KR20160016618A - Manufacturing method of electronic device and manufacturing method of glass laminate - Google Patents

Abstract

(1) a step (1) of forming, on a temporary support, a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent; and a step A step (2) of arranging a glass substrate to obtain a glass laminate, a step (3) of arranging a member for an electronic device on the surface of the glass substrate to obtain a glass laminate provided with the member, and (4) of removing the temporary support from the glass laminate thus obtained to obtain an electronic device including the polyimide resin layer, the glass substrate, and the electronic device member .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an electronic device,

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

The present application is based on Japanese Patent Application No. 2014-158116 filed on August 1, 2014, the contents of which are incorporated herein by reference.

In recent years, devices (electronic devices) such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED) have been made thinner and lighter in weight. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate in the manufacturing process of the device is lowered.

Accordingly, a technique of reinforcing a glass substrate by disposing a resin layer or the like on a glass substrate has been disclosed (for example, Patent Document 1). However, the size of the thinned glass substrate is further enlarged, and it is difficult to form a resin layer having excellent properties on such a glass substrate. For example, when a composition for forming a resin layer is provided 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, as a method of forming a resin layer on a glass substrate, a transfer method has been proposed (Patent Document 2). More specifically, in the example of Patent Document 2, a pre-cured laminate having an uncured curable resin composition layer and a glass substrate in this order is formed on the surface showing ease of peeling of the releasable auxiliary substrate, Thereafter, the uncured curable resin composition layer in the pre-cured laminate is cured to obtain a cured laminate having a resin layer, and a cured resin composition layer is obtained from the cured laminate by using a glass substrate and a resin layer , A glass substrate provided with a resin layer is obtained.

Japanese Patent Publication No. 2002-542971 International Publication No. 2013/054792

In recent years, the polyimide resin layer has attracted attention due to its excellent heat resistance.

The inventors of the present invention attempted to prepare a glass substrate provided with the resin layer by using a composition containing a polyamic acid corresponding to a precursor of a polyimide resin as a curable resin composition with reference to the transfer method described in Patent Document 2 . More specifically, a composition comprising a polyamic acid was applied onto a releasable auxiliary substrate to form an uncured curable resin composition layer, a glass substrate was laminated thereon, and heat treatment was performed. As a result, the obtained resin layer ( Foaming occurred at the interface between the glass substrate and the polyimide resin layer. It is presumed that foaming is caused by so-called volatilization of water which occurs during imidization. As a result, the surface of the glass substrate at the portion where foaming occurred swells and the flatness of the surface of the glass substrate is damaged. When the flatness on the surface of the glass substrate deteriorates as described above, positional deviations are likely to occur when various electronic device members are arranged on the surface of the glass substrate, and as a result, the productivity of the electronic device is deteriorated.

Further, 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 deteriorated.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide an electronic device comprising a member for an electronic device, a glass substrate, and a polyimide resin layer for reinforcing the glass substrate, And an object of the present invention is to provide an electronic device manufacturing method which suppresses the occurrence of foaming between the substrate and the polyimide resin layer, and which is excellent in adhesion between the substrate and the polyimide resin layer.

Another object of the present invention is to provide a method for producing a glass laminate including a temporary support, a polyimide resin layer and a glass substrate, which can be suitably used for the production of the electronic device.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems and have completed the present invention.

That is, a first aspect of the present invention is a method for producing a polyimide resin sheet, comprising the steps of: (1) forming a polyimide resin layer on the temporary support, the surface of which is treated with a silane coupling agent on the side opposite to the temporary support; A step (2) of arranging a glass substrate having a thickness of 0.2 mm or less to obtain a glass laminate, a step (3) of arranging a member for an electronic device on the surface of the glass substrate to obtain a glass laminate having the member, (4) of removing the temporary support from the glass laminate provided with the polyimide resin layer, the glass substrate and the electronic device member.

(A) a step (A) of applying a composition containing a polyamic acid on a temporary support to form a coating film containing a polyamic acid, and a step A step (B) of applying a ligneous agent to the coating film, and a step (C) of applying a heat treatment to the coating film to obtain a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent.

(D) a step (D) of forming a polyimide resin layer on a temporary support, and a step (D) of applying a silane coupling agent on the surface of the polyimide resin layer to form a (E) of obtaining a polyimide resin layer whose surface has been treated with a silane coupling agent.

In the first aspect, the step (2) is characterized in that a glass substrate having an external dimension smaller than the external dimensions of the polyimide resin layer is formed on the polyimide resin layer so that the peripheral region that does not contact the glass substrate remains in the polyimide resin layer (5 ') of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer periphery of the glass substrate between the step (2) and the step (3) .

A second mode of the present invention is a method for manufacturing a semiconductor device comprising a temporary support, a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent, and a glass substrate in this order, A method for producing a glass laminate, which is used for obtaining an electronic device including a polyimide resin layer, a glass substrate, and a member for an electronic device by disposing a member and then removing the temporary support, A step (1) of forming a polyimide resin layer whose surface on the side opposite to the temporary support side is treated with a silane coupling agent, and a step of arranging a glass substrate having a thickness of 0.2 mm or less on the polyimide resin layer to obtain a glass laminate (2). ≪ / RTI >

(A) a step (A) of applying a composition comprising a polyamic acid on a temporary support to form a coating film containing a polyamic acid, and a step A step (B) of applying a ligneous agent to the coating film, and a step (C) of applying a heat treatment to the coating film to obtain a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent.

(D) a step (D) of forming a polyimide resin layer on the temporary support, and a step (D) of applying a silane coupling agent on the surface of the polyimide resin layer to form a (E) of obtaining a polyimide resin layer whose surface has been treated with a silane coupling agent.

In the second aspect, it is preferable that the step (2) is a method in which a glass substrate having an external dimension smaller than the external dimensions of the polyimide resin layer is formed on the polyimide resin layer so that a peripheral region not contacting the glass substrate remains in the polyimide resin layer (2 '), and after the step (2), it is preferable to further include a step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer periphery of the glass substrate.

According to the present invention, an electronic device including a member for an electronic device, a glass substrate, and a polyimide resin layer for reinforcing the glass substrate can be easily manufactured. In the obtained electronic device, the glass substrate and the polyimide resin layer It is possible to provide a method of manufacturing an electronic device which is excellent in adhesion between the two.

According to the present invention, it is also possible to provide a method for producing a glass laminate including a temporary support, a polyimide resin layer, and a glass substrate, which can be suitably used for manufacturing the electronic device.

1 is a flowchart showing a manufacturing process of a first embodiment of a method of manufacturing an electronic device of the present invention.
2 (A) to 2 (D) are schematic sectional views showing a first embodiment of a method for manufacturing an electronic device according to the present invention in the order of steps.
Fig. 3 is a flowchart showing the manufacturing process of the second embodiment of the method for manufacturing an electronic device of the present invention.
4A to 4E are schematic cross-sectional views showing a second embodiment of the method for manufacturing an electronic device of the present invention in the order of steps.
5 (A) is a top view of the glass laminate obtained in the step (2 '). 5 (B) is an enlarged cross-sectional view of the vicinity of the periphery of the polyimide resin layer. FIG. 5C is an enlarged cross-sectional view of a glass substrate laminated on the polyimide resin layer in FIG. 5B. FIG.

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 various modifications and substitutions may be made without departing from the scope of the present invention. .

One characteristic feature of the electronic device and the method for producing a glass laminate of the present invention is that a polyimide resin layer whose surface is treated with a silane coupling agent is disposed on a temporary support and is transferred onto a glass substrate have.

It is difficult to form a uniform coating film on the surface of a thinned glass substrate and various materials are added to the surface of the thinned glass substrate. Even if a coating film is formed, a subsequent treatment (for example, a drying treatment) The glass substrate is warped to cause irregularities in the thickness of the coating film, resulting in cracking of the layer (for example, a resin layer) formed on the glass substrate surface. When various materials are directly applied on the surface of the glass substrate, the surface opposite to the side to which the glass substrate is provided usually comes in contact with a member for supporting the glass substrate. If such members are brought into contact with each other, scratches may occur on the surface of the glass substrate, which may deteriorate the surface properties, which may adversely affect the subsequent production of the electronic device member. In addition, when the glass substrate is coated on the vacuum adsorption table in many cases, it is often fixed to the vacuum adsorption table. If the thickness of the glass substrate is small, the temperature difference between the suction holes and the contact portion tends to cause unevenness of the liquid film and dryness.

On the other hand, in the present invention, since the polyimide resin layer is once formed on the temporary support and transferred to the glass substrate, the number of times the glass substrate is handled is reduced, and the damage to the glass substrate surface can be reduced. Further, since the polyimide resin layer is first formed on the temporary support, the thickness of the polyimide resin layer can be more easily controlled. Further, since the surface of the polyimide resin layer is treated with a silane coupling agent, adhesion to a glass substrate is excellent. Thereby, as described later, after the member for electronic devices is formed on the glass substrate in the glass laminate, the temporary support can be easily removed by peeling the interface between the temporary support and the polyimide resin layer.

As described above, according to the present invention, a predetermined electronic device can be manufactured easily. The glass laminate of the present invention can also be suitably used for easily manufacturing an electronic device including a glass substrate and a polyimide resin layer serving as a reinforcing layer of a thin glass substrate.

[First Embodiment]

1 is a flowchart showing a manufacturing process in a first embodiment of a method of manufacturing an electronic device of the present invention. As shown in Fig. 1, a method of manufacturing 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, a glass A glass substrate lamination step S104 (corresponding to the step (2)) for disposing the substrate, a member forming step S106 (corresponding to the step (3)) for disposing the electronic device member on the glass substrate, And step S108 (step (4)).

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

Hereinafter, with reference to Figs. 1 and 2 (A) to 2 (D), the materials used in each step and the procedure thereof will be described in detail. First, the polyimide resin layer forming step S102 will be described in detail.

≪ Process (1): polyimide resin layer formation process S102 >

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

Hereinafter, the members and materials used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Temporary support)

The temporary support 10 is a substrate for supporting the polyimide resin layer until the step (4) described later and is separated from the polyimide resin layer 12 at the step (4). That is, the temporary support 10 is in peelable contact with the polyimide resin layer 12.

As the temporary support 10, there is no particular limitation on the kind of the temporary support 10 as long as it can be peeled off from the polyimide resin layer 12, and a known substrate can be used. As the temporary support, for example, a glass plate, a plastic plate (for example, a silicon substrate), a metal plate such as an SUS plate, a substrate laminated thereon, and the like are used.

Further, as described later, when a leveling agent (surface conditioner) is used in manufacturing the polyimide resin layer 12 (in other words, when the leveling agent is contained in the polyimide resin layer), by the effect of the leveling agent, Both the temporary support 10 and the polyimide resin layer 12 are easily peeled off regardless of the kind of the support material.

The thickness of the temporary support 10 is not particularly limited and may be thicker or thinner than the polyimide resin layer 12 to be laminated. 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 existing manufacturing apparatus and handling property.

If necessary, the surface of the temporary support 10 may be treated with a silicone-based releasing agent (for example, a silicone oil such as dimethylpolysiloxane) or other releasing agent to improve the releasability of the polyimide resin layer 12. As a specific method of the mold releasing treatment as described above, there is a method in which the silicone releasing agent is brought into contact with the surface of the temporary support 10 to perform a baking treatment (for example, about 350 캜).

(Polyimide resin layer)

The polyimide resin layer 12 is a layer disposed on the temporary support 10 and the surface 12a (the surface opposite to the side of the temporary support 10) is treated with a silane coupling agent. The polyimide resin layer 12 is transferred onto the glass substrate 14 by contacting the surface 12a with the glass substrate 14 in the glass substrate laminating step S104 as described later.

Although the thickness of the polyimide resin layer 12 is not particularly limited, it is preferable that the thickness of the polyimide resin layer 12 is 1 占 퐉 More preferably not less than 2 탆, more preferably not less than 4 탆 from the viewpoint of releasability. The upper limit is not particularly limited, but is preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less from the viewpoint of thinning.

The thickness means an average thickness, and the thickness of any five points of the polyimide resin layer 12 is measured and arithmetically averaged.

The polyimide resin layer 12 is a layer containing a polyimide resin, but the structure of the polyimide resin is not particularly limited, and a known polyimide resin may be used. It is preferable to include a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the following formula (1) from the viewpoints of heat resistance and handleability. The polyimide resin contains the repeating unit represented by the formula (1) as the main component (preferably 95 mol% or more based on the total repeating units), but other repeating units other than the repeating units (for example, -1) or (2-2)).

The residue (X) of the tetracarboxylic acid means a tetracarboxylic acid residue excluding the carboxyl group in the tetracarboxylic acids, and the residue (A) of the diamines means the diamine residue excluding the amino group in the diamines.

In the formula (1), X represents a tetracarboxylic acid residue excluding a carboxyl group in a tetracarboxylic acid, and A represents a diamine residue excluding an amino group in a diamine.

In the formula (1), X represents a tetracarboxylic acid residue excluding a carboxy group in tetracarboxylic acids and includes at least one group selected from the group consisting of the following formulas (X1) to (X4) . Among them, 50 mol% or more (preferably 80 to 100 mol%) of the total number of X is preferably represented by the following formulas (X1) to (X4) in view of better heat resistance of the polyimide resin layer 12 And at least one group selected from the group consisting of R < 1 > It is more preferable that the substantially total number (100 mol%) of the total number of X includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4). A is preferably a diamine residue other than an amino group in the diamines and preferably contains at least one group selected from the group consisting of the following formulas (A1) to (A8). Among them, 50 mol% or more (preferably 80 to 100 mol%) of the total number of A is preferably represented by the following formulas (A1) to (A8) in view of better heat resistance of the polyimide resin layer 12 And at least one group selected from the group consisting of R < 1 > It is more preferable that the substantially total number (100 mol%) of the total number of A contains at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

It is preferable that 80 to 100 mol% of the total number of X is at least one kind selected from the group consisting of the groups represented by the following formulas (X1) to (X4) from the viewpoint that the polyimide resin layer (12) Group and more preferably 80 to 100 mol% of the total number of A comprises at least one group selected from the group consisting of the following formulas (A1) to (A8), and the total number of X (100 mol%) substantially contains the total number of the total number of A (100 mol%) and at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4) More preferably at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

Among them, X is preferably a group represented by the formula (X1) and a group represented by the formula (X4), and the group represented by the formula (X1) is preferably a group represented by the formula desirable.

The group represented by the formula (A1) and the group represented by the formula (A6) are preferable, and the group represented by the formula (A1) is more preferable for A from the viewpoint of the heat resistance of the polyimide resin layer .

As the polyimide resin containing a proper combination of the groups represented by the formulas (X1) to (X4) and the groups represented by the formulas (A1) to (A8), it is preferable that X is a group represented by the formula (X1) And polyimide resin 2 in which X is a group represented by the formula (X4) and A is a group represented by the formula (A6). In the case of polyimide resin 1, heat resistance is better. Further, polyimide resin 2 is preferable from the viewpoint of colorless transparency.

The number of repeating units (n) of the repeating unit represented by the formula (1) in the polyimide resin is not particularly limited, but is preferably an integer of 2 or more, and the heat resistance of the polyimide resin layer 12 and the film- Is preferably from 10 to 10000, more preferably from 15 to 1000.

The polyimide resin may contain at least one member selected from the group consisting of the following groups as the residue (X) of the tetracarboxylic acid within a range that does not impair the heat resistance. In addition, two or more groups exemplified below may be included.

The polyimide resin may contain at least one selected from the group consisting of the following groups as residues (A) of the diamines within a range that does not impair the heat resistance. In addition, two or more groups exemplified below may be included.

Although the content of the polyimide resin in the polyimide resin layer 12 is not particularly limited, it is preferably 50 to 100 mass% with respect to the total mass of the resin layer in view of better heat resistance of the polyimide resin layer 12 , More preferably from 75 to 100 mass%, and still more preferably from 90 to 100 mass%.

The polyimide resin layer 12 may contain components other than the polyimide resin (for example, a filler that does not hinder the heat resistance) if necessary.

Examples of the filler that does not impair the heat resistance include fibrous fillers or non-fibrous fillers such as plate-shaped, rounded, granular, irregular, and crushed products. Specific examples thereof include glass fibers, PAN- , Stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate Silica glass, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, and the like. , Metal powder, metal flake, metal ribbon, metal oxide, carbon powder, graphite, carbon flake, And the present nanotubes. Specific examples of the metal species of the metal powder, the metal flake and the metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chrome and tin.

The polyimide resin layer 12 is formed of polyamic acid (a curable resin which is a polyimide resin due to thermal curing) in view of easy chemical control of the silane coupling agent to be described later and the carboxylic acid of the side chain, As shown in FIG. That is, the polyimide resin layer 12 is preferably a layer formed by subjecting a layer containing a polyamic acid to a heat treatment. Further, the polyimide resin layer 12 is preferably a layer formed by thermally curing the residue of the tetracarboxylic acid represented by the formula (1) (Polyamide acid) layer made of a polyimide resin containing a repeating unit having a repeating unit (X) and a residue of a diamine (A). The heat treatment may be performed stepwise by changing the temperature.

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

The kind of the silane coupling agent to be used is not particularly limited, but it is preferable that the silane coupling agent has a reactive group capable of reacting with the polyamic acid used for 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 via the reactive group, and forms a bond with the glass substrate 14 via the silanol group contained in the silane coupling agent Bonds are formed, and the adhesion between the two is further improved.

The reactive group is not particularly limited as long as it is capable of reacting with a functional group in the polyamic acid. Examples of the reactive group include a group capable of reacting with a carboxylic acid group or a secondary amino group (-NH-) in polyamic acid. More specifically, A primary amino group, a secondary amino group, a hydroxyl group, a carboxylic acid group, and an epoxy group.

A suitable form of the silane coupling agent is a compound represented by the following formula (3).

(3) XL-Si (Y) ₃

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

The definitions of the reactive groups are as described above.

Examples of the divalent linking group include -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an arylene group, a heterocyclic group (a heteroarylene group) And combinations thereof.

The hydrolyzable group represents a group capable of forming a silanol group or a siloxane condensate, and specific examples thereof include a halogen group, an alkoxy group, an acyloxy group, and an isocyanate group. Among them, an alkoxy group (preferably having 1 to 2 carbon atoms) is preferable.

(Process procedure)

The procedure of the step (1) is not particularly limited as long as the polyimide resin layer treated with the silane coupling agent can be formed on the surface of the temporary support opposite to the temporary support side, and known methods can be employed .

Of these, the following two types are preferable, and the form X is more preferable because the adhesion between the polyimide resin layer and the glass substrate is more excellent.

(Form X) A process for producing a polyamic acid, comprising the steps of: (A) applying a composition containing a polyamic acid on a temporary support to form a coating film containing polyamic acid; (B) applying a silane coupling agent on the coating film surface; And a step (C) of applying a heat treatment to the coated film to obtain a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent

(D) a step (D) of forming a polyimide resin layer on the temporary support (Form Y); and a step (D) of forming a polyimide resin layer on the surface of the polyimide resin layer on the surface opposite to the temporary support side with a silane coupling agent A step (E) of obtaining a polyimide resin layer

The difference between the form X and the form Y lies in that the timing of giving the silane coupling agent is different. In Form X, a silane coupling agent is provided on a coating film containing a polyamic acid, and then a heating treatment (cyclization treatment (imidization treatment)) is carried out to cure the coating film, And a mid resin layer is obtained. On the other hand, Form Y is a form in which a polyimide resin layer is once formed, and then a silane coupling agent is applied to the polyimide resin layer to obtain a polyimide resin layer whose surface is treated with a silane coupling agent.

Comparing the above two forms, Form X shows that the interface between the layer of the silane coupling agent and the coating film containing polyamic acid can easily be mixed with each other, so that the adhesion between the layer and the polyimide resin layer is excellent, The adhesion of the glass substrate is more excellent. Further, when the silane coupling agent has a reactive group capable of reacting with the polyamic acid, the adhesion between the polyimide resin layer and the glass substrate is particularly excellent in the form X.

Hereinafter, the procedure of Forms X and Y will be described in detail.

(Form X)

In Form X, first, a step (A) of applying a composition containing a polyamic acid on a temporary support to form a coating film containing a polyamic acid is carried out.

First, the material (polyamic acid or the like) used in the present step will be described in detail below.

The polyamic acid is a curable resin that is made of a polyimide resin by thermosetting and is preferably a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and at least a part of the tetracarboxylic acid dianhydride is represented by the following formula And at least one tetracarboxylic acid dianhydride selected from the group consisting of compounds represented by the following formulas (Y1) to (Y4), wherein at least a part of the diamines is represented by the following formulas (B1) to (B8) And at least one kind of diamine selected from the group consisting of a compound represented by the general formula

Further, the polyamic acid is usually represented by a structural formula containing a repeating unit represented by the following formula (2-1) and / or formula (2-2). The definitions of X and A in the formulas (2-1) and / or (2-2) are as described above.

The reaction conditions of the tetracarboxylic acid dianhydride and the diamines are not particularly limited and the reaction is preferably carried out at -30 to 70 占 폚 (preferably -20 to 40 占 폚) since polyamic acid can be efficiently synthesized desirable.

The mixing ratio of the tetracarboxylic acid dianhydride to the diamine is not particularly limited, but the tetracarboxylic acid dianhydride is preferably used in an amount of 0.66 to 1.5 mol, more preferably 0.9 to 1.1 mol, , The reaction is carried out at 0.97 to 1.03 mole.

When a tetracarboxylic acid dianhydride is reacted with a diamine, an organic solvent may be used if necessary. The kind of the organic solvent to be used is not particularly limited, and examples thereof include N, N-dimethylacetamide, N, N, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p- chlorophenol, Diglyme, triglyme, tetraglyme, dioxane, gamma -butyrolactone, dioxolane, cyclohexanone, cyclopentanone, and the like, or two or more of them may be used in combination.

In the above reaction, other tetracarboxylic acid dianhydrides other than the tetracarboxylic acid dianhydrides selected from the group consisting of the compounds represented by the above-mentioned formulas (Y1) to (Y4) may be used together if necessary.

In the above reaction, diamines other than the diamines selected from the group consisting of the compounds represented by the above-mentioned formulas (B1) to (B8) may be used together if necessary.

The composition containing the polyamic acid may contain components other than the polyamic acid, if necessary.

For example, the composition may contain a solvent. As the solvent, an organic solvent is particularly preferable in view of the solubility of the polyamic acid. As the organic solvent to be used, an organic solvent used in the reaction of the above-mentioned polyamic acid can be mentioned.

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, but it is generally preferably 5 to 95 mass% , More preferably from 10 to 90 mass%.

If necessary, a dehydrating agent or a dehydrating ring-closing catalyst may be used together to promote dehydration ring closure of the polyamic acid. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used.

If necessary, the composition may contain a leveling agent. A leveling agent is a compound which lowers the surface tension of a coating and improves wetting to the coating. As a leveling agent, a general leveling agent can be used, and examples thereof include a fluorine leveling agent (for example, a fluorine surfactant), an acrylic leveling agent, a silicone leveling agent (for example, a silicone surfactant) Or two or more species can be used.

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

The thickness of the coating film obtained by the above treatment is not particularly limited and is appropriately adjusted so as to obtain the above-described polyimide resin layer having an appropriate thickness.

After the application, if necessary, a drying treatment may be performed to remove volatile components (for example, solvent) contained in the coating film. The method of the drying treatment is not particularly limited as far as it is a method in which the cyclization reaction (imidization reaction) of the polyamic acid does not proceed. For example, a method of performing a heat treatment or a method of performing air drying treatment.

The heating conditions vary depending on the structure of the polyamic acid to be used, but the heating temperature is usually 40 to 200 占 폚, and 40 to 150 占 폚 is preferable in that foaming of the resin layer is suppressed. In particular, in the range of the above-mentioned heating temperature, it is preferable to heat to less than the boiling point of the solvent. As the heating time, an optimum time is appropriately selected according to the structure of the polyamic acid to be used, but it is preferably 5 to 60 minutes, and more preferably 10 to 30 minutes, from the viewpoint of further preventing the depolymerization of the polyamic acid.

The atmosphere of heating is not particularly limited, and is carried out, for example, in air, under vacuum, or under an inert gas. When the reaction is carried out under vacuum, it is possible to remove the volatile components in a shorter time even if heating is carried out at a low temperature, and furthermore, depolymerization of the polyamic acid can be more controlled.

The drying treatment may also be carried out stepwise under different temperature conditions.

Next, a step (B) of applying a silane coupling agent to the surface of the coating film containing the polyamic acid obtained in the above step (A) is carried out.

The method of applying the silane coupling agent is not particularly limited, and a known method may be employed. For example, a method of applying a composition containing a silane coupling agent on the surface of a coating film (coating method), or a method of immersing a support provided with the coating film in a composition containing a silane coupling agent (immersion method) . Among them, the coating method is preferable in that the amount of the silane coupling agent can be adjusted easily. In the coating method, a method of applying a composition containing a silane coupling agent is not particularly limited, and the above-mentioned method of applying a composition containing a polyamic acid can be mentioned.

The composition containing the silane coupling agent includes the silane coupling agent described above.

In addition, the composition containing the silane coupling agent may contain a solvent if necessary. As the solvent, there may be mentioned a solvent which may be included in the composition containing the polyamic acid.

After the application of the silane coupling agent, if necessary, a drying treatment may be performed to remove volatile components (e.g., solvent) contained in the coating film. The method of the drying treatment is not particularly limited as long as it is a method in which the cyclization reaction (imidization reaction) of the polyamic acid does not proceed rapidly. For example, a method of performing a heat treatment or a method of performing air drying treatment. Examples of conditions for the heat treatment include the conditions of the heat treatment (heating temperature, heating time, atmosphere) that may be performed in the above-mentioned step (A).

Next, a step (C) of obtaining a polyimide resin layer whose surface is treated with a silane coupling agent by applying a heat treatment to the coating film containing the polyamic acid to which the silane coupling agent is attached on the surface obtained in the step (B) . In the present step (C), a so-called ring closing reaction (imidization reaction) proceeds.

The heating temperature in the present step (C) is not particularly limited, but is preferably 250 to 500 ° C, more preferably 300 to 450 ° C in terms of lowering the residual solvent ratio and further increasing the imidization rate, Is more preferable.

The heating time is not particularly limited and the optimum time is appropriately selected according to the structure of the polyamic acid to be used. However, since the residual solvent ratio is lowered and the imidization rate is further elevated, 120 minutes is preferable, and 30 to 60 minutes is more preferable.

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

The heat treatment may also be carried out stepwise at different temperatures.

By the above-mentioned step (C), a polyimide resin layer containing a polyimide resin is formed.

The imidization ratio of the polyimide resin is not particularly limited, but is preferably 99.0% or more, and more preferably 99.5% or more, from the viewpoint of more excellent heat resistance of the polyimide resin layer.

A method of measuring the imidization ratio is a method in which a polyamic acid is heated at 350 DEG C for 2 hours under a nitrogen atmosphere at an imidization rate of 100% Is derived from the intensity ratio of the peak intensity from the imidecarbonyl group to the peak intensity of about 1780 cm ^-1 to the intensity (for example, the peak derived from the benzene ring: about 1500 cm ^-1 ).

(Form Y)

In Form Y, first, a step (D) of forming a polyimide resin layer on the temporary support is carried out.

The method of forming the polyimide resin layer is not particularly limited, and a known method can be employed. For example, there are a method (method 1) of obtaining a polyimide resin layer by applying a composition containing the above-mentioned polyamic acid on a temporary support to form a coating film, and thereafter conducting a heat treatment, or a method comprising a polyimide resin layer (A method 2) of applying a composition for forming a polyimide resin layer on a temporary support and, if necessary, applying a drying treatment to obtain a polyimide resin layer. Among them, the method 1 is preferable in that the thickness of the polyimide resin layer can be adjusted more easily. Method 1 corresponds to a mode in which the step (A) and the step (C) in the above-mentioned Form X are carried out, and the respective procedures and conditions are the same as the above-mentioned steps (A) and (C).

Next, a step (E) of applying a silane coupling agent to the surface of the polyimide resin layer obtained in the step (D) to obtain a polyimide resin layer whose surface is treated with a silane coupling agent is carried out.

The method of applying the silane coupling agent is not particularly limited, and for example, the same procedure as the step (B) in the above-mentioned Form X can be mentioned.

≪ Process (2): Glass substrate lamination step 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 the above step (1). 2B, the glass substrate 14 is placed on the surface 12a of the polyimide resin layer 12 treated with the silane coupling agent to form a temporary support (FIG. 2B) 10, the polyimide resin layer 12, and the glass substrate 14 in this order. Further, the polyimide resin layer 12 and the glass substrate 14 are closely contacted via a silane coupling agent.

Hereinafter, the members and materials used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Glass substrate)

The glass substrate 14 is provided with the electronic device member on the second main surface 14b which is in contact with the polyimide resin layer 12 on the first main surface 14a and on the opposite side from the polyimide resin layer 12 side . That is, the glass substrate 14 is a substrate used for forming an electronic device to be described later.

The type of the glass substrate 14 may be a general one, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 14 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage ratio. The coefficient of thermal expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio.

When the coefficient of linear expansion of the glass substrate 14 is large, various processes are likely to occur because the member forming process to be described later involves heat treatment in many cases. For example, in the case of forming a TFT (thin film transistor) on the glass substrate 14, if the glass substrate 14 on which the TFT is formed under cooling is cooled, the positional deviation of the TFT becomes excessive due to heat shrinkage of the glass substrate 14 There is a concern.

The glass substrate 14 is obtained by melting a glass raw material and molding the molten glass into a plate. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a pull call method, a lubrication method, or the like is used. In particular, the glass substrate 14 having a small thickness can be obtained by heating the glass molded into a plate shape at one time and heating the glass at a moldable temperature and stretching it by stretching or the like (thinning method) (lead-down method).

The type of the glass of the glass substrate 14 is not particularly limited, but is preferably an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90 mass% in terms of an oxide is preferable.

As the glass of the glass substrate 14, glass suitable for the kind of the electronic device member and the manufacturing process thereof is employed. For example, a glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free of an alkali metal component since the elution of the alkali metal component is likely to affect the liquid crystal (note that generally, Is included). Thus, the glass of the glass substrate 14 is appropriately selected based on the type of device to be applied and the manufacturing process thereof.

The thickness of the glass substrate 14 is 0.2 mm or less, preferably 0.15 mm or less, more preferably 0.10 mm or less from the viewpoints of reducing the thickness and / or weight of the glass substrate 14. When the thickness is 0.2 mm or less, it is possible to impart good flexibility to the glass substrate 14. When the thickness is 0.15 mm or less, the glass substrate 14 can be rolled up in a roll form.

The thickness of the glass substrate 14 is preferably 0.03 mm or more for ease of manufacture of the glass substrate 14 and ease of handling of the glass substrate 14.

Further, the glass substrate 14 may include two or more layers, and in this case, the material forming each layer may be a homogeneous material or a heterogeneous material. In this case, the "thickness of the glass substrate 14" means the total thickness of all the layers.

(Process procedure)

The method of laminating the glass substrate 14 on the surface of the polyimide resin layer 12 (on the surface opposite to the side of the temporary support 10 of the polyimide resin layer 12) is not particularly limited, Can be adopted.

For example, a method in which the glass substrate 14 is superimposed on the surface of the polyimide resin layer 12 under an atmospheric pressure environment. If necessary, the glass substrate 14 may be overlaid on the surface of the polyimide resin layer 12, and then the glass substrate 14 may be pressed onto the polyimide resin layer 12 using a roll or press. The bubbles mixed in between the layers of the polyimide resin layer 12 and the glass substrate 14 are relatively easily removed by pressing by roll or press.

The vacuum lamination method or the vacuum press method is more preferable because it suppresses mixing of bubbles and secures good adhesion. Even when minute bubbles remain, the bubbles do not grow due to heating, and there is an advantage that it is difficult to lead to distortion defects of the glass substrate 14. Further, bubbles are less likely to remain by compression bonding under vacuum heating.

When the glass substrate 14 is laminated, it is preferable that the surface of the glass substrate 14 contacting the polyimide resin layer 12 is sufficiently cleaned and laminated in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 14 is.

Further, after the glass substrate 14 is laminated, a pre-annealing treatment (heat treatment) may be performed if necessary. By performing the pre-annealing process, adhesion of the laminated glass substrate 14 to the polyimide resin layer 12 is improved, and positional deviation or the like of the electronic device member is unlikely to occur in the step (4) described later And the productivity of the electronic device is improved.

The conditions of the pre-annealing process are appropriately selected in accordance with the kind of the polyimide resin layer 12 to be used, but the peeling strength between the glass substrate 14 and the polyimide resin layer 12 is made more suitable (Preferably 200 to 400 占 폚) for 5 minutes or longer (preferably 5 to 30 minutes).

(Glass laminate)

The glass laminate 100 of the present invention obtained by the above process can be used for various purposes. For example, the glass laminate 100 can be used as a display panel, a PV, a thin film secondary battery, a semiconductor wafer And the like. Further, in the above applications, the glass laminate 100 is often exposed to high temperature conditions (for example, 400 DEG C or more) (for example, 1 hour or more).

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

This glass laminate 100 is used up to the step (4). That is, this 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. Thereafter, the glass laminate in which the member for an electronic device is formed is separated into the temporary support 10 and the electronic device, and the temporary support 10 does not constitute a part constituting the electronic device.

In the glass laminate 100, the polyimide resin layer 12 is fixed on the glass substrate 14, and the temporary support 10 is adhered to the polyimide resin layer 12 in a peelable manner. In the present invention, the above-mentioned fixation and releasable adhesion means a difference in peel strength (i.e., stress required for peeling), and fixing means a larger peeling strength than adhesion. That is, the peel strength of the interface between the polyimide resin layer 12 and the glass substrate 14 becomes larger than the peel strength between the interface of the polyimide resin layer 12 and the temporary support 10. In other words, peelable adhesion means that peeling is possible, and peeling is possible 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 a peeling strength x is applied to the interface between the glass substrate 14 and the polyimide resin layer 12. [ , The interface between the glass substrate 14 and the polyimide resin layer 12 is peeled off. The interface between the polyimide resin layer 12 and the temporary support 10 has a peel strength y and is exerted on the interface between the polyimide resin layer 12 and the temporary support 10 in the peeling direction The interface between the polyimide resin layer 12 and the temporary support 10 is peeled off.

In the glass laminate 100 (also referred to as a glass laminate having a member described later), the peel strength x is higher than the peel strength y. The glass laminate 100 of the present invention can be obtained by forming the temporary support 10 and the polyimide resin layer 10 in such a manner that stress is applied to the glass laminate 100 in the direction in which the temporary support 10 and the glass substrate 14 are peeled off. 12 and is separated into a laminate including the temporary support 10, the polyimide resin layer 12, and the glass substrate 14.

In addition, the adhesion between the polyimide resin layer 12 and the glass substrate 14 is enhanced by the above-mentioned silane coupling agent.

≪ Process (3): Member forming process S106 >

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

First, the electronic device member 16 used in the present step will be described in detail, and the procedure of the subsequent step will be described in detail.

(Member for electronic device (functional element))

The member 16 for the electronic device is a member formed on the glass substrate 14 in the glass laminate 100 and constituting at least a part of the electronic device. More specifically, as the member 16 for the electronic device, a member used for a display device panel, a solar cell, a thin film secondary battery, or an electronic part such as a semiconductor wafer on which a circuit is formed on a surface (for example, Members for solar cells, members for thin film secondary batteries, circuits for electronic parts).

For example, as a member for a solar cell, in a silicon type, a transparent electrode such as a tin oxide of a positive electrode, a silicon layer represented by a p layer / an i layer / an n layer and a metal of a negative electrode, Various types of members corresponding to the type, the quantum dot type, and the like.

Examples of members for a thin film secondary battery include a transparent electrode such as metal or metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, and a resin as a sealing layer in the lithium ion type. Various kinds of members corresponding to a small size, a polymer type, a ceramics electrolyte type, and the like.

Examples of the circuit for electronic parts include a metal of a conductive part, a silicon oxide of an insulating part and silicon nitride in a CCD or a CMOS, and various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board, Various members corresponding to substrates and the like.

(Process procedure)

The method of manufacturing the glass laminate 110 having the above-described members is not particularly limited, and the glass substrate 14 of the glass laminate 100 may be formed by a conventionally known method, depending on the types of the constituent members of the electronic device member. The member 16 for an electronic device is formed on the surface of the second main surface 14b.

The electronic device member 16 is not limited to all of the members finally formed on the second main surface 14b of the glass substrate 14 (hereinafter, referred to as "Quot; partial member "). A glass substrate provided with a partial member obtained by peeling off the temporary support 10 may be made a glass substrate (corresponding to an electronic device described later) provided with an entire member in a subsequent step.

Alternatively, the electronic device may be manufactured by assembling a laminate provided with an entire member, and thereafter peeling the temporary support 10 from the laminate provided with the entire member. In addition, the electronic device is assembled by using two laminated bodies provided with the entire members, and then the two temporary supporting bodies 10 are peeled from the laminated body provided with the entire member to obtain an electronic device having two glass substrates May be produced.

The surface of the glass substrate 14 on the opposite side of the polyimide resin layer 12 side of the glass laminate 100 (the surface of the second main surface of the glass substrate 14 14b), a transparent electrode may be formed, or a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, or the like may be further deposited on the surface on which the transparent electrode is formed, or a back electrode may be formed , Sealing with a sealing plate, or the like is performed. Specific examples of these layer formation and treatment include film forming treatment, vapor deposition treatment, adhesion treatment of a sealing plate, and the like.

For example, in the case of manufacturing a TFT-LCD, a resist solution is used on the second main surface 14b of the glass substrate 14 of the glass laminate 100, and a general film forming method such as a CVD method and a sputtering method is used A TFT forming step of forming a thin film transistor (TFT) by patterning a metal film and a metal oxide film formed on the glass substrate 14 formed on the glass substrate 14 of the other glass laminate 100; A CF film forming step of forming a color filter CF by pattern formation, a laminate provided with TFTs obtained in the TFT forming step, and a lamination body obtained by CF forming step And the like.

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

Further, the second main surface 14b of the glass substrate 14 may be cleaned before forming the TFT or the CF, if necessary. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

In the bonding step, the thin film transistor formation surface of the laminate provided with the TFT and the color filter formation surface of the laminate provided with CF are opposed to each other with a sealing agent (for example, ultraviolet curing type sealing agent for forming a cell) do. Thereafter, the liquid crystal material is injected into the cell formed by the laminated body having the TFT and the laminated body provided with the CF. As a method of injecting the liquid crystal material, for example, there are a reduced pressure injection method and a dropping injection method.

≪ Process (4): Separation Step S108 >

Step (4) is a step of obtaining an electronic device including the polyimide resin layer, the glass substrate, and the electronic device member by removing the temporary support obtained from the glass laminate provided in the step (3). 2 (D), when the interface between the temporary support 10 and the polyimide resin layer 12 is peeled off from the glass laminate 110 provided with the member obtained in the above step (3) The temporary support 10 is separated and removed to obtain the electronic device 120 including the polyimide resin layer 12, the glass substrate 14 and the electronic device member 16.

If the electronic device member 16 on the glass substrate 14 at the time of peeling is a part of the formation of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 14 after the detachment.

The method of separating the temporary support 10 and the electronic device 120 is not particularly limited. Specifically, for example, a blade having a sharp blade shape is inserted at the interface between the temporary support 10 and the polyimide resin layer 12 to give a moment of peeling, and then a mixed fluid of water and compressed air is sprayed to peel off . Preferably, the temporary support 10 of the glass laminate 110 provided with the member is provided on the table so that the upper side and the side of the electronic device member 16 are downward, and the side of the electronic device member 16 In this state, first, the blade is infiltrated into the interface of the temporary support (10) and the polyimide resin layer (12). Then, the side of the temporary support body 10 is adsorbed by the plurality of vacuum adsorption pads, and the vacuum adsorption pads are raised in order from the vicinity of the point where the blade is inserted. By doing so, 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 surface of the interface, so that the temporary support 10 can be easily peeled off.

When separating the temporary support 10 and the electronic device 120 from each other, it is preferable to peel off the release auxiliary agent while spraying the release auxiliary agent to the interface between the temporary support 10 and the polyimide resin layer 12. The release auxiliary means a solvent such as the above-mentioned water. Examples of the release aid to be used include water and an organic solvent (for example, ethanol), a mixture thereof, and the like.

In addition, when separating the temporary support 10 from the glass laminate 110 provided with the member, the injection or humidity of the ionizer is controlled so that the pieces of the polyimide resin layer 12 are prevented from entering the temporary support 10, Adsorption can be further inhibited.

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

As the electronic device 120 manufactured by the above method, there can be used a display panel having a glass substrate and a display device member, a solar cell having a glass substrate and a member for a solar cell, a thin film secondary having a glass substrate and a member for a thin film secondary battery A battery, an electronic part having a glass substrate and a member for an electronic device, and the like. The display panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

[Second Embodiment]

Fig. 3 is a flowchart showing the manufacturing process in the second embodiment of the method for manufacturing an electronic device of the present invention. 3, the method of manufacturing 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, a shape of a polyimide resin layer A glass substrate laminating step S110 (corresponding to step (2 ')) of laminating a glass substrate having an external dimension smaller than the dimension on the polyimide resin layer so that a peripheral region not contacting the glass substrate remains on the polyimide resin layer; A cutting step S112 (corresponding to step (5)) of cutting the polyimide resin layer and the temporary support along the outer periphery of the substrate, a member forming step S106 (corresponding to step (3)) of arranging the electronic device member on the glass substrate , And a separation step S108 (step (4)) for separating and obtaining the electronic device.

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

The steps shown in Fig. 3 are the same as the steps shown in Fig. 1 except for the steps of the glass substrate laminating step S110 and the cutting step S112. The same steps are denoted by the same reference numerals, The glass substrate laminating step S110 and the cutting step S112 will be described.

≪ Process (2 '): Glass substrate laminating process S110 >

In the step (2 '), a glass substrate having an external dimension smaller than the external dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region that is not in contact with the glass substrate remains in the polyimide resin layer, . 4A, the polyimide resin layer 12 is disposed on the temporary support 10 in the polyimide resin layer forming step S102. Next, as shown in FIG. 4B, The glass substrate 14 having external dimensions smaller than the external dimensions of the polyimide resin layer 12 is disposed on the polyimide resin layer 12 by performing the main step S110 as described above. The glass substrate 14 is laminated on the polyimide resin layer 12 such that a peripheral region that does not contact the glass substrate 14 remains. In other words, the glass substrate 14 is laminated on the polyimide resin layer 12 so that the polyimide resin layer 12 is exposed on the outer periphery of the glass substrate 14. [

More specifically, as shown in Fig. 5 (A), the glass substrate 14 is made of polyimide resin such that the peripheral region 12b that does not contact the glass substrate 14 remains in the polyimide resin layer 12, Are laminated on the paper layer (12). That is, the glass substrate 14 is laminated on the polyimide resin layer 12 such that all the edges of the outer periphery of the glass substrate 14 do not contact the outer periphery of the polyimide resin layer 12.

Generally, on the exposed surface of the polyimide resin layer 12, a convex portion is apt to occur near the periphery due to the influence of its surface tension (see Fig. 5 (B)). When the glass substrate 14 is brought into contact with such convex portions when the glass substrate 14 is laminated, the central portion of the glass substrate 14 is curved so as to be recessed, and the flatness of the glass substrate 14 may be impaired (see ). The flatness of the glass substrate 14 is deteriorated and there is a possibility that the position of the electronic device member disposed on the glass substrate 14 may be displaced. As a result, the yield of the electronic device may be lowered.

The glass substrate 14 can be brought into contact with the polyimide resin layer 12 without contacting the convex portion by using the glass substrate 14 having an outer shape smaller than the outer shape of the polyimide resin layer 12. [ As a result, the occurrence of warpage of the glass substrate 14 is suppressed, and the lowering of the yield of the 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 to the total area B of the polyimide resin layer 12 is preferably 0.98 or less, More preferably 0.95 or less. Within this range, the occurrence of warping of the glass substrate 14 is further suppressed. The lower limit is not particularly limited, but is preferably 0.75 or more, more preferably 0.80 or more from the viewpoint of productivity and the like.

The length from the outer periphery of the glass substrate 14 to the outer periphery of the polyimide resin layer 12 is preferably 10 mm or more, more preferably 15 mm or more. Within this range, occurrence of thickness irregularity of the polyimide resin layer 12 is further suppressed. The upper limit is not particularly limited, but is preferably 100 mm or less from the viewpoint of productivity and the like.

As a method for laminating the glass substrate 14, the method of the step (2) of the first embodiment can be mentioned.

By carrying out this step, a glass laminate 200 having a temporary support 10, a polyimide resin layer 12, and a 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 periphery of the glass substrate. In other words, the outer support of each of the temporary support and the polyimide resin layer in the glass laminate is cut to align the entire periphery of the 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 periphery of the glass substrate 14 by the present step S112, A post-laminate body 300 (laminated body subjected to cutting treatment) is obtained.

The method of 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, etc.) can be adopted. For example, the methods described in paragraphs 0079 to 0095 of Japanese Patent Laid-Open Publication No. 2013-82182.

4 (D), the electronic device member 16 is disposed on the glass substrate 14, and the electronic device member 16 is mounted on the glass substrate 14, as shown in Fig. 4 (D) The glass laminate 110 is formed. 4 (E), the temporary support 10 is removed from the glass laminate 110 provided with the member to form the polyimide resin layer 12, And the electronic device 120 having the glass substrate 14 and the electronic device member 16 are obtained.

[Example]

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited to these examples.

In the following examples and comparative examples, a glass plate (150 mm in length, 150 mm in width, 0.1 mm in plate thickness, and a linear expansion coefficient of 38 x 10 &lt; ^-7 &gt; / [deg.] C, manufactured by Asahi Glass Co., Trade name &quot; AN100 &quot;) was used. As the temporary support, a glass plate (200 mm in length, 200 mm in width, 0.5 mm in plate thickness, and a coefficient of linear expansion of 38 x 10 ^-7 / 占 폚, manufactured by Asahi Glass Co., Ltd., trade name "AN100") containing an alkali- Respectively.

(Production of polyamic acid solution (A)) [

Para-phenylenediamine (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 acid dianhydride (29.4 g, 0.1 mol) was added over 1 minute, and the mixture was stirred at room temperature for 2 hours, A polyamic acid solution (A) having a solid concentration of 20% by mass and containing a polyamic acid having a repeating unit represented by the formula (2-2). The viscosity of this solution was measured and found to be 3000 centipoise at 20 占 폚.

The viscosity was measured at 20 캜 using a DVL-B II type digital viscometer (B-type viscometer) manufactured by Toray Industries, Inc. The viscosity was measured.

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

(Preparation of Silane Coupling Agent Solution (B)) [

After adding a silane coupling agent (3-aminopropyltrimethoxysilane, trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) to isopropyl alcohol (IPA), the solution was stirred for about 1 hour with a mixer Solution B was prepared. The content of the silane coupling agent was adjusted to 0.1% by mass with respect to the total mass of the isopropyl alcohol.

&Lt; Example 1 >

The solution A was coated on a temporary support subjected to cleaning by a die coater, followed by drying treatment at 90 占 폚 for 10 minutes and further drying treatment at 150 占 폚 for 10 minutes to give a polyamic acid To form a coating film.

Next, the above solution B was coated on the surface of the coating film with a die coater, and then dried at 120 캜 for 10 minutes to obtain a coated film to which the silane coupling agent was applied.

Next, the coating film was subjected to heat treatment at 350 占 폚 under nitrogen for 1 hour to promote the cyclization reaction of polyamic acid to obtain a polyimide resin layer whose surface was treated with a silane coupling agent.

Next, a glass substrate having an external dimension smaller than the external dimensions of the polyimide resin layer is stacked while aligning the center positions of the substrates so that a peripheral region that is not in contact with the glass substrate remains in the polyimide resin layer, &Lt; / RTI &gt; Further, 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 interface peel strength (y) between the polyimide resin layer and the temporary support.

Subsequently, the glass substrate of the glass laminate S1 is fixed on the surface plate on which the positioning jig is provided, and the second main surface of the temporary support body (the polyimide resin layer After forming a cutting line with a diamond wheel cutter on the main surface on the side opposite to the side of the temporary support body, then the outside of the cutting line of the temporary support body was sandwiched and broken by the sandwiching jig. Likewise, after breaking the outer side of the temporary support overlapping with the remaining three sides of the outer periphery of the glass substrate, the broken surface of the temporary support is polished by the grinding wheel having a curved surface to be chamfered, SA.

Next, heat treatment at 450 占 폚 for 1 hour, which is carried out when the electronic device member is disposed on the glass substrate, is performed on the glass laminate SA. After the heat treatment, the glass laminate SA was cooled to room temperature, and no apparent changes such as separation of the glass substrate and the temporary support and foaming and whitening of the polyimide resin layer were observed.

Then, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the temporary support and the polyimide resin layer at the corners of one of the four places of the glass laminate SA to form the notch portion of the peeling, The vacuum adsorption pad is adsorbed on the surface of each of the support members not on the release surface and water is sprayed onto the interface between the temporary support and the polyimide resin layer to apply an external force in the direction in which the glass substrate and the temporary support member are separated from each other, Without breaking the temporary support. Here, the insertion of the blade was performed while blowing an antistatic fluid from the ionizer (manufactured by KYENS) to the interface.

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

&Lt; Example 2 >

The solution A was coated on a temporary support subjected to cleaning by a die coater, followed by drying treatment at 90 占 폚 for 10 minutes and further drying treatment at 150 占 폚 for 10 minutes to give a polyamic acid To form a coating film.

Next, the coating film was subjected to heat treatment at 350 占 폚 under nitrogen for 1 hour to promote the cyclization reaction of the polyamic acid to obtain a polyimide resin layer.

Next, the solution B was coated on the surface of the polyimide resin layer with a die coater and then dried at 120 캜 for 10 minutes to obtain a polyimide resin layer whose surface was treated with a silane coupling agent.

Next, a glass substrate having external dimensions smaller than the external dimensions of the polyimide resin layer is stacked while aligning the center positions of the substrates so that the peripheral region that does not contact the glass substrate remains in the polyimide resin layer, and the glass laminate S2 . 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 interface peel strength (y) between the polyimide resin layer and the temporary support.

Subsequently, the glass substrate of the glass laminate S2 is fixed on the base plate on which the positioning jig is provided, and a diamond wheel cutter is formed on the second main surface of the temporary support so as to overlap with one side of the outer periphery of the glass substrate from the upper surface of the base plate. , And then the outer side of the cutting line of the temporary support was sandwiched and broken by the sandwiching jig. Likewise, after breaking the outer side of the temporary support overlapping with the remaining three sides of the outer periphery of the glass substrate, the broken surface of the temporary support is polished by the grinding wheel having a curved surface to be chamfered, SB.

Next, the glass laminate SB was subjected to a heat treatment at 450 占 폚 for 1 hour, which is a heat treatment performed when the electronic device member was placed on the glass substrate. After the heat treatment, the glass laminate SB was cooled to room temperature, and there were no apparent changes such as separation of the glass substrate and the temporary support and foaming and whitening of the polyimide resin layer.

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

From the above results, it was also confirmed that the peel strength (x) at the interface between the glass substrate and the polyimide resin layer was higher than the interface peel strength (y) 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, no foaming occurred between the polyimide resin layer and the glass substrate, and thus a glass laminate including a glass substrate having excellent surface flatness could be manufactured . Further, the glass laminate can be peeled off at the interface between the temporary support and the polyimide resin layer after the heat treatment at 450 占 폚 for one hour, which is a condition for manufacturing the electronic device member, so that the polyimide resin layer and the glass substrate Can be separated from the temporary support. From these results, it was confirmed that the adhesion between the polyimide resin layer and the glass substrate was excellent. It has also been found that after the electronic device is manufactured on a glass substrate by a predetermined heat treatment, the temporary support can be separated from the glass laminate provided with the member.

(Evaluation of adhesion)

The adhesiveness of the polyimide resin layer to the glass substrate was evaluated by comparing the presence or absence of exfoliation defects (adhesion failure of the polyimide resin layer) generated when the temporary support was peeled off in Examples 1 and 2. The term &quot; gliding defect &quot; means a defect in which a part of the polyimide resin layer is pulled to the temporary support at the time of peeling off the temporary support, and the polyimide resin layer is locally peeled off from the glass substrate.

As a method of the adhesion evaluation, five glass laminates were prepared in each of Examples 1 and 2, and the temporary support was peeled off from each sample and excitation defects were observed. As a method of observing the excitation defects, the presence or absence of defects having a size of 1 mm or more under a fluorescent lamp was visually checked, and a case with a defect was designated as &quot; X &quot;, and a case without a defect was defined as &quot;

In all of the five samples of Example 1, there was no &quot; floating defect &quot;. On the other hand, for two of the five samples of Example 2, the temporary support could be peeled off, but an immobile defect was found.

From these results, it was confirmed that the adhesion between the glass substrate and the polyimide resin layer was superior to that of the embodiment 2 (corresponding to the above-mentioned form Y) in the form of the embodiment 1 (corresponding to the above-mentioned form X).

It was also confirmed that a desired effect can be obtained even when the temporary support on which the releasing treatment has been carried out is used as the temporary support used in Examples 1 and 2 and the following procedure is used.

(Release process)

Dimethylpolysiloxane was brought into contact with the surface of the glass plate containing the alkali-free borosilicate glass and baking treatment was performed at 350 ° C.

&Lt; Comparative Example 1 &

The solution A was coated on a temporary support subjected to cleaning by a die coater, followed by drying treatment at 90 占 폚 for 10 minutes and further drying treatment at 150 占 폚 for 10 minutes to give a polyamic acid To form a coating film.

Next, the above solution B was coated on the surface of the coating film with a die coater, and then dried at 120 캜 for 10 minutes to obtain a coated film to which the silane coupling agent was applied.

Next, the glass substrates having external dimensions smaller than the outer dimensions of the coating film were stacked while aligning the center positions of the substrates so that the peripheral region that does not contact the glass substrate remained on the coating film.

Thereafter, the coating film was subjected to a heat treatment at 350 占 폚 under nitrogen for 1 hour to promote the cyclization reaction of polyamic acid.

After the heat treatment, innumerable foaming occurred between the polyimide resin layer and the glass substrate, and the flatness of the glass substrate surface was impaired.

The configuration of Comparative Example 1 corresponds to the configuration of Patent Document 2, and it was impossible to manufacture a predetermined glass laminate and an electronic device by this method.

&Lt; Example 3 >

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 deposited in this order on the second main surface of the glass substrate in the glass laminate SA by the plasma CVD method. Next, a low concentration of boron was injected into the amorphous silicon layer by an ion doping apparatus, followed by heat treatment in a nitrogen atmosphere to carry out a 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 from an etching and ion doping apparatus using a photolithography method to form N-type and P-type TFT areas. Next, a silicon oxide film was formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and thereafter molybdenum was formed by sputtering and a gate electrode was formed by etching using a photolithography method . Next, high-concentration boron and phosphorus were implanted into desired areas of 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 the silicon oxide film formation by the plasma CVD method, and a TFT electrode was formed by the sputtering method by aluminum film formation and etching using the photolithography method. Next, after heat treatment in a hydrogen atmosphere to perform hydrogenation treatment, a passivation layer was formed by film formation of nitrogen silicon by the plasma CVD method. Next, a UV-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, indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as the hole injection layer on the second main surface side of the glass substrate, and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-2-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) (BSN-BCN) was mixed in an amount of 40 vol%, and Alq ₃ was formed in this order as an electron transporting layer. Next, aluminum was deposited by a sputtering method, and etching was performed by photolithography Next, another glass substrate was bonded to the second main surface side of the glass substrate via an ultraviolet curing type adhesive layer and sealed, and an organic EL structure was formed on the glass substrate by the above procedure . A glass laminate S1 having an organic EL structure on a glass substrate (hereinafter referred to as &quot; Referred to as A) is a laminate comprising a glass according to the present invention, a member.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the temporary support at the corner of the panel A and the polyimide resin layer, after the sealing member side of the panel A was vacuum-adsorbed on the surface of the plate, and the temporary support and the polyimide resin layer And the interface was given a moment of peeling. After the surface of the temporary support of Panel A was adsorbed on the vacuum adsorption pad, the adsorption pad was elevated. Here, the insertion of the blade was performed while blowing an antistatic fluid from the ionizer (manufactured by KYENS) to the interface. Next, the vacuum adsorption pad was pulled up while spraying the antistatic fluid continuously from the ionizer toward the formed voids, and also placing water on the peeling wire. As a result, the temporary support could be peeled off, and an electronic device was obtained.

Subsequently, the separated glass substrate is cut by a laser cutter or a scribe-break method to be 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, Respectively. The OLED thus obtained did not cause any problems due to its characteristics.

The temperature of the heat treatment at the time of manufacturing the electronic device was 450 ° C at the maximum.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

10: temporary support
12: polyimide resin layer
14: glass substrate
16: member for electronic device
100, 200: Glass laminate
110: Glass laminate with members
120: electronic device
300: Post-cut laminate

Claims (8)

A step (1) of forming, on a temporary support, a polyimide resin layer whose surface on the side opposite to the temporary support side is treated with a silane coupling agent;
(2) of arranging a glass substrate having a thickness of 0.2 mm or less on the polyimide resin layer to obtain a glass laminate,
A step (3) of disposing a member for an electronic device on the surface of the glass substrate to obtain a glass laminate provided with the member,
(4) of removing the temporary support from the glass laminate provided with the member to obtain an electronic device including the polyimide resin layer, the glass substrate, and the electronic device member, Way. The method according to claim 1,
(A) a step (A) of applying a composition containing a polyamic acid on a temporary support to form a coating film containing polyamic acid, and a step (A) of applying a silane coupling agent on the coating film surface And a step (C) of performing a heat treatment on the coating film to obtain a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent. . The method according to claim 1,
(D) a step (D) of forming a polyimide resin layer on a temporary support, and a step of applying a silane coupling agent on the surface of the polyimide resin layer so that the surface opposite to the temporary support side is a silane And a step (E) of obtaining a polyimide resin layer treated with a coupling agent. 4. The method according to any one of claims 1 to 3,
Wherein the step (2) is a step of forming a polyimide resin layer on the polyimide resin layer so that a glass substrate having an external dimension smaller than the external dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region, (2 '),
Further comprising a step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer periphery of the glass substrate between the step (2) and the step (3) &Lt; / RTI &gt; A temporary support, a polyimide resin layer whose surface opposite to the temporary support side is treated with a silane coupling agent, and a glass substrate in this order,
A step of disposing a member for an electronic device on the surface of the glass substrate and then removing the temporary support to obtain an electronic device including the polyimide resin layer, the glass substrate, and the member for the electronic device, In the method for producing a glass laminate,
A step (1) of forming, on a temporary support, a polyimide resin layer whose surface on the side opposite to the temporary support side is treated with a silane coupling agent;
And (2) placing a glass substrate having a thickness of 0.2 mm or less on the polyimide resin layer to obtain the glass laminate. 6. The method of claim 5,
(A) a step (A) of applying a composition containing a polyamic acid on a temporary support to form a coating film containing polyamic acid, and a step (A) of applying a silane coupling agent on the coating film surface And a step (C) of subjecting the coating film to a heat treatment to obtain a polyimide resin layer whose surface on the side opposite to the temporary support side is treated with a silane coupling agent. Way. 6. The method of claim 5,
(D) a step (D) of forming a polyimide resin layer on a temporary support, and a step of applying a silane coupling agent on the surface of the polyimide resin layer so that the surface opposite to the temporary support side is a silane And a step (E) of obtaining a polyimide resin layer treated with a coupling agent. 8. The method according to any one of claims 5 to 7,
Wherein the step (2) is a step of forming a polyimide resin layer on the polyimide resin layer so that a glass substrate having an external dimension smaller than the external dimension of the polyimide resin layer is laminated on the polyimide resin layer so that a peripheral region, (2 '),
Further comprising a step (5) of cutting the polyimide resin layer and the temporary support in the glass laminate along the outer periphery of the glass substrate after the step (2).

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