JP2016035832A - Method of manufacturing electronic device, method of manufacturing glass laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an electronic device, including a member for electronic device and a glass substrate and a polyimide resin layer for reinforcing the glass substrate, conveniently, while suppressing occurrence of foaming between the glass substrate and polyimide resin layer in the electronic device thus obtained, and further excellent in adhesion properties.SOLUTION: A method of manufacturing an electronic device includes a step (1) of forming, on a temporary support, a polyimide resin layer having a surface treated with a silane coupling agent on the side opposite to the temporary support side, a step (2) of obtaining a glass laminate by arranging a glass substrate of 0.2 mm thick or less on the polyimide resin layer, a step (3) of obtaining a glass laminate with a member, by arranging a member for electronic device on the surface of the glass substrate, and a step (4) of obtaining an electronic device including a polyimide resin layer, a glass substrate and a member for electronic device, by removing the temporary support from the glass laminate with a member.SELECTED DRAWING: Figure 1

Description

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

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.
Therefore, a technique for reinforcing a glass substrate by disposing a resin layer or the like on the glass substrate is disclosed (for example, Patent Document 1). However, recently, the size of the thinned glass substrate has further increased, and it is difficult to form a resin layer having excellent properties on such a glass substrate. For example, when a resin layer forming composition is applied on 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, a transfer method has been proposed as one method for forming a resin layer on a glass substrate (Patent Document 2). More specifically, in the Example section of Patent Document 2, a pre-cure laminate having an uncured curable resin composition layer and a glass substrate in this order on the surface showing the easy peelability of the peelable auxiliary substrate. And then curing the uncured curable resin composition layer in the laminate before curing to obtain a cured laminate having a resin layer, and from the cured laminate, a glass substrate and The aspect which obtains the glass substrate with a resin layer which has the resin layer which is contacting the surface is disclosed.

Special Table 2002-542971 International Publication No. 2013/054792

In recent years, polyimide resin layers have attracted attention because of their excellent heat resistance.
With reference to the transfer method described in Patent Document 2, the present inventors used a composition containing a polyamic acid corresponding to a polyimide resin precursor as a curable resin composition, and used for the above glass substrate with a resin layer. Tried to manufacture. More specifically, a composition containing polyamic acid is applied on a peelable auxiliary substrate to form an uncured curable resin composition layer, a glass substrate is laminated thereon, and heat treatment is performed. When applied, foaming occurred at the interface between the obtained resin layer (polyimide resin layer) and the glass substrate. Foaming is presumed to be due to water volatilization that occurs during so-called imidization. Therefore, the surface of the glass substrate where foaming occurred was raised and the flatness of the glass substrate surface was impaired. Thus, when the flatness on the surface of the glass substrate deteriorates, misalignment tends to occur when various electronic device members are arranged on the surface of the glass substrate, resulting in poor productivity of the electronic device.
Moreover, if foaming occurs at the interface between the resin layer (polyimide resin layer) and the glass substrate, the adhesion between the resin layer and the glass substrate may be impaired.

This invention is made in view of the said subject, Comprising: The electronic device containing the member for electronic devices, a glass substrate, and the polyimide resin layer for reinforcing the said glass substrate can be manufactured simply, and obtained. An object of the present invention is to provide a method for producing an electronic device in which the occurrence of 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.
Another object of the present invention is to provide a method for producing a glass laminate comprising a temporary support, a polyimide resin layer, and a glass substrate, which can be suitably used for producing the electronic device.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first aspect of the present invention includes a step (1) of forming a polyimide resin layer on the temporary support, the surface opposite to the temporary support being treated with a silane coupling agent, and the polyimide resin layer. A step (2) of obtaining a glass laminate by disposing a glass substrate having a thickness of 0.2 mm or less on the surface, and a step of obtaining a glass laminate with a member by disposing an electronic device member on the surface of the glass substrate ( 3) and a step (4) of removing the temporary support from the glass laminate with a member to obtain an electronic device including a polyimide resin layer, a glass substrate, and a member for an electronic device. is there.
1st aspect WHEREIN: The process (1) apply | coats the composition containing a polyamic acid on a temporary support body, the process (A) which forms the coating film containing a polyamic acid, and a silane cup on the coating-film surface. A step (B) of applying a ring agent, and a step (C) of obtaining a polyimide resin layer in which the surface opposite to the temporary support side is treated with a silane coupling agent by applying heat treatment to the coating film. Is preferred.
In the first aspect, the step (1) is the step (D) of forming a polyimide resin layer on the temporary support, and a silane coupling agent is applied on the surface of the polyimide resin layer, opposite to the temporary support side. It is preferable to include a step (E) of obtaining a polyimide resin layer whose surface on the side is treated with a silane coupling agent.
In the first aspect, in the step (2), a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is placed on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer. A step (2 ′) of laminating, and a step of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer peripheral edge of the glass substrate between the steps (2) and (3) ( 5) is preferably further provided.
The second aspect of the present invention includes a temporary support, a polyimide resin layer whose surface opposite to the temporary support is treated with a silane coupling agent, and a glass substrate in this order. Manufacture of a glass laminate used to obtain an electronic device including a polyimide resin layer, a glass substrate, and an electronic device member by disposing the electronic device member on the surface and then removing the temporary support. In the method, a step (1) of forming a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent on the temporary support, and a thickness of 0.2 mm or less on the polyimide resin layer It is a manufacturing method of the manufacturing method of a glass laminated body provided with the process (2) which arrange | positions a glass substrate and obtains a glass laminated body.
2nd aspect WHEREIN: The process (1) apply | coats the composition containing a polyamic acid on a temporary support body, the process (A) which forms the coating film containing a polyamic acid, and a silane cup on the coating-film surface. A step (B) of applying a ring agent, and a step (C) of obtaining a polyimide resin layer in which the surface opposite to the temporary support side is treated with a silane coupling agent by applying heat treatment to the coating film. Is preferred.
In the second aspect, the step (1) is the step (D) of forming a polyimide resin layer on the temporary support, and a silane coupling agent is applied on the polyimide resin layer surface, opposite to the temporary support side. It is preferable to include a step (E) of obtaining a polyimide resin layer whose surface on the side is treated with a silane coupling agent.
In the second aspect, in the step (2), a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is placed on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer. It is a step (2 ′) of laminating, and further comprising a step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer peripheral edge of the glass substrate after the step (2). preferable.

ADVANTAGE OF THE INVENTION According to this invention, the electronic device containing the member for electronic devices, a glass substrate, and the polyimide resin layer for reinforcing the said glass substrate can be manufactured simply, and a glass substrate and polyimide are obtained in the obtained electronic device. It is possible to provide a method for manufacturing an electronic device in which the occurrence of foaming between the resin layer and the resin layer is suppressed and the adhesiveness between the two is excellent.
Moreover, according to this invention, the manufacturing method of the glass laminated body containing the temporary support body, polyimide resin layer, and glass substrate which can be used conveniently for manufacture of the said electronic device can also be provided.

It is a flowchart which shows the manufacturing process of 1st Embodiment of the manufacturing method of the electronic device of this invention. It is typical sectional drawing which shows 1st Embodiment of the manufacturing method of the electronic device of this invention to process order. It is a flowchart which shows the manufacturing process of 2nd Embodiment of the manufacturing method of the electronic device of this invention. It is typical sectional drawing which shows 2nd Embodiment of the manufacturing method of the electronic device of this invention to process order. (A) It is a top view of the glass laminated body obtained at the process (2 '). (B) It is an expanded sectional view of the peripheral part vicinity of a polyimide resin layer. (C) It is an expanded sectional view at the time of laminating | stacking a glass substrate on the polyimide resin layer in FIG.5 (B).

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

One of the features of the method for producing an electronic device and a glass laminate of the present invention is that a polyimide resin layer whose surface is treated with a silane coupling agent is placed on a temporary support and transferred onto a glass substrate. There are some points.
As described above, when a layer is formed on the surface of the thinned glass substrate and various materials are applied to the surface, it is difficult to form a uniform coating film, even if a coating film is formed. If an attempt is made to transport the glass substrate to perform subsequent processing (for example, drying processing), the glass substrate will bend, causing unevenness in the thickness of the coating film, leading to cracking of the resin layer. Moreover, when providing various materials directly on the glass substrate surface, the surface on the opposite side to the side which provides the material of a glass substrate normally contacts the member for supporting a glass substrate. When such a member comes into contact, it may cause a deterioration in surface properties such as scratching on the surface of the glass substrate, which may adversely affect the subsequent production of the electronic device member. In addition, it is often fixed to a vacuum suction stand during application onto a glass substrate. However, if the glass substrate is thin, the liquid on the coating film and uneven drying occur due to the temperature difference between the suction hole and the contact area. Cheap.
On the other hand, in the present invention, since the polyimide resin layer is once provided on the temporary support and transferred to the glass substrate, the number of times of handling the glass substrate is reduced, and damage to the glass substrate surface can be reduced. In addition, since the polyimide resin layer is first formed on the temporary support, it is easier to control the thickness of the polyimide resin layer. Furthermore, since the polyimide resin layer surface is treated with a silane coupling agent, the adhesion to the glass substrate is excellent. Therefore, as will be described later, after the electronic device member is formed on the glass substrate in the glass laminate, the temporary support can be easily removed using the interface between the temporary support and the polyimide resin layer as a release surface. it can.
Thus, according to the present invention, a predetermined electronic device can be easily manufactured. Moreover, it can be said that the glass laminated body of this invention can be used conveniently in order to manufacture easily the electronic device containing the polyimide resin layer and glass substrate which function as a reinforcement layer of a thin glass substrate.

[First Embodiment]
FIG. 1 is a flowchart showing manufacturing steps in the first embodiment of the electronic device manufacturing method of the present invention. As shown in FIG. 1, the manufacturing method of an electronic device includes a polyimide resin layer forming step S102 (corresponding to step (1)) in which a predetermined polyimide resin layer is disposed on a temporary support, and a glass substrate on the polyimide resin layer. Glass substrate lamination step S104 (corresponding to step (2)) to be arranged, member forming step S106 (corresponding to step (3)) to arrange the electronic device member on the glass substrate, and separation obtained by separating the electronic device Step S108 (step (4)) is provided.
Moreover, FIG. 2 is typical sectional drawing which shows in order each manufacturing process in 1st Embodiment of the manufacturing method of the electronic device of this invention.
Hereinafter, the materials used in each step and the procedure thereof will be described in detail with reference to FIGS. 1 and 2. First, the polyimide resin layer forming step S102 will be described in detail.

<Step (1): Polyimide resin layer forming step S102>
Step (1) is a step of forming on the temporary support a polyimide resin layer whose surface opposite to the temporary support is treated with a silane coupling agent. As shown in FIG. 2A, by carrying out this step, a laminate in which the polyimide resin layer 12 whose surface 12a is treated with a silane coupling agent is disposed on the temporary support 10 is obtained.
Below, the member and material used at this process are explained in full detail first, and the procedure of the post process is explained in full detail.

(Temporary support)
The temporary support 10 is a substrate that supports the polyimide resin layer until step (4) described later, and is separated from the polyimide resin layer 12 during the step (4). That is, the temporary support 10 is in close contact with the polyimide resin layer 12 in a peelable manner.
The type of 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 glass plate, a plastic plate (for example, a silicone substrate), a metal plate such as a SUS plate, or a substrate in which these are laminated is used.
As will be described later, when the polyimide resin layer 12 is produced, when a leveling agent (surface conditioning agent) is used (in other words, when the leveling agent is included in the polyimide resin layer), Due to the effect of the leveling agent, both the temporary support 10 and the polyimide resin layer 12 easily peel off regardless of the type of material of the temporary support.

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

  If necessary, the surface of the temporary support 10 can be treated with a silicone-based mold release agent (for example, silicone oil such as dimethylpolysiloxane) or other mold release agents so as to make the polyimide resin layer 12 peelable. It may be improved. As a specific method of the mold release treatment as described above, there is a method in which the silicone mold release agent is brought into contact with the surface of the temporary support 10 to perform a baking treatment (for example, about 350 ° C.).

(Polyimide resin layer)
The polyimide resin layer 12 is a layer disposed on the temporary support 10, and the surface 12a (surface opposite to the temporary support 10 side) is treated with a silane coupling agent. As described later, the polyimide resin layer 12 is transferred onto the glass substrate 14 when the surface 12a is in contact with the glass substrate 14 in the glass substrate lamination step S104.

The thickness of the polyimide resin layer 12 is not particularly limited. However, in the step (4), the thickness is 1 μm or more from the viewpoint that a blade easily enters between the temporary support 10 and the polyimide resin layer 12 to cause a separation start point. Preferably, it is preferably 2 μm or more, more preferably 4 μm or more from the viewpoint of peelability. The upper limit is not particularly limited, but is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of thinning.
In addition, the said thickness intends average thickness, measures the thickness of arbitrary 5 points | pieces of the polyimide resin layer 12, and arithmetically averages them.

Although the polyimide resin layer 12 is a layer containing a polyimide resin, the structure of the polyimide resin is not particularly limited, and a known polyimide resin can be used. From the viewpoint of heat resistance and handleability, the following formula (1) It is preferably composed of a repeating unit having a tetracarboxylic acid residue (X) and a diamine residue (A). In addition, although polyimide resin contains the repeating unit represented by Formula (1) as a main component (95 mol% or more with respect to all the repeating units is preferable), other repeating units (for example, mentioned later) The repeating unit represented by formula (2-1) or (2-2) may be included.
The tetracarboxylic acid residue (X) is a tetracarboxylic acid residue obtained by removing a carboxy group from a tetracarboxylic acid, and the diamine residue (A) is a diamine obtained by removing an amino group from a diamine. Intended for residues.

  In formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and A represents a diamine residue obtained by removing an amino group from diamines.

In the formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and at least one selected from the group consisting of groups represented by the following formulas (X1) to (X4) It preferably consists of a group. Among these, groups in which 50 mol% or more (preferably 80 to 100 mol%) of the total number of X are represented by the following formulas (X1) to (X4) are more excellent in the heat resistance of the polyimide resin layer 12. More preferably, it consists of at least one group selected from the group consisting of: More preferably, substantially all (100 mol%) of the total number of X is composed of at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4).
A represents a diamine residue obtained by removing an amino group from diamines, and preferably comprises at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8). Among them, the group represented by the following formulas (A1) to (A8) is 50 mol% or more (preferably 80 to 100 mol%) of the total number of A in that the heat resistance of the polyimide resin layer 12 is more excellent. More preferably, it consists of at least one group selected from the group consisting of: More preferably, substantially all (100 mol%) of the total number of A is composed of at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8).

  In addition, at the point which the heat resistance of the polyimide resin layer 12 is more excellent, 80-100 mol% of the total number of X is at least 1 sort (s) chosen from the group which consists of group represented by the following formula | equation (X1)-(X4). It is preferable that 80 to 100 mol% of the total number of A consists of at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8), The total number (100 mol%) of the total number consists of at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4), and substantially the total number of A It is more preferable that the total number (100 mol%) is composed of at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8).

Among these, X is preferably a group represented by the formula (X1) and a group represented by the formula (X4) in terms of more excellent heat resistance of the polyimide resin layer 12, and is represented by the formula (X1). Groups are more preferred.
Further, as A, a group represented by the formula (A1) and a group represented by the formula (A6) are preferable, and the group represented by the formula (A1) is more preferable because the heat resistance of the polyimide resin layer 12 is more excellent. Is more preferable.

  As a polyimide resin comprising a suitable combination of groups represented by formulas (X1) to (X4) and groups represented by formulas (A1) to (A8), a group in which X is represented by formula (X1) A polyimide resin 1 in which A is a group represented by the formula (A1), and a polyimide in which X is a group represented by the formula (X4) and A is a group represented by the formula (A6) Resin 2 is preferred. In the case of the polyimide resin 1, it is more excellent in heat resistance. Moreover, in the case of the polyimide resin 2, it is preferable at the point of colorless transparency.

  The number of repeating units (n) represented by the above formula (1) in the polyimide resin is not particularly limited, but is preferably an integer of 2 or more, the heat resistance of the polyimide resin layer 12 and the film formation of the coating film. From the viewpoint of property, 10 to 10000 are preferable, and 15 to 1000 are more preferable.

  The polyimide resin may contain at least one selected from the group consisting of the groups exemplified below as the residue (X) of the tetracarboxylic acids within a range that does not impair the heat resistance. Moreover, 2 or more types of groups illustrated below may be included.

  Moreover, the said polyimide resin may contain 1 or more types chosen from the group which consists of group illustrated below as a residue (A) of diamine within the range which does not impair heat resistance. Moreover, 2 or more types of groups illustrated below may be included.

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

In the polyimide resin layer 12, other components other than the polyimide resin (for example, a filler that does not impair heat resistance) may be included as necessary.
Examples of fillers that do not impair heat resistance include fibrous or non-fibrous fillers such as plate-like, scaly, granular, indeterminate, and crushed products. Specific examples include glass fiber, PAN-based fillers, and the like. Pitch-based carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber and brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, titanic acid Potassium whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flake, glass microballoon, clay, molybdenum disulfide, wollastonite, titanium oxide, oxidation Zinc, calcium polyphosphate, Rafaito, metal powders, metal flakes, metal ribbons, metal oxides, carbon powder, graphite, carbon flake, scaly carbon, and carbon nanotubes. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

  The polyimide resin layer 12 is preferably formed from a layer containing polyamic acid (a curable resin that becomes a polyimide resin by thermosetting) in terms of easy control of film thickness and surface shape. That is, the polyimide resin layer 12 is preferably a layer formed by subjecting a layer containing polyamic acid to heat treatment, and further, a tetracarboxylic acid represented by the above formula (1) by thermosetting. It may be a layer formed by subjecting a layer of a curable resin (polyamic acid) to be a polyimide resin composed of repeating units having a residue (X) and a diamine residue (A) to heat treatment. More preferred. In addition, you may implement heat processing in steps, changing temperature.

Moreover, the surface 12a (surface on the opposite side to the temporary support body 10 side) of the polyimide resin layer 12 is processed with the silane coupling agent. In other words, a layer of a silane coupling agent is disposed on the surface of the polyimide resin layer 12. In addition, the process by a silane coupling agent may be the whole surface 12a of the polyimide resin layer 12, or may be a part.
Although the kind of silane coupling agent used is not particularly limited, it preferably has a reactive group capable of reacting with the polyamic acid used when forming the polyimide resin layer. When the silane coupling agent has the reactive group, the silane coupling agent forms a bond with the polyimide resin layer 12 through the reactive group, and the glass substrate through the silanol group contained in the silane coupling agent. 14 and a bond are formed, and the adhesion between them is further improved.
The reactive group is not particularly limited as long as it can react with a functional group in the polyamic acid, and examples thereof include a group capable of reacting with a carboxylic acid group or a secondary amino group (—NH—) in the polyamic acid. More specifically, a primary amino group, a secondary amino group, a hydroxyl group, a carboxylic acid group, an epoxy group, and the like can be given.
As a suitable aspect of a silane coupling agent, the compound represented by the following formula | equation (1) is mentioned.
Formula (1) X-L-Si (Y) ₃
X represents a reactive group, L represents a single bond or a divalent linking group, and Y 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 arylene group, and a heterocyclic group (heteroarylene). Group) and a combination thereof.
The hydrolyzable group represents a group capable of forming a silanol group or a group capable of forming a siloxane condensate, and specific examples thereof include a halogen group, an alkoxy group, an acyloxy group, and an isocyanate group. . Especially, an alkoxy group (C1-C2 is preferable) is mentioned preferably.

(Process procedure)
The procedure of the step (1) is not particularly limited as long as a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent can be formed on the temporary support, and is a known method. Can be adopted.
Especially, the following two aspects are preferable and aspect X is more preferable at the point which the adhesiveness of a polyimide resin layer and a glass substrate is more excellent.
(Aspect X) The process (A) which forms the coating film containing a polyamic acid by apply | coating the composition containing a polyamic acid on a temporary support body, and the process (B) which provides a silane coupling agent on the coating-film surface And a step (C) of obtaining a polyimide resin layer in which the surface opposite to the temporary support side is treated with a silane coupling agent is applied to the coating film (the mode Y) on the temporary support side. A step (D) of forming a polyimide resin layer on the surface, a silane coupling agent on the surface of the polyimide resin layer, and a polyimide resin layer whose surface opposite to the temporary support side is treated with the silane coupling agent. The aspect provided with the process (E) to obtain The difference between the aspect X and the aspect Y differs in the time which provides a silane coupling agent. In aspect X, a silane coupling agent is applied on a coating film containing polyamic acid, and then a heat treatment (ring-closing treatment (imidation treatment)) is applied to cure the coating film. The surface is a silane coupling agent. In this embodiment, a treated polyimide resin layer is obtained. On the other hand, mode Y is a mode in which after a polyimide resin layer is once manufactured, a silane coupling agent is applied onto the polyimide resin layer to obtain a polyimide resin layer whose surface is treated with the silane coupling agent.
When comparing the above two aspects, the aspect X is more easily mixed with the interface between the silane coupling agent layer and the coating film containing polyamic acid, and the adhesion between them is excellent, resulting in a polyimide resin layer. The adhesion between the glass substrate and the glass substrate is more excellent. Moreover, when the silane coupling agent has a reactive group that can react with the polyamic acid, in particular, in the aspect X, the adhesion between the polyimide resin layer and the glass substrate is more excellent.
Hereinafter, the procedures of the above aspects X and Y will be described in detail.

(Aspect X)
In aspect X, first, the step (A) of applying a composition containing polyamic acid on the temporary support to form a coating film containing polyamic acid is performed.
Below, the material (polyamic acid etc.) used at this process is explained in full detail first.

  The polyamic acid is a curable resin that becomes a polyimide resin by thermosetting, preferably a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine, and at least a part of the tetracarboxylic dianhydride is It consists of at least one tetracarboxylic dianhydride selected from the group consisting of compounds represented by the following formulas (Y1) to (Y4), and at least some of the diamines are represented by the following formulas (B1) to (B8). More preferably, it consists of at least one diamine selected from the group consisting of compounds represented by:

  In addition, a polyamic acid is normally represented as a structural formula containing the repeating unit represented by Formula (2-1) and / or Formula (2-2) below. In addition, in the formula (2-1) and / or the formula (2-2), the definitions of X and A are as described above.

The reaction conditions of tetracarboxylic dianhydride and diamines are not particularly limited, and it is preferable to react at −30 to 70 ° C. (preferably −20 to 40 ° C.) from the viewpoint that polyamic acid can be efficiently synthesized.
Although the mixing ratio in particular of tetracarboxylic dianhydride and diamines is not restrict | limited, Preferably tetracarboxylic dianhydride is 0.66-1.5 mol with respect to 1 mol of diamines, More preferably, it is 0.8. The reaction may be 9 to 1.1 mol, more preferably 0.97 to 1.03 mol.
In the reaction of tetracarboxylic dianhydride and diamines, an organic solvent may be used as necessary. The type of organic solvent to be used is not particularly limited. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, Dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone and the like can be used, and two or more kinds may be used in combination.

In the case of the said reaction, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride selected from the group which consists of a compound represented by said formula (Y1)-(Y4) as needed are added. You may use together.
Moreover, in the case of the said reaction, you may use together other diamines other than the diamine selected from the group which consists of a compound represented by said formula (B1)-(B8) as needed. Good.

In the composition containing a polyamic acid, components other than the polyamic acid may be contained as necessary.
For example, the composition may contain a solvent. As the solvent, an organic solvent is particularly preferable from the viewpoint of the solubility of the polyamic acid. As an organic solvent used, the organic solvent used in the case of reaction of the polyamic acid mentioned above is mentioned.
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 can be improved. On the other hand, 5-95 mass% is preferable and 10-90 mass% is more preferable.
Further, if necessary, a dehydrating agent or a dehydrating ring closure catalyst for promoting dehydration ring closure of the polyamic acid may be used together. For example, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example.
Furthermore, a leveling agent may be contained in the composition as needed. A leveling agent is a compound that reduces the surface tension of a coated material and improves the wettability of the coated material. As the leveling agent, general leveling agents can be used. For example, fluorine leveling agents (for example, fluorine surfactants), acrylic leveling agents, silicone leveling agents. (For example, a silicone-based surfactant) and the like, and one or more of these can be used.

The method for applying the composition on the surface of the temporary support is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating.
The thickness of the coating film obtained by the said process is not restrict | limited in particular, It adjusts suitably so that the polyimide resin layer of the suitable thickness mentioned above may be obtained.
After the application, if necessary, a drying treatment may be performed to remove volatile components (for example, a solvent) contained in the coating film. The method for the drying treatment is not particularly limited as long as the ring closing reaction (imidation reaction) of the polyamic acid does not proceed. For example, a method of performing a heat treatment, a method of performing an air drying treatment, or the like can be given.
Although the heat treatment conditions vary depending on the structure of the polyamic acid used, the heating temperature is usually preferably 40 to 200 ° C., and 40 to 150 ° C. is preferable in that foaming of the resin layer is suppressed. In particular, it is preferable to heat at a temperature lower than the boiling point of the solvent within the above heating temperature range. As the heating time, an optimal time is appropriately selected depending on the structure of the polyamic acid to be used, but it is preferably 5 to 60 minutes, more preferably 10 to 30 minutes, from the point that the depolymerization of the polyamic acid can be further prevented.
The heating atmosphere is not particularly limited, and is performed, for example, in the air, under vacuum, or under an inert gas. It is preferable to carry out under vacuum because even when heated at a low temperature, volatile components can be removed in a shorter time and the depolymerization of the polyamic acid can be more controlled.
In addition, you may implement a drying process in steps under different temperature conditions.

Next, the process (B) which provides a silane coupling agent on the coating-film surface containing a polyamic acid obtained by the said process (A) is implemented.
The method for applying the silane coupling agent is not particularly limited, and a known method can be adopted. For example, there are a method of applying a composition containing a silane coupling agent on the surface of the coating film (application method) and a method of immersing the support with a coating film in a composition containing the silane coupling agent (immersion method). Can be mentioned. Among these, a coating method is preferable because the amount of the silane coupling agent applied can be easily adjusted. In the application method, the method for applying the composition containing the silane coupling agent is not particularly limited, and examples thereof include the method for applying the above-described composition containing polyamic acid.

The composition containing the silane coupling agent includes the silane coupling agent described above.
Moreover, the composition containing the silane coupling agent may contain a solvent as necessary. As for the kind of solvent, the solvent which may be contained in the composition containing the said polyamic acid is mentioned.
In addition, after application | coating of the said silane coupling agent, in order to remove the volatile component (for example, solvent) contained in a coating film, you may give a drying process as needed. The method for the drying treatment is not particularly limited as long as the ring closing reaction (imidation reaction) of the polyamic acid does not proceed rapidly. For example, a method of performing a heat treatment, a method of performing an air drying treatment, or the like can be given. Examples of the heat treatment conditions include heat treatment conditions (heating temperature, heating time, atmosphere) that may be performed in the above-described step (A).

Next, heat treatment is applied to the coating film containing polyamic acid having a silane coupling agent applied to the surface obtained in the step (B) to obtain a polyimide resin layer whose surface is treated with the silane coupling agent. Step (C) is performed. In this step (C), a so-called ring closure reaction (imidation reaction) proceeds.
The heating temperature in this step (C) is not particularly limited, but is preferably 250 to 500 ° C., and the residual solvent ratio is lowered, the imidization ratio is further increased, and the effect of the present invention is more excellent. 300 to 450 ° C. is more preferable.
The heating time is not particularly limited, and an optimal time is appropriately selected depending on the structure of the polyamic acid used, but the residual solvent ratio is lowered and the imidization ratio is further increased, and the effects of the present invention are more excellent. 15 to 120 minutes are preferable, and 30 to 60 minutes are more preferable.
The heating atmosphere is not particularly limited, and is performed, for example, in the air, under vacuum, or under an inert gas.
Note that the heat treatment may be performed stepwise at different temperatures.

By passing through the said process (C), the polyimide resin layer containing a polyimide resin is formed.
The imidation ratio of the polyimide resin is not particularly limited, but is preferably 99.0% or more and more preferably 99.5% or more in terms of more excellent heat resistance of the polyimide resin layer.
The method for measuring the imidization rate is that the polyamic acid is heated at 350 ° C. for 2 hours under a nitrogen atmosphere as 100% imidation rate, and the peak intensity that remains unchanged before and after the heat treatment in the spectrum of polyamic acid by IR (for example, peak derived from a benzene ring: for about 1500 cm ^-1), a peak derived from the imide carbonyl groups: determined by the intensity ratio of a peak intensity of about 1780 cm ^-1.

(Aspect Y)
In the aspect Y, the process (D) which forms a polyimide resin layer on a temporary support body first is implemented.
The method for forming the polyimide resin layer is not particularly limited, and a known method can be employed. For example, the composition containing the polyamic acid mentioned above is applied on a temporary support to form a coating film, and then subjected to heat treatment to obtain a polyimide resin layer (Method 1), or a composition containing a polyimide resin layer Examples include a method (Method 2) of applying a product on a temporary support and applying a drying treatment as necessary to obtain a polyimide resin layer. Especially, the said method 1 is preferable from the point that adjustment of the thickness of a polyimide resin layer is easier. The method 1 corresponds to an embodiment in which the step (A) and the step (C) in the above-described embodiment X are performed, and the respective procedures and conditions are the same as those in the step (A) and the step (C). .

Next, a step (E) of applying a silane coupling agent on the surface of the polyimide resin layer obtained in the step (D) to obtain a polyimide resin layer whose surface is treated with the silane coupling agent is performed.
The method in particular of providing a silane coupling agent is not restrict | limited, For example, the procedure similar to the process (B) in aspect X mentioned above is mentioned.

<Process (2): Glass substrate lamination process S104>
Step (2) is a step of obtaining a glass laminate by disposing a glass substrate having a thickness of 0.2 mm or less on the polyimide resin layer obtained in step (1). As shown in FIG. 2B, by carrying out this step, the glass substrate 14 is disposed on the surface 12a of the polyimide resin layer 12 treated with the silane coupling agent, and the temporary support 10 and the polyimide resin layer. A glass laminate 100 having 12 and the glass substrate 14 in this order is obtained. In addition, the polyimide resin layer 12 and the glass substrate 14 adhere | attach through a silane coupling agent.
Below, the member and material used at this process are explained in full detail first, and the procedure of the post process is explained in full detail.

(Glass substrate)
As for the glass substrate 14, the 1st main surface 14a touches the polyimide resin layer 12, and the member for electronic devices is provided in the 2nd main surface 14b on the opposite side to the polyimide resin layer 12 side. That is, the glass substrate 14 is a substrate used for forming an electronic device described later.
The glass substrate 14 may be of a general type, 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, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  If the linear expansion coefficient of the glass substrate 14 is large, the member forming process described later often involves heat treatment, and thus various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 14, if the glass substrate 14 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 14.

  The glass substrate 14 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. Further, the glass substrate 14 having a particularly small thickness can be obtained by molding a glass once formed into a plate shape by a method (redraw method) by heating the glass to a moldable temperature and stretching the glass by means such as stretching.

  The type of glass of the glass substrate 14 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

  As the glass of the glass substrate 14, glass suitable for the type of electronic device member and its manufacturing process is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate 14 is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 14 is 0.2 mm or less, and is preferably 0.15 mm or less, more preferably 0.10 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 14. In the case of 0.2 mm or less, it is possible to give good flexibility to the glass substrate 14. In the case of 0.15 mm or less, the glass substrate 14 can be rolled up.
Moreover, the thickness of the glass substrate 14 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 14 and easy handling of the glass substrate 14.

  The glass substrate 14 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate 14” means the total thickness of all the layers.

(Process procedure)
The method for laminating the glass substrate 14 on the surface of the polyimide resin layer 12 (on the surface opposite to the temporary support 10 side of the polyimide resin layer 12) is not particularly limited, and a known method can be adopted.
For example, a method of stacking the glass substrate 14 on the surface of the polyimide resin layer 12 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 14 is overlaid on the surface of the polyimide resin layer 12, the glass substrate 14 may be pressure-bonded to the polyimide resin layer 12 using a roll or a press. It is preferable because bubbles mixed between the polyimide resin layer 12 and the glass substrate 14 are relatively easily removed by pressure bonding using a roll or a press.

When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause a distortion defect of the glass substrate 14. Moreover, bubbles are less likely to remain by pressure bonding under vacuum heating.
When laminating the glass substrate 14, it is preferable that the surface of the glass substrate 14 in contact with the polyimide resin layer 12 is sufficiently washed and laminated in an environment with a high degree of cleanliness. The higher the degree of cleanness, the better the flatness of the glass substrate 14, which is preferable.

In addition, after laminating | stacking the glass substrate 14, you may perform a pre-annealing process (heat processing) 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 position of the electronic device member is less likely to occur during the step (4) described later. Productivity is improved.
The optimum conditions for the pre-annealing treatment are appropriately selected according to the type of the polyimide resin layer 12 to be used. From the point of making the peel strength between the glass substrate 14 and the polyimide resin layer 12 more appropriate, It is preferable to perform heat treatment 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 through the above steps can be used for various applications, for example, a display device panel, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface, which will be described later. The use etc. which manufacture electronic parts, such as these, are mentioned. In this application, the glass laminate 100 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 400 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

  This glass laminate 100 is used up to step (4). That is, the glass laminate 100 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 14b of the glass substrate 14. Then, the glass laminated body in which the member for electronic devices was formed is isolate | separated into the temporary support body 10 and an electronic device, and the temporary support body 10 does not become a part which comprises an electronic device.

In addition, in the glass laminated body 100, the polyimide resin layer 12 is being fixed on the glass substrate 14, and the temporary support body 10 adheres to the polyimide resin layer 12 so that peeling is possible. In the present invention, the fixing and peelable adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the adhesion. That is, the peel strength at the interface between the polyimide resin layer 12 and the glass substrate 14 is greater than the peel strength at the interface between the polyimide resin layer 12 and the temporary support 10. In other words, the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling 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 the interface between the glass substrate 14 and the polyimide resin layer 12 has a peeling direction stress exceeding the peel strength (x). When added, the interface between the glass substrate 14 and the polyimide resin layer 12 is peeled off. When the interface between the polyimide resin layer 12 and the temporary support 10 has a peel strength (y) and a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the polyimide resin layer 12 and the temporary support 10, The interface between the polyimide resin layer 12 and the temporary support 10 is peeled off.
In the glass laminate 100 (which also means a glass laminate with a member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when a stress in the direction of peeling the temporary support 10 and the glass substrate 14 is applied to the glass laminate 100, the glass laminate 100 of the present invention peels off at the interface between the temporary support 10 and the polyimide resin layer 12. Then, the temporary support 10 and the laminate including the polyimide resin layer 12 and the glass substrate 14 are separated.
In addition, the adhesiveness of the polyimide resin layer 12 and the glass substrate 14 is improved with the silane coupling agent mentioned above.

<Step (3): Member forming step S106>
A process (3) is a process of arrange | positioning the member for electronic devices on the surface of the glass substrate in the glass laminated body obtained at the process (2), and obtaining the glass laminated body with a member. As shown in FIG. 2C, by carrying out this step, the electronic device member 16 is disposed on the second surface 14b of the glass substrate (on the surface opposite to the polyimide resin layer 12). The glass laminate 110 with a member which has the support body 10, the polyimide resin layer 12, the glass substrate 14, and the member 16 for electronic devices in this order is obtained.
Below, the member 16 for electronic devices used at this process is explained in full detail first, and the procedure of the post process is explained in full detail.

(Electronic device components (functional elements))
The electronic device member 16 is a member that is formed on the glass substrate 14 in the glass laminate 100 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 16, a member used for a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer having a circuit formed on its surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, 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 current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the glass laminated body 110 with a member mentioned above is not specifically limited, The 2nd main surface 14b of the glass substrate 14 of the glass laminated body 100 by a conventionally well-known method according to the kind of structural member of the member for electronic devices. The electronic device member 16 is formed on the surface.
The electronic device member 16 is not all of the members finally formed on the second main surface 14b of the glass substrate 14 (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member obtained by peeling off the temporary support 10 can be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the temporary support 10 from the laminate with all members. Furthermore, it is also possible to assemble by using two laminates with all members, and then peel off the two temporary supports 10 from the laminate with all members to produce a member-attached glass substrate having two glass substrates. it can.

  For example, when an OLED is manufactured as an example, an organic EL is formed on the surface of the glass laminate 100 opposite to the polyimide resin layer 12 side of the glass substrate 14 (corresponding to the second main surface 14b of the glass substrate 14). In order to form a structure, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed. Various layers are formed and processed, such as sealing with a plate. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

  Further, for example, when manufacturing a TFT-LCD, a resist film is used on the second main surface 14b of the glass substrate 14 of the glass laminate 100 by a general film forming method such as a CVD method or a sputtering method. A pattern is formed on the formed metal film, metal oxide film, etc. to form a thin film transistor (TFT), and a resist solution is patterned on the second main surface 14b of the glass substrate 14 of another glass laminate 100. Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 14b of the glass substrate 14 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 14b of the glass substrate 14 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other using a sealing agent (for example, an ultraviolet curable sealing agent for cell formation). Thereafter, a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

<Process (4): Separation process S108>
Step (4) is a step of removing the temporary support from the member-attached glass laminate obtained in step (3) to obtain an electronic device including a polyimide resin layer, a glass substrate, and an electronic device member. As shown in FIG. 2D, the temporary support 10 is separated from the glass laminate 110 with a member obtained in the above step (3) using the interface between the temporary support 10 and the polyimide resin layer 12 as a release surface. It is a process of removing and obtaining the electronic device 120 containing the polyimide resin layer 12, the glass substrate 14, and the member 16 for electronic devices.
When the member 16 for electronic devices on the glass substrate 14 at the time of peeling is a part of formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 14 after separation.

The method for separating the temporary support 10 and the electronic device 120 is not particularly limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the temporary support 10 and the polyimide resin layer 12 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off. Preferably, the temporary support 10 of the glass laminate 110 with a member is installed on a surface plate so that the electronic device member 16 side is on the lower side, and the electronic device member 16 side is vacuum-adsorbed on the surface plate. In this state, first, the cutter is caused to enter the interface between the temporary support 10 and the polyimide resin layer 12. Thereafter, the temporary support 10 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed at the interface between the temporary support 10 and the polyimide resin layer 12, and the air layer spreads over the entire interface, so that the temporary support 10 can be easily peeled off.
When the temporary support 10 and the electronic device 120 are separated, it is preferable that the temporary support 10 and the electronic device 120 are separated while spraying a peeling aid on the interface between the temporary support 10 and the polyimide resin layer 12. The peeling aid intends a solvent such as water described above. Examples of the peeling aid to be used include water, an organic solvent (for example, ethanol) or a mixture thereof.

  When separating the temporary support 10 from the glass laminate 110 with a member, it is more possible that the fragments of the polyimide resin layer 12 are electrostatically adsorbed to the temporary support 10 by controlling the spraying and humidity with an ionizer. Can be suppressed.

  The above-described method for manufacturing the electronic device 120 is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

  As the electronic device 120 manufactured by the above method, a display panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, and a thin film having a glass substrate and a thin film secondary battery member. Examples thereof include a secondary battery, an electronic component having a glass substrate and an electronic device member. Examples of the display device panel include 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 flowchart showing manufacturing steps in the second embodiment of the method for manufacturing an electronic device of the present invention. As shown in FIG. 3, the manufacturing method of an electronic device is based on a polyimide resin layer forming step S102 (corresponding to step (1)) in which a predetermined polyimide resin layer is disposed on a temporary support, and the outer dimensions of the polyimide resin layer. A glass substrate lamination step S110 (corresponding to step (2 ′)) for laminating a glass substrate having a small external dimension on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer, A cutting step S112 for cutting the polyimide resin layer and the temporary support along the outer peripheral edge (corresponding to step (5)), a member forming step S106 for arranging the electronic device member on the glass substrate (corresponding to step (3)) ), And a separation step S108 (step (4)) obtained by separating the electronic device.
Moreover, FIG. 4 is typical sectional drawing which shows in order each manufacturing process in 2nd Embodiment of the manufacturing method of the electronic device of this invention.
Each step shown in FIG. 3 is the same procedure as the step shown in FIG. 1 except for the glass substrate laminating step S110 and the cutting step S112. Will be mainly described, and the glass substrate lamination step S110 and the cutting step S112 will be mainly described.

<Process (2 '): Glass substrate lamination process S110>
In step (2 ′), a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer. This is a step of obtaining a laminate. As shown in FIG. 4 (A), the polyimide resin layer 12 is disposed on the temporary support 10 in the polyimide resin layer forming step S102, and then this step S110 is performed as shown in FIG. 4 (B). By doing so, the glass substrate 14 having an outer dimension smaller than the outer dimension of the polyimide resin layer 12 is disposed on the polyimide resin layer 12. The glass substrate 14 is laminated on the polyimide resin layer so that a peripheral region that does not contact the glass substrate 14 remains in the polyimide resin layer 12. In other words, the glass substrate 14 is laminated on the polyimide resin layer 12 such that the polyimide resin layer 12 is exposed on the outer periphery of the glass substrate 14.
More specifically, as shown in FIG. 5A, the glass substrate 14 is laminated on the polyimide resin layer 12 so that the glass substrate 14 does not contact the peripheral region 12 b of the polyimide resin layer 12.
In general, the exposed surface of the polyimide resin layer 12 is likely to have a convex portion near the peripheral edge due to the influence of the surface tension (see FIG. 5B). When the glass substrate 14 is laminated, if it comes into contact with such a convex portion, the central portion of the glass substrate 14 is bent so as to be recessed, and the flatness of the glass substrate 14 may be impaired (see FIG. 5C). ). When the flatness of the glass substrate 14 is impaired, there is a risk that the position of the electronic device member disposed on the glass substrate 14 may be displaced, and as a result, the yield of the electronic device may be reduced.
Therefore, by using the glass substrate 14 having an outer shape smaller than that of the polyimide resin layer 12, the glass substrate 14 can be brought into contact with the polyimide resin layer 12 without being brought into contact with the convex portion. As a result, generation | occurrence | production of the bending of the glass substrate 14 is suppressed and the fall of an electronic device is suppressed.

In this embodiment, the outer shape of the polyimide resin layer 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 polyimide resin layer 12 in contact with the glass substrate 14 and the total area B of the polyimide resin layer 12 is preferably 0.98 or less, 0.95 The following is more preferable. If it is in the said range, generation | occurrence | production of the bending of the glass substrate 14 will be suppressed more. Although a minimum in particular is not restrict | limited, From points, such as productivity, it is preferable that it is 0.75 or more, and it is more preferable that it is 0.80 or more.
Further, the length from the outer peripheral edge of the glass substrate 14 to the outer peripheral edge of the polyimide resin layer 12 is preferably 10 mm or more, and more preferably 15 mm or more. If it is in the said range, generation | occurrence | production of the thickness nonuniformity of the polyimide resin layer 12 will be suppressed more. The upper limit is not particularly limited, but is preferably 100 mm or less from the viewpoint of productivity.

In addition, as a lamination | stacking method of the glass substrate 14, the method of the process (2) of 1st Embodiment mentioned above is mentioned.
By carrying out this step, a glass laminate 200 including the temporary support 10, the polyimide resin layer 12, and the glass substrate 14 is obtained.

<Step (5): Cutting step S112>
Step (5) is a step of cutting the polyimide resin layer and the temporary support in the glass laminate obtained in the step (2 ′) along the outer peripheral edge of the glass substrate. In other words, it is a step of cutting the outer periphery of each of the temporary support and the polyimide resin layer in the glass laminate to align the entire outer periphery of each of the temporary support, the polyimide resin layer, and the glass substrate. . More specifically, as shown in FIG. 4C, the temporary support 10 and the polyimide resin layer 12 are cut along the outer peripheral edge of the glass substrate 14 by this step S112, and the laminated body 300 (after cutting) A laminate that has been subjected to a cutting treatment is obtained.
A method for cutting the temporary support 10 and the polyimide resin layer 12 is not particularly limited, and a known method (cutting with a cutter, cutting with a laser, or the like) can be employed. For example, the method of Paragraph 0079-0095 of Unexamined-Japanese-Patent No. 2013-82182 is mentioned.

  After the step (5), by carrying out the step (3) described above, the electronic device member 16 is disposed on the glass substrate 14 as shown in FIG. Is formed. Further, by performing the above-described step (4), as shown in FIG. 4E, the temporary support 10 is removed from the member-attached glass laminate 110, and the polyimide resin layer 12, the glass substrate 14, and the electrons are removed. An electronic device 120 including the device member 16 is obtained.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the following examples and comparative examples, a glass plate made of non-alkali borosilicate glass (150 mm long, 150 mm wide, 0.1 mm thick, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., manufactured by Asahi Glass Co., Ltd.) The name “AN100”) was used. Further, as a temporary support, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.5 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) )It was used.

(Production of polyamic acid solution (A))
Paraphenylenediamine (10.8 g, 0.1 mol) was dissolved in 1-methyl-2-pyrrolidone (226.0 g) and stirred at room temperature. To this, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (29.4 g, 0.1 mol) was added over 1 minute, and the mixture was stirred at room temperature for 2 hours. The above formula (2-1) and // A polyamic acid solution (A) having a solid content concentration of 20% by mass containing a polyamic acid having a repeating unit represented by the formula (2-2) was obtained. When the viscosity of this solution was measured, it was 3000 centipoise at 20 ° C.
The viscosity is measured by measuring the rotational viscosity at 20 ° C. using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd.
In addition, 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 (X1), and A is represented by the formula (A1). It was a group.

(Manufacture of silane coupling agent solution (B))
After adding a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane, brand KBM903) to isopropyl alcohol (IPA), stirring the solution for about 1 hour with a mix rotor, B was produced. In addition, it added so that content of a silane coupling agent might be 0.1 mass% with respect to the total mass of isopropyl alcohol.

<Example 1>
The solution A is applied to the cleaned temporary support with a die coater, then dried at 90 ° C. for 10 minutes, and further dried at 150 ° C. for 10 minutes. A coating film containing acid was formed.
Next, the solution B was applied on the surface of the coating film with a die coater, and then dried at 120 ° C. for 10 minutes to obtain a coating film to which a silane coupling agent was applied.
Next, the coating film is subjected to a heat treatment at 350 ° C. for 1 hour under nitrogen to advance a polyamic acid ring-closing reaction to obtain a polyimide resin layer whose surface is treated with a silane coupling agent. It was.
Next, a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is laminated in alignment with the center of each substrate so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer, S1 was obtained. In the glass laminate S1, the peel strength (x) at the interface between the glass substrate and the polyimide resin layer was higher than the peel strength (y) at the interface between the polyimide resin layer and the temporary support.
Subsequently, the glass substrate of the glass laminate S1 is fixed on the surface plate to which the positioning jig is attached, and the second main body of the temporary support is overlapped with one of the outer peripheral edges of the glass substrate from the upper surface of the surface plate. After a cut line was cut on the surface with a diamond wheel cutter, the outside of the cut line of the temporary support was sandwiched with a clamping jig and cleaved. Similarly, after cleaving the outside of the temporary support that overlaps the remaining three sides of the outer peripheral edge of the glass substrate, the cut surface of the temporary support is ground and chamfered with a grindstone having a curved surface, and the cutting process is performed. The obtained glass laminate SA was obtained.
Next, a heat treatment at 450 ° C. for 1 hour, which is performed when the electronic device member is placed on the glass substrate, was performed on the glass laminate SA. After the heat treatment, when cooled to room temperature, changes in appearance such as separation of the glass substrate and temporary support, foaming and whitening of the polyimide resin layer were not observed in the glass laminate SA.
And while forming the notch part of peeling by inserting the stainless steel cutting tool of thickness 0.1mm in the interface of the temporary support body and polyimide resin layer in the corner part of one place among four places of glass laminated body SA, glass While adsorbing the vacuum suction pad to the surface that is not the release surface of the substrate and the temporary support, and spraying water on the interface between the temporary support and the polyimide resin layer, an external force is applied in the direction in which the glass substrate and the temporary support are separated from each other. Then, the temporary support was separated from the glass laminate SA without breaking. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
The polyimide resin layer was 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 resin layer was higher than the peel strength (y) at the interface between the polyimide resin layer and the temporary support.

<Example 2>
The solution A is applied to the cleaned temporary support with a die coater, then dried at 90 ° C. for 10 minutes, and further dried at 150 ° C. for 10 minutes. A coating film containing acid was formed.
Next, the coating film was subjected to a heat treatment at 350 ° C. for 1 hour under nitrogen to advance the ring closing reaction of the polyamic acid to obtain a polyimide resin layer.
Next, the solution B was applied on the surface of the polyimide resin layer with a die coater, and then a drying treatment was performed at 120 ° C. for 10 minutes to obtain a polyimide resin layer whose surface was treated with a silane coupling agent.
Next, a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is laminated in alignment with the center of each substrate so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer, S2 was obtained. In the glass laminate S2, the peel strength (x) at the interface between the glass substrate and the polyimide resin layer was higher than the peel strength (y) at the interface between the polyimide resin layer and the temporary support.
Subsequently, the glass substrate of the glass laminate S2 is fixed on the surface plate to which the positioning jig is attached, and the second main body of the temporary support is overlapped with one of the outer peripheral edges of the glass substrate from the upper surface of the surface plate. After a cut line was cut on the surface with a diamond wheel cutter, the outside of the cut line of the temporary support was sandwiched with a clamping jig and cleaved. Similarly, after cleaving the outside of the temporary support that overlaps the remaining three sides of the outer peripheral edge of the glass substrate, the cut surface of the temporary support is ground and chamfered with a grindstone having a curved surface, and the cutting process is performed. The obtained glass laminate SB was obtained.
Next, the glass laminate SB was subjected to a heat treatment at 450 ° C. for 1 hour, which is a heat treatment performed when the electronic device member is disposed on the glass substrate. After cooling to room temperature, no changes in appearance such as separation of the glass substrate and temporary support, foaming or whitening of the polyimide resin layer were observed in the glass laminate SB.
Then, the temporary support body was removed according to the procedure similar to Example 1 except having used glass laminated body SB instead of glass laminated body SA.
From the above results, it was confirmed that the peel strength (x) at the interface between the glass substrate and the polyimide resin layer was higher than the peel strength (y) at the interface between the polyimide resin layer and the temporary support.

  As shown in Examples 1 and 2 above, according to the method of the present invention, a glass laminate including a glass substrate having excellent surface flatness is produced without foaming between the polyimide resin layer and the glass substrate. We were able to. In addition, the glass laminate is subjected to heat treatment at 450 ° C. for 1 hour, which is a condition for producing the electronic device member, and then peeled off at the interface between the temporary support and the polyimide resin layer. The laminated body which consists of a polyimide resin layer and a glass substrate was able to be isolate | separated from the temporary support body. From these results, it was confirmed that the adhesion between the polyimide resin layer and the glass substrate was excellent. Moreover, even after manufacturing an electronic device on a glass substrate by a predetermined heat treatment, it has become clear that the temporary support can be separated from the glass laminate with a member.

(Adhesion evaluation)
In Examples 1 and 2, the adhesion of the polyimide resin layer to the glass substrate was evaluated by comparing the presence or absence of a floating defect (adhesion failure of the polyimide resin layer) generated when the temporary support was peeled off. The “floating defect” means a defect in which a part of the polyimide resin layer is pulled on the temporary support and the polyimide resin layer is locally peeled from the glass substrate when the temporary support is peeled off.
As a method for evaluating adhesion, five glass laminates were prepared in each of Examples 1 and 2, and the temporary support was peeled off in each sample, and floating defects were observed. As a method for observing floating defects, the presence or absence of a defect having a size of 1 mmΦ or more was visually confirmed under a fluorescent lamp, and “x” was given when there was a defect, and “◯” when there was no defect.
None of the five samples of Example 1 had “floating defects”. On the other hand, regarding two of the five samples of Example 2, although the temporary support could be peeled off, floating defects were found.
From these results, the aspect of Example 1 (corresponding to aspect X described above) is more excellent in adhesion between the glass substrate and the polyimide resin layer than the aspect of Example 2 (corresponding to aspect Y described above). It was confirmed.

In addition, as a temporary support body used in Examples 1 and 2, it was confirmed that a desired effect can be obtained even when a temporary support body that has been subjected to a mold release treatment obtained by the following procedure is used.
(Release processing)
Dimethylpolysiloxane was brought into contact with the surface of a glass plate made of alkali-free borosilicate glass, and a baking treatment at 350 ° C. was performed.

<Comparative Example 1>
The solution A is applied to the cleaned temporary support with a die coater, then dried at 90 ° C. for 10 minutes, and further dried at 150 ° C. for 10 minutes. A coating film containing acid was formed.
Next, the solution B was applied on the surface of the coating film with a die coater, and then dried at 120 ° C. for 10 minutes to obtain a coating film to which a silane coupling agent was applied.
Next, a glass substrate having an outer dimension smaller than the outer dimension of the coating film was laminated in alignment with the center of each substrate so that a peripheral region that did not contact the glass substrate remained in the coating film.
Thereafter, the coating film was subjected to a heat treatment at 350 ° C. for 1 hour under nitrogen to advance the ring closing reaction of the polyamic acid.
After the heat treatment, countless foaming occurred between the polyimide resin layer and the glass substrate, and the flatness of the glass substrate surface was impaired.
The form of the comparative example 1 corresponds to the form of Patent Document 2, and it was impossible to manufacture a predetermined glass laminate and an electronic device by this method.

<Example 4>
In this example, an OLED was manufactured using the glass laminate SA obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon were formed in this order on the second main surface of the glass substrate in the glass laminate SA by the plasma CVD method. Next, low concentration boron was injected into the amorphous silicon layer by an ion doping apparatus, and heat treatment was performed in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer was crystallized by a laser annealing apparatus. Next, low concentration phosphorus was injected into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method to form N-type and P-type TFT areas. Next, a silicon 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, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method. A gate electrode was formed. Next, high concentration boron and phosphorus were implanted into desired areas of the N-type and P-type, respectively, by photolithography and an ion doping apparatus to form a source area and a drain area. Next, on the second main surface side of the glass substrate, an interlayer insulating film was formed by silicon oxide film formation by a plasma CVD method, and a TFT electrode was formed by aluminum film formation by sputtering and etching using a photolithography method. Next, after performing heat treatment and hydrogenation treatment in a hydrogen atmosphere, a passivation layer was formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin was applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole were formed by photolithography. Next, a film of indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as the hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then aluminum was formed by a sputtering method. Next, another glass substrate was attached to the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure was formed on a glass substrate, and a glass laminate S1 (hereinafter referred to as panel A) having the organic EL structure on the glass substrate was a member of the present invention. It is a glass laminated body.
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm was inserted into the interface between the temporary support body and the polyimide resin layer at the corner portion of the panel A, Peeling was given to the interface between the temporary support and the polyimide resin layer. And after adsorb | sucking the support glass surface of the panel A with a vacuum suction pad, the suction pad was raised. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad was pulled up while continuing to spray a neutralizing fluid from the ionizer toward the formed gap and while supplying water to the peeling front. As a result, the temporary support could be peeled off and an electronic device was obtained.
Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module. The process was carried out to produce an OLED. The OLED obtained in this way did not have any problems in characteristics.
Note that the temperature of the heat treatment for manufacturing the electronic device was 450 ° C. at the maximum.

DESCRIPTION OF SYMBOLS 10 Temporary support body 12 Polyimide resin layer 14 Glass substrate 16 Electronic device member 100,200 Glass laminated body 110 Glass laminated body with member 120 Electronic device 300 Laminated body after cutting

Claims (8)

On the temporary support, a step (1) of forming a polyimide resin layer whose surface opposite to the temporary support is treated with a silane coupling agent;
Placing a glass substrate having a thickness of 0.2 mm or less on the polyimide resin layer to obtain a glass laminate (2);
Placing the electronic device member on the surface of the glass substrate to obtain a glass laminate with the member (3);
A method of manufacturing an electronic device, comprising: removing the temporary support from the glass laminate with members to obtain an electronic device including the polyimide resin layer, the glass substrate, and the electronic device member (4). .   The step (1) is a step (A) of applying a composition containing polyamic acid on a temporary support to form a coating film containing polyamic acid, and a silane coupling agent is applied on the coating film surface. A step (B) of performing, and a step (C) of obtaining a polyimide resin layer in which the surface opposite to the temporary support side is treated with a silane coupling agent by subjecting the coating film to a heat treatment. 2. A method for producing an electronic device according to 1.   The step (1) includes a step (D) of forming a polyimide resin layer on the temporary support, and a surface opposite to the temporary support by applying a silane coupling agent on the surface of the polyimide resin layer. And a step (E) of obtaining a polyimide resin layer treated with a silane coupling agent. In the step (2), a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer. Step (2 ′)
A step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer peripheral edge of the glass substrate between the step (2) and the step (3) is further performed. The manufacturing method of the electronic device of any one of Claims 1-3 provided. A temporary support, a polyimide resin layer treated with a silane coupling agent on the surface opposite to the temporary support, and a glass substrate in this order;
To arrange an electronic device member on the surface of the glass substrate, and then remove the temporary support to obtain an electronic device including the polyimide resin layer, the glass substrate, and the electronic device member. In the manufacturing method of the glass laminate used,
On the temporary support, a step (1) of forming a polyimide resin layer whose surface opposite to the temporary support is treated with a silane coupling agent;
The manufacturing method of a glass laminated body provided with the process (2) which arrange | positions the glass substrate of thickness 0.2mm or less on the said polyimide resin layer, and obtains the said glass laminated body.   The step (1) is a step (A) of applying a composition containing polyamic acid on a temporary support to form a coating film containing polyamic acid, and a silane coupling agent is applied on the coating film surface. A step (B) of performing, and a step (C) of obtaining a polyimide resin layer in which the surface opposite to the temporary support side is treated with a silane coupling agent by subjecting the coating film to a heat treatment. 5. A method for producing a glass laminate according to 5.   The step (1) includes a step (D) of forming a polyimide resin layer on the temporary support, and a surface opposite to the temporary support by applying a silane coupling agent on the surface of the polyimide resin layer. The manufacturing method of the glass laminated body of Claim 5 provided with the process (E) which obtains the polyimide resin layer processed with the silane coupling agent. In the step (2), a glass substrate having an outer dimension smaller than the outer dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region that does not contact the glass substrate remains in the polyimide resin layer. Step (2 ′)
The process of (5) further comprising a step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer peripheral edge of the glass substrate after the step (2). The manufacturing method of the glass laminated body of any one.