysine is formed.

Next, the solution B was applied onto the surface of the coating film by a die coater, and then dried at 120 ° C for 10 minutes to obtain a coating film to which a decane coupling agent was applied.

Next, a glass substrate having a shape smaller than the outer diameter of the coating film is placed so as to have a peripheral region which is not in contact with the glass substrate, and the center positions of the substrates are aligned and laminated.

Thereafter, the coating film was subjected to heat treatment at 350 ° C for 1 hour under nitrogen gas to carry out a ring closure reaction of polyglycine.

After the heat treatment, innumerable foaming occurs between the polyimide layer and the glass substrate, and the flatness of the surface of the glass substrate is impaired.

The form of the above Comparative Example 1 corresponds to the form of Patent Document 2, and a specific glass laminate and an electronic device cannot be manufactured by this method.

<Example 4>

In this example, an OLED was produced using the glass laminate SA obtained in Example 1.

First, tantalum nitride, ruthenium oxide, and amorphous ruthenium are sequentially formed on the second main surface of the glass substrate in the glass laminate SA by a plasma CVD method. Ion doping A low concentration of boron is injected into the amorphous germanium layer, and subjected to heat treatment in a nitrogen atmosphere to carry out dehydrogenation treatment. Then, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing device. Then, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Then, a ruthenium oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and thereafter, molybdenum is formed by sputtering, and etching by photolithography is performed. A gate electrode is formed. Then, by using a photolithography method and an ion doping apparatus, a high concentration of boron and phosphorus is implanted into a desired region of each of the N-type and the P-type to form a source region and a drain region. Then, on the second main surface side of the glass substrate, an interlayer insulating film is formed by film formation of ruthenium oxide by a plasma CVD method, and aluminum is formed by sputtering to form a film by using a photolithography method. The etching is performed to form a TFT electrode. Then, the heat treatment was carried out in a hydrogen atmosphere to carry out a hydrogenation treatment, and thereafter, a passivation layer was formed by film formation of nitrogen argon by a plasma CVD method. Then, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Then, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

Then, 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine was formed as a hole injection layer on the second main surface side of the glass substrate by vapor deposition. , as a hole transport layer, bis[(N-naphthyl)-N-phenyl]benzidine, as a light-emitting layer in an 8-hydroxyquinoline aluminum complex (Alq ₃ ), mixed with 40% by volume , 6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN), and as Alq _{3 of the} electron transport layer. Then, aluminum is formed into a film by sputtering, and the counter electrode is formed by etching by photolithography. Then, on the second main surface side of the glass substrate, the ultraviolet curing type is formed. The other glass substrate is bonded to the next layer and sealed. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate S1 (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used. A glass laminate with a member of the present invention.

Then, after the sealing body side of the panel A is vacuum-adsorbed to the pressure plate, the thickness is 0.1 mm. The stainless steel cutter is inserted into the interface between the temporary support of the corner portion of the panel A and the polyimide resin layer, and the opening of the interface between the temporary support and the polyimide resin layer is given. Then, the surface of the temporary support of the panel A is adsorbed by the vacuum adsorption pad, and then the adsorption pad is raised. Here, the inserting of the cutter is performed while the electrostatic fluid is blown from the ionizer (manufactured by Keyence Corporation) to the interface. Then, the electrostatic adsorption fluid is continuously blown from the ionizer to the formed void, and the vacuum adsorption pad is pulled while the water is injected into the peeling front. As a result, the temporary support can be peeled off and an electronic device can be obtained.

Then, the separated glass substrate is cut by a laser cutting or scribing-fracture method, and is divided into a plurality of cells. Thereafter, the glass substrate and the counter substrate which are formed with the organic EL structure are assembled, and the module forming step is performed. Making OLEDs. The OLED thus obtained has no problem in characteristics.

Further, the temperature of the heat treatment in the manufacture of the above electronic device is at most 450 °C.

The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2014-158116, filed on Jan.

Claims (8)

A method for producing an electronic device, comprising: a step (1) of forming a polyimine resin layer treated with a decane coupling agent on a surface of a temporary support opposite to the side of the temporary support; a glass substrate having a thickness of 0.2 mm or less disposed on the polyimide layer of the polyimide to obtain a glass laminate; and a step (3) of disposing a member for an electronic device on a surface of the glass substrate a glass laminate with a member; and a step (4) of removing the temporary support from the glass laminate with the member, and obtaining the polyimide layer, the glass substrate, and the electronic device The electronic device of the component. The method of manufacturing an electronic device according to claim 1, wherein the step (1) comprises: a step (A) of applying a composition comprising polylysine to a temporary support to form a polyglycine-containing composition. a coating film; a step (B) of applying a decane coupling agent to the surface of the coating film; and a step (C) of subjecting the coating film to heat treatment to obtain a surface opposite to the temporary support side A layer of a polyimide resin treated with a decane coupling agent. The method of manufacturing the electronic device of claim 1, wherein the step (1) comprises: a step (D) of forming a polyimide layer on the temporary support; and a step (E) of A decane coupling agent is applied to the surface of the quinone imine resin layer, and a polyimide quinone resin layer treated with a decane coupling agent on the surface opposite to the side of the temporary support is obtained. The method of manufacturing an electronic device according to any one of claims 1 to 3, wherein the step (2) is the following step (2'), the step (2') having a shape other than the polyimine resin layer a small-sized outer-sized glass substrate for the above-mentioned polyimide film layer The layered on the polyimide layer is laminated on the polyimide substrate without leaving a peripheral region in contact with the glass substrate, and further includes the following step (5) between the step (2) and the step (3). (5) The polyimine resin layer and the temporary support in the glass laminate are cut along the outer periphery of the glass substrate. A method for producing a glass laminate, which comprises a temporary support, a polyimide layer treated with a decane coupling agent on a surface opposite to the side of the temporary support, and a glass substrate, and is used for The electronic device member is disposed on the surface of the glass substrate, and then the temporary support is removed to obtain an electronic device including the polyimide layer, the glass substrate, and the electronic device member, and the glass The method for producing a laminate includes the step (1) of forming a polyimine resin layer treated with a decane coupling agent on a surface of the temporary support opposite to the side of the temporary support; and the step (2), A glass substrate having a thickness of 0.2 mm or less is placed on the polyimide layer of the polyimide to obtain the glass laminate. The method for producing a glass laminate according to claim 5, wherein the step (1) comprises: a step (A) of coating a composition comprising polylysine on a temporary support to form a poly-proline a coating film; a step (B) of applying a decane coupling agent to the surface of the coating film; and a step (C) of subjecting the coating film to heat treatment to obtain a side opposite to the temporary support side A layer of a polyimide resin treated with a decane coupling agent. The method for producing a glass laminate according to claim 5, wherein the step (1) comprises: a step (D) of forming a polyimide layer on the temporary support; and a step (E) of the above The decane coupling agent is imparted on the surface of the polyimide resin layer, and the surface of the opposite side of the temporary support side is obtained by a decane coupling agent. Amine resin layer. The method for producing a glass laminate according to any one of claims 5 to 7, wherein the step (2) is the following step (2'), the step (2') having a layer of the polyimine resin a glass substrate having a small outer size and a size is laminated on the polyimide layer on the polyimide layer to leave a peripheral region not in contact with the glass substrate, and in the above step (2) Further, the method further includes the step (5) of cutting the polyimine resin layer and the temporary support in the glass laminate along the outer periphery of the glass substrate.