JP2017113880A - Glass laminate, glass substrate with resin layer, and support base material with resin layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass laminate comprising a resin layer which can be easily cut by bending.SOLUTION: A glass laminate has a support base material, a resin layer, and a glass substrate in the stated order, the resin layer having an indentation elastic modulus of 5.5 GPa or more and an elastic power of less than 70%.SELECTED DRAWING: Figure 2

Description

The present invention relates to a glass laminate, and more particularly, to a glass laminate including a resin layer exhibiting a predetermined indentation elastic modulus and elastic power.
The present invention also relates to a glass substrate with a resin layer and a support substrate with a resin layer.

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, Patent Document 1 discloses a method for manufacturing an electronic device using a glass / resin laminate of a resin layer containing a predetermined polyimide and a glass substrate. More specifically, it is disclosed that a component of an electronic device is disposed on a glass substrate using a glass laminate including a glass / resin laminate and a support that supports the glass / resin laminate. ing.

International Publication No. 2011/030716

On the other hand, when or after the constituent members of the electronic device are arranged, it is necessary to cut the glass laminate containing the resin layer into a predetermined size.
As a method of cutting, there is a method of cutting using a high output long wavelength pulse laser or a CO ₂ laser, but there is a problem that the quality of the cut surface is deteriorated. Therefore, it is desired that a scribe line (cut line) is put on the surface of the glass laminate, and the glass laminate can be bent and cut (cleaved) along the scribe line without using a laser or the like.
On the other hand, the present inventors put a scribe line on the surface of the glass laminate specifically disclosed in Patent Document 1 and bend it, so that the resin layer portion is not cut and the glass laminate can be cleaved. could not.

This invention is made | formed in view of the said subject, Comprising: It aims at providing the glass laminated body containing the resin layer which can be cut | disconnected easily by bending.
Another object of the present invention is to provide a glass substrate with a resin layer and a supporting substrate with a resin layer, which are used as a part of the glass laminate and can be easily cut by bending.

  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 is a glass laminate having a support base, a resin layer, and a glass substrate in this order, and the indentation elastic modulus of the resin layer is 5.5 GPa or more, and the resin A glass laminate in which the elastic power of the layer is less than 70%.
In the first aspect, the resin layer is preferably a polyimide resin layer.
In the first embodiment, the polyimide resin is composed of a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) described later, 50 mol% or more of the total number of residues (X) of carboxylic acids is composed of a group represented by the formula (X1) described later, and 50 mol% or more of the total number of residues (A) of diamines is a formula (described later) It preferably consists of a group represented by A1).
1st aspect WHEREIN: It is preferable that a support base material is a glass plate.
A second aspect of the present invention is a glass substrate and a glass substrate with a resin layer having a resin layer formed on the glass substrate, wherein the glass substrate with a resin layer is formed by laminating a support base material on the resin layer. The glass substrate with a resin layer is used for producing a glass laminate, the indentation elastic modulus of the resin layer is 5.5 GPa or more, and the elastic work modulus of the resin layer is less than 70%. .
In the second aspect, the resin layer is preferably a polyimide resin layer.
In the second embodiment, the polyimide resin is composed of a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine, which is represented by the formula (1) described later. 50 mol% or more of the total number of residues (X) of carboxylic acids is composed of a group represented by the formula (X1) described later, and 50 mol% or more of the total number of residues (A) of diamines is a formula (described later) It preferably consists of a group represented by A1).
A third aspect of the present invention is a support substrate with a resin layer having a support substrate and a resin layer formed on the support substrate, wherein the support substrate with a resin layer is a glass substrate on the resin layer. Is used to produce a glass laminate, and the resin layer has an indentation elastic modulus of 5.5 GPa or more, and the resin layer has an elastic work modulus of less than 70%. It is a substrate.
In the third aspect, a polyimide resin layer is preferable.
In the third embodiment, the polyimide resin is composed of a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) described later, 50 mol% or more of the total number of residues (X) of carboxylic acids is composed of a group represented by the formula (X1) described later, and 50 mol% or more of the total number of residues (A) of diamines is a formula (described later) It preferably consists of a group represented by A1).

ADVANTAGE OF THE INVENTION According to this invention, the glass laminated body containing the resin layer which can be cut | disconnected easily by bending can be provided.
Moreover, according to this invention, the glass substrate with a resin layer and the support base material with a resin layer which are used as a part of this glass laminated body and can be easily cut | disconnected by bending can also be provided.

It is typical sectional drawing of one Embodiment of the support base material with a resin layer which concerns on this invention. It is typical sectional drawing of one Embodiment of the glass laminated body which concerns on this invention. It is typical sectional drawing which shows one Embodiment of the manufacturing method of the glass substrate with a member which concerns on this invention in process order. It is a typical sectional view of one embodiment of a glass substrate with a resin layer concerning the present invention. It is typical sectional drawing of one Embodiment of the glass laminated body which concerns on this invention. It is typical sectional drawing which shows the procedure of a cutting process.

  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 glass laminate of the present invention is that a resin layer (hereinafter also simply referred to as “resin layer”) exhibiting a predetermined indentation elastic modulus and a predetermined elastic power is used. When the glass laminate is folded and broken (cut), the resin layer can be cut together with the supporting substrate and the glass substrate at a predetermined position by the resin layer exhibiting the predetermined indentation elastic modulus and elastic power. it can. The indentation elastic modulus mainly indicates hardness, and the elastic power is an index indicating deformability. When a resin layer that satisfies only one of the indentation elastic modulus and elastic power is used, it is difficult to break (cut) the glass together with bending.
Moreover, the glass substrate with a resin layer and the support substrate with a resin layer can also be cut (cleaved) by bending for the same reason as described above.

In the glass laminate, the peel strength at the interface of the resin layer to the glass substrate layer is usually different from the peel strength at the interface of the resin layer to the support base material layer. For example, in the first embodiment, the peel strength at the interface between the resin layer and the glass substrate layer is lower than the peel strength at the interface between the resin layer and the support base layer, and the resin layer and the glass substrate layer peel off. Then, it is separated into a laminate of a resin layer and a supporting substrate and a glass substrate. In the second embodiment, the peel strength at the interface between the resin layer and the glass substrate layer is higher than the peel strength at the interface between the resin layer and the support substrate, and the resin layer and the support substrate layer peel off. And it isolate | separates into the laminated body of a glass substrate and a resin layer, and a support base material.
Below, it divides into 1st embodiment and 2nd embodiment, and demonstrates.

<Supporting substrate with resin layer and glass laminate (first embodiment)>
In the following, first, an embodiment (first embodiment) of a support substrate with a resin layer according to the present invention and a glass laminate including the support substrate with a resin layer will be described in detail.
FIG. 1 is a schematic cross-sectional view of an example of a support substrate with a resin layer according to the present invention.
As shown in FIG. 1, the support substrate 18 with a resin layer is a laminate having a layer of the support substrate 12 and a resin layer 14 formed on the support substrate 12. The surface 14b of the resin layer 14 is in contact with the first main surface of the support base 12, and no other material is in contact with the surface 14a.
As shown in FIG. 2, the support base material 18 with the resin layer is usually laminated on the glass substrate 16 for an electronic device such as a liquid crystal panel by laminating the resin layer 14 so that the surface 14 a contacts the glass substrate 16. It is used for the member formation process which manufactures a member.
FIG. 2 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 2, the glass laminated body 10 is a laminated body in which the layer of the supporting base 12 and the layer of the glass substrate 16 and the resin layer 14 exist between them. The resin layer 14 has one surface in contact with the layer of the support base 12 and the other surface in contact with the first main surface 16 a of the glass substrate 16.
The two-layer portion composed of the layer of the support base 12 and the resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel.

  This glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 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 16b of the glass substrate 16. Then, the glass laminated body in which the member for electronic devices was formed is isolate | separated into the support base material 18 with a resin layer, and the glass substrate with a member, and the support base material 18 with a resin layer does not become a part which comprises an electronic device. A new glass substrate 16 is laminated on the support base material 18 with the resin layer, and can be reused as a new glass laminate 10.

In addition, in the glass laminated body 10 of FIG. 2, the resin layer 14 is being fixed on the support base material 12, and the glass substrate 16 is laminated | stacked on the resin layer 14 of the support base material 18 with a resin layer so that peeling (adhesion) is carried out. ) In the present invention, the fixation and peelable lamination (adhesion) has a difference in peel strength (that is, stress required for peeling), and fixation means that the peel strength is greater than the adhesion. That is, the peel strength at the interface between the resin layer 14 and the support base 12 is greater than the peel strength at the interface between the resin layer 14 and the glass substrate 16. In other words, the peelable lamination (adhesion) means that the peelable layer can be peeled at the same time without causing peeling of the fixed surface.
More specifically, the interface between the support base 12 and the resin layer 14 has a peel strength (x), and the interface between the support base 12 and the resin layer 14 has a stress in the peeling direction exceeding the peel strength (x). When added, the interface between the support base 12 and the resin layer 14 is peeled off. The interface between the resin layer 14 and the glass substrate 16 has a peel strength (y). When a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the resin layer 14 and the glass substrate 16, The interface of the glass substrate 16 peels off.
In the glass laminate 10 (which also means a laminate with an electronic device member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when a stress is applied to the glass laminate 10 in the direction of peeling the support substrate 12 and the glass substrate 16, the glass laminate 10 is peeled off at the interface between the resin layer 14 and the glass substrate 16 and the glass substrate 16. It isolate | separates into the support base material 18 with a resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion than the glass substrate 16 can be maintained after the heat treatment.
Increasing the adhesion of the resin layer 14 to the support base 12 is a method of forming the resin layer 14 on the support base 12 (preferably, repeating by the formula (1) by thermosetting, as will be described later. A curable resin to be a unitary polyimide resin is cured on the support substrate 12 to form a predetermined resin layer 14). The resin layer 14 bonded to the support base 12 with a high bonding force can be formed by the adhesive force at the time of formation.
On the other hand, the bonding force of the cured resin layer 14 to the glass substrate 16 is generally lower than the bonding force generated during the formation. Therefore, by forming the resin layer 14 on the support base 12 and then laminating the glass substrate 16 on the surface of the resin layer 14, the glass laminate 10 satisfying a desired peeling relationship can be manufactured.

  Below, each layer (the support base material 12, the glass substrate 16, the resin layer 14) which comprises the support base material 18 with a resin layer and the glass laminated body 10 is explained in full detail, Then, the support base material with a resin layer, a glass laminated body Will be described in detail.

[Supporting substrate]
The plate-like support base 12 supports and reinforces the glass substrate 16, and the deformation of the glass substrate 16 during the manufacture of the electronic device member in the member forming step (step of manufacturing the electronic device member) described later, Prevents scratches and damage.
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Usually, since the member forming process involves heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16 and more preferably formed of the same material as the glass substrate 16. Preferably, the support base 12 is a glass plate. In particular, the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

  The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is selected based on the thickness of the glass substrate 16, the thickness of the resin layer 14, and the thickness of the glass laminate 10. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the resin layer 14 is 0.1 mm, the support is provided. The thickness of the base material 12 is 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 0.5 mm, and is preferably thicker than the glass substrate 16.

  When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as easy handling and difficulty in cracking. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient at 25 to 300 ° C. between the support base 12 and the glass substrate 16 is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less. More preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 10 may be severely warped or the support substrate 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

[Glass substrate]
As for the glass substrate 16, the 1st main surface 16a touches the resin layer 14, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the resin layer 14 side. That is, the glass substrate 16 is a substrate used for forming an electronic device described later.
The glass substrate 16 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 16 is excellent in chemical resistance and moisture permeability 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.

  When the linear expansion coefficient of the glass substrate 16 is large, the member forming process often involves a heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.

  The glass substrate 16 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. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

  The glass type of the glass substrate 16 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 16, 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 16 is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.10 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. It is. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

  The glass substrate 16 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or different materials. In this case, “the thickness of the glass substrate 16” means the total thickness of all the layers.

[Resin layer]
The resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support base 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation. In the glass laminate 10, the surface 14 a of the resin layer 14 in contact with the glass substrate 16 is detachably laminated (adhered) to the first main surface 16 a of the glass substrate 16. As described above, the resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) at the interface is between the resin layer 14 and the support base 12. Lower than the peel strength (x) at the interface.
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first main surface 16 a of the glass substrate 16 and the resin layer 14, and at the interface between the support base material 12 and the resin layer 14. Hard to peel. For this reason, the resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. Are bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In this invention, the property which can peel this resin layer 14 surface easily is called peelability. On the other hand, the 1st main surface of the support base material 12 and the resin layer 14 are couple | bonded by the bonding force which cannot be peeled relatively.

The resin layer 14 and the layer of the glass substrate 16 are considered to be bonded by a bonding force resulting from weak adhesive force or van der Waals force. When the resin layer 14 is a polyimide resin layer, when the glass substrate 16 is laminated on the surface after the resin layer 14 is formed, the polyimide resin in the resin layer 14 is sufficiently imidized so as not to exhibit an adhesive force. Are considered to be connected by a binding force resulting from van der Waals force. However, the polyimide resin in the resin layer 14 often has a certain weak adhesive force. Even when the adhesiveness is extremely low, when the electronic device member is formed on the laminated body after the glass laminated body 10 is manufactured, the polyimide resin in the resin layer 14 is heated to the glass substrate 16 by a heating operation or the like. It is considered that the bonding force between the resin layer 14 and the glass substrate 16 is increased by bonding to the surface.
In some cases, the surface of the resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination can be laminated by performing a treatment for weakening the bonding force between them. In addition, you may implement the process which inserts peeling adjuvant (water etc.) in an interface at the time of peeling. By performing non-adhesive treatment or the like on the surface to be laminated and then laminating, the bonding strength at the interface between the resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

The resin layer 14 is bonded to the surface of the support base 12 with a strong bonding force such as an adhesive force or an adhesive force. As described above, the method for increasing the adhesive force is achieved by forming the resin layer 14 on the support base 12. For example, by curing a curable resin that becomes a polyimide resin composed of a repeating unit represented by the formula (1) described later by thermosetting on the surface of the support base 12, the polyimide resin adheres to the surface of the support base 12. High binding force can be obtained. Moreover, a high bond strength can also be obtained by bringing a composition containing a polyimide resin into contact with the surface of the support substrate 12 and performing a heat treatment as necessary to form the resin layer 14. Furthermore, the process (for example, process using a coupling agent) which produces strong bond strength between the support base material 12 surface and the resin layer 14 is given, and the bond between the support base material 12 surface and the resin layer 14 is performed. The power can be increased.
That the resin layer 14 and the layer of the support base material 12 are bonded with a high bonding force means that the peel strength (x) at the interface between the two is high.

The indentation elastic modulus of the resin layer 14 is 5.5 GPa or more, and is 5.7 GPa or more because it is more easily cut by bending (hereinafter also referred to simply as “the effect of the present invention is more excellent”). Preferably, 6.0 GPa or more is more preferable. The upper limit is not particularly limited, but is usually 20 GPa or less, and preferably 10 GPa or less.
When the indentation elastic modulus is less than 5.5 GPa, the resin layer extends at the same time as bending, and thus the glass laminate is inferior in cracking properties.
As a method of measuring the indentation elastic modulus, a Vickers pyramid indenter is attached to a microhardness tester (Fisco Instruments Picodenter HM500), a load-unload test is performed, and a load / penetration depth curve is measured. Here, the load speed (load speed) F = 0.1 mN / sec is applied at the load speed, 0.5 mN is held as the maximum load for 5 seconds, and then the condition for unloading at the same load speed is applied. Measure the indentation modulus. As a measurement target, a resin layer having a thickness of 5 μm is used. Here, the thickness is intended to mean the average thickness, which is obtained by measuring the thickness of any 10 points and arithmetically averaging them. Although measurement is possible even with a resin layer having a thickness of less than 5 μm, the correct physical properties of the film may not be evaluated due to the influence of the elastic modulus of the substrate. In that case, an equivalent evaluation is possible if the maximum indentation load is set lower than 0.5 mN and it is confirmed that the substrate is not affected by the depth dependency of the Martens hardness.

The elastic power of the resin layer 14 is less than 70%, and 68% or less is preferable and 66% or less is more preferable in that the effect of the present invention is more excellent. The lower limit is not particularly limited, but is usually 20% or more, and preferably 30% or more.
When the elastic power is 70% or more, the crackability of the glass laminate is inferior.
The elastic power will be described below.
When a load is applied to the solid material, only a part of the mechanical work Wtotal spent during pushing is used as the plastic deformation work Wplast, and the rest is the elastic recovery work (elastic deformation work when removing the load). Amount) released as Welast. The elastic recovery work (elastic deformation work) Welast includes an instantaneous elastic deformation component and a delayed elastic deformation component. The elastic power represents the viscoelasticity of the material and is a parameter that contributes particularly to elastic recovery. The elastic power is expressed by Welast / Wtotal × 100.
In addition, the measurement conditions for the elastic power are the same as the measurement conditions for the indentation elastic modulus described above.

  The type of the resin constituting the resin layer 14 is not particularly limited as long as it is a resin that can form the resin layer exhibiting the above-described predetermined indentation elastic modulus and elastic power. For example, examples of the resin constituting the resin layer 14 include polyimide resin, polyester resin, polyolefin resin, polycarbonate resin, and polyethersulfone resin. Especially, a polyimide resin is preferable at the point which the effect of this invention is more excellent. That is, the resin layer 14 is preferably a polyimide resin layer.

The polyimide resin in the resin layer 14 is preferably a resin obtained by dehydrating and ring-closing polyamic acid, and the polyamic acid preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 1,000 to 50,000. Preferably, it is 2000-30000.
When the weight average molecular weight is in the above range, the coating properties of the resin layer are more excellent, and a resin layer that satisfies a desired relationship is easily formed.
As a measuring method of a weight average molecular weight, it can obtain | require by gel permeation chromatography (GPC) (polystyrene conversion).
The structure of the polyamic acid is not particularly limited, but as will be described later, a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine is preferable, and at least a part of the tetracarboxylic dianhydride is particularly preferable. Is more preferably composed of a compound represented by the formula (Y1) described later, and at least a part of the diamines is composed of a compound represented by the formula (B1) described later.

Moreover, the structure of the terminal group of the polyamic acid is not particularly limited, but it is preferable that the terminal group is blocked with a non-reactive group. More specifically, it is preferable that the terminal of the polyamic acid is end-capped with a structure containing no acid anhydride group or active hydrogen.
By sealing the terminal of the polyamic acid, an increase in the molecular weight of the polyimide resin can be easily suppressed, and a resin layer satisfying the above-described relationship can be easily formed.
In addition, as a method of end-capping with a structure containing no acid anhydride group or active hydrogen, for example, in the case of an amine-terminated polyimide precursor, a method of amidation with acetic anhydride, phthalic anhydride, And a method in which the terminal is an amic acid with an acid anhydride such as 3-naphthalic anhydride.

Although the thickness of the resin layer 14 is not specifically limited, It is preferable that it is 0.1-100 micrometers, It is more preferable that it is 0.5-50 micrometers, It is further more preferable that it is 1-20 micrometers. When the thickness of the resin layer 14 is within such a range, even if bubbles or foreign matter may be present between the resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 can be suppressed. Can do. Further, if the thickness of the resin layer 14 is too thick, it takes time and materials to form the resin layer 14, which is not economical and the heat resistance may be lowered. Moreover, when the thickness of the resin layer 14 is too thin, the adhesiveness of the resin layer 14 and the glass substrate 16 may fall.
The resin layer 14 may be composed of two or more layers. In this case, “the thickness of the resin layer 14” means the total thickness of all the layers.

The surface roughness Ra of the surface of the resin layer 14 on the glass substrate 16 side is preferably 0 to 2.0 nm, more preferably 0 to 1.0 nm, and further preferably 0.05 to 0.5 nm. When the surface roughness Ra is within the above range, the glass substrate 16 is excellent in adhesion to the resin layer 14 and the glass substrate 16 is not easily displaced.
When the resin layer 14 is a polyimide resin layer, the method of forming a polyimide resin into a layer generally includes a method of extrusion molding after manufacturing a thermoplastic polyimide resin, or a curable resin that becomes a polyimide resin by thermosetting. There is a method in which the solution is cured on the substrate surface after the solution is applied on the substrate. In the present invention, the resin layer 14 having a surface roughness Ra in the above range can be easily obtained by molding by the latter method.
Here, the surface roughness Ra is measured by an atomic force microscope (manufactured by Pacific Nanotechnology, Nano Scope IIIa; Scan Rate 1.0 Hz, Sample Lines 256, Off-line Modify Flatten order-2, Planefit order-2). (Measurement method of surface roughness of fine ceramic thin film by atomic force microscope JIS R 1683: 2007 compliant)

When the resin layer 14 is a polyimide resin layer, the polyimide resin of the resin layer 14 includes a residue (X) of tetracarboxylic acids and a residue (A) of diamines represented by the following formula (1). It preferably consists of repeating units. 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 formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and 50 mol% or more of the total number of X is preferably composed of a group represented by the following formula (X1). . Especially, it is preferable that 80-100 mol% of the total number of X consists of group represented by the following formula | equation (X1) at the point which the peelability of the glass substrate 16 or the heat resistance of the resin layer 14 is more excellent. . It is more preferable that substantially all (100 mol%) of the total number of X is composed of a group represented by the following formula (X1).
A represents a diamine residue obtained by removing an amino group from diamines, and 50 mol% or more of the total number of A is preferably composed of a group represented by the following formula (A1). Especially, it is preferable that 80-100 mol% of the total number of A consists of group represented by the following formula | equation (A1) at the point which the peelability of the glass substrate 16 or the heat resistance of the resin layer 14 is more excellent. .

In addition, as said X, groups other than group represented by the following formula | equation (X1) may be contained, for example, group represented by formula (X2)-(X4) is mentioned.
Moreover, as said A, groups other than group represented by the following formula | equation (A1) may be contained, for example, group represented by a formula (A2)-(A7) is mentioned.

  In addition, 80-100 mol% of the total number of X consists of group represented by the following formula | equation (X1) by the point which the peelability of the glass substrate 16 or the heat resistance of the resin layer 14 is more excellent, and A It is preferable that 80 to 100 mol% of the total number of the compounds consists of a group represented by the following formula (A1), and substantially all (100 mol%) of the total number of X is represented by the following formula (X1). More preferably, it consists of a group, and substantially all (100 mol%) of the total number of A consists of groups represented by the following formula (A1).

  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 resin layer 14 and the film formability of the coating film. In this respect, 10 to 10000 are preferable, and 15 to 1000 are more preferable.

  The molecular weight of the polyimide resin is preferably 500 to 100,000 in terms of coatability and heat resistance.

  Even if the said polyimide resin is 1 or more types chosen from the group which consists of the group illustrated below in less than 50 mol% of the total number of the residue (X) of tetracarboxylic acids in the range which does not impair heat resistance. Good. Moreover, 2 or more types of groups illustrated below may be included.

  Further, the polyimide resin is one or more selected from the group consisting of the groups exemplified below, in which less than 50 mol% of the total number of residues (A) of the diamine is within a range not impairing heat resistance. Also good. Moreover, 2 or more types of groups illustrated below may be included.

  The content of the resin (for example, polyimide resin) in the resin layer 14 is not particularly limited, but the releasability of the glass substrate 16 or the heat resistance of the resin layer 14 is more excellent with respect to the total mass of the resin layer. 50-100 mass% is preferable, 75-100 mass% is more preferable, 90-100 mass% is further more preferable.

In the resin layer 14, other components (for example, a filler that does not impair heat resistance) other than the resin 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.

  When the resin layer 14 is a polyimide resin layer, the resin layer 14 is preferably a polyimide resin layer formed by performing heat treatment on a curable resin layer that becomes a polyimide resin by thermosetting, Furthermore, in the layer of the curable resin which becomes a polyimide resin composed of a repeating unit having the residue (X) of the tetracarboxylic acid represented by the above formula (1) and the residue (A) of the diamine by heat curing. More preferably, it is a polyimide resin layer formed by heat treatment. In addition, you may implement heat processing in steps, changing temperature.

[Production method of supporting substrate with resin layer and glass laminate]
As a manufacturing method of the support base material 18 with a resin layer of this invention, and the glass laminated body 10, for example, the resin layer 14 is formed on the support base material 12 using the curable resin mentioned later, Then, on the resin layer 14 A method of manufacturing the glass laminate 10 by laminating the glass substrate 16 on the substrate.
When the curable resin is cured on the surface of the support substrate 12, it is considered that the curable resin adheres due to the interaction with the surface of the support substrate 12 during the curing reaction, and the peel strength between the resin layer 14 and the surface of the support substrate 12 is increased.
Hereinafter, the step of forming the resin layer 14 on the support base 12 using the curable resin is a resin layer forming step, and the step of laminating the glass substrate 16 on the resin layer 14 to form the glass laminate 10 is a laminating step. Good, the procedure of each step will be described in detail. In the following, an embodiment in which the resin layer 14 is a polyimide resin layer will be described in detail.
In the following, the embodiment using a curable resin will be described in detail, but is not limited thereto, a predetermined polyimide resin is brought into contact with the support base 12 and, if necessary, heat treatment is performed. A resin layer may be formed. In particular, when a solution in which a polyimide resin is dissolved in a solvent is used, it is preferable to perform heat treatment in order to volatilize the solvent. You may implement the lamination process mentioned later using the support base material with a resin layer obtained by this process.

(Resin layer forming process)
The resin layer forming step is a curable resin that is formed on a supporting substrate and becomes a polyimide resin composed of repeating units having a residue of tetracarboxylic acids (X) and a residue of diamines (A) by thermosetting. In this step, a polyimide resin layer is obtained by subjecting this layer to heat treatment. In addition, as mentioned above, 50 mol% or more of the total number of residues (X) of tetracarboxylic acids consists of the group represented by the above formula (X1), and 50 mol of the total number of residues (A) of diamines. % Or more is preferably composed of a group represented by the above formula (A1). As shown in FIG. 3A, in this step, a resin layer is formed on the surface of at least one side of the support base 12.
Hereinafter, the resin layer forming step will be described by dividing it into the following two steps.
Step (1): Step of obtaining a coating film by applying a curable resin to be a polyimide resin represented by the above formula (1) on the support substrate 12 by thermosetting (2): Heating the coating film The process of performing a process and forming a resin layer Hereinafter, the procedure of each process is explained in full detail.

(Process (1): Coating film forming process)
Step (1) is a step of obtaining a coating film by applying a curable resin, which becomes a polyimide resin having a repeating unit represented by the above formula (1), by thermosetting on the support substrate 12.
In addition, curable resin contains the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and at least one part of tetracarboxylic dianhydride is from the compound represented by a following formula (Y1). It is preferable that at least a part of the diamine is composed of a compound represented by the following formula (B1).
In addition to the compound represented by the formula (Y1), other compounds may be used as the tetracarboxylic dianhydride. For example, the group consisting of compounds represented by the following (Y2) to (Y4) And at least one tetracarboxylic dianhydride selected from:
In addition to the compound represented by the formula (B1), other compounds may be used as the diamine, for example, selected from the group consisting of compounds represented by the following formulas (B2) to (B7). It is preferable to consist of at least one diamine.

  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 formula (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)-(B7) as needed. Good.

In addition to the polyamic acid obtained by reacting the tetracarboxylic dianhydride and diamine, the curable resin used in this step is a tetracarboxylic dianhydride or diamine capable of reacting with a polyamic acid. You may use what added the kind. In addition to polyamic acid, when tetracarboxylic dianhydride or diamines are added, two or more polyamic acid molecules having a repeating unit represented by formula (2-1) or formula (2-2) are converted to tetracarboxylic diacid. It can be coupled through anhydrides or diamines.
In the case of having an amino group at the terminal of the polyamic acid, tetracarboxylic dianhydride may be added, and added so that the carboxyl group is 0.9 to 1.1 mol with respect to 1 mol of the polyamic acid. It's okay. When it has a carboxyl group at the terminal of the polyamic acid, diamines may be added, and the amino group may be added in an amount of 0.9 to 1.1 mol with respect to 1 mol of the polyamic acid. In addition, when it has a carboxyl group at the terminal of polyamic acid, the acid terminal may be obtained by adding water or any alcohol to open the terminal acid anhydride group.
The tetracarboxylic dianhydride added later is more preferably a compound represented by the formulas (Y1) to (Y4). The diamine added later is preferably a diamine having an aromatic ring, and more preferably a compound represented by the formulas (B1) to (B7).
When tetracarboxylic dianhydrides or diamines are added later, the polymerization degree (n) of the polyamic acid having a repeating unit represented by the formula (2-1) or the formula (2-2) is 1 to 20. Is preferred. When the degree of polymerization (n) is within this range, the viscosity of the curable resin solution can be reduced even when the polyamic acid concentration in the curable resin solution is 30% by mass or more.

In this step, components other than the curable resin may be used.
For example, a solvent may be used. More specifically, the curable resin may be dissolved in a solvent and used as a curable resin solution (curable resin solution). 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 the reaction mentioned above is mentioned.
In addition, when the organic solvent is contained in the curable resin solution, 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. 5-90 mass% is preferable with respect to the total mass of a solution, and 10-80 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.

The method for applying the curable resin (or curable resin solution) on the surface of the support substrate 12 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 resin layer 14 of the desired thickness mentioned above may be obtained.

(Process (2): Heat treatment process)
Step (2) is a step of forming a resin layer 14 by subjecting the coating film to heat treatment. By carrying out this step, for example, a ring closing reaction of polyamic acid contained in the curable resin proceeds, and a desired resin layer is formed.
The method for the heat treatment is not particularly limited, and a known method (for example, a method in which a support substrate with a coating film is left standing in a heating oven and heated) is appropriately used.
The heating temperature is preferably 250 ° C. or more and 500 ° C. or less, and the residual solvent ratio is lowered, the imidization ratio is further increased, and the effect of the present invention is more preferable, and 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 curable resin to be used. However, the residual solvent ratio is lowered, the imidization ratio is further increased, and the effect of the present invention is further improved. In this respect, 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 (2), the resin layer 14 containing a polyimide resin is formed on the support base material 12. FIG.
Although the imidation ratio of a polyimide resin is not particularly limited, it is preferably 99.0% or more and more preferably 99.5% or more in terms of more excellent effects of the present invention.
The imidation rate is measured by measuring the curable resin heated at 350 ° C. for 2 hours in a nitrogen atmosphere as 100% imidation rate, and the peak intensity (invariant before and after the heat treatment in the IR spectrum of the curable resin) ( For example, it is determined by the intensity ratio of the peak intensity derived from the imide carbonyl group: about 1780 cm ^{−1 to} the peak derived from the benzene ring: about 1500 cm ⁻¹ ).

(Lamination process)
In the laminating step, the glass substrate 16 is laminated on the surface of the resin layer 14 obtained in the resin layer forming step, and the layer of the support base 12, the resin layer 14, and the layer of the glass substrate 16 are provided in this order. This is a step of obtaining the glass laminate 10. More specifically, as shown in FIG. 3B, a glass substrate 16 having a surface 14a opposite to the support base 12 side of the resin layer 14 and a first main surface 16a and a second main surface 16b. The resin layer 14 and the glass substrate 16 are laminated | stacked by using the 1st main surface 16a as a lamination | stacking surface, and the glass laminated body 10 is obtained.

The method in particular of laminating | stacking the glass substrate 16 on the resin layer 14 is not restrict | limited, A well-known method is employable.
For example, a method of stacking the glass substrate 16 on the surface of the resin layer 14 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 16 is overlaid on the surface of the resin layer 14, the glass substrate 16 may be pressure-bonded to the resin layer 14 using a roll or a press. It is preferable because air bubbles mixed between the resin layer 14 and the glass substrate 16 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 not likely to lead to a distortion defect of the glass substrate 16. Moreover, bubbles are less likely to remain by pressure bonding under vacuum heating.

  When laminating the glass substrate 16, it is preferable that the surface of the glass substrate 16 in contact with the resin layer 14 is sufficiently washed and laminated in an environment with a high degree of cleanliness. The higher the degree of cleanliness, the better the smoothness of the glass substrate 16, which is preferable.

In addition, after laminating | stacking the glass substrate 16, you may perform a pre-annealing process (heat processing) as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the resin layer 14 can be improved and an appropriate peel strength (y) can be obtained. This makes it difficult to cause misalignment and improves the productivity of electronic devices.
The conditions for the pre-annealing treatment are appropriately selected according to the type of the resin layer 14 to be used. From the viewpoint of making the peel strength (y) between the glass substrate 16 and the resin layer 14 more appropriate. Heat treatment is preferably performed 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 10 of the present invention can be used for various applications, for example, manufacturing electronic parts such as 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 to do is mentioned. In this application, the glass laminate 10 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.

<Glass substrate with resin layer and glass laminate (second embodiment)>
Below, one embodiment (2nd embodiment) of the glass substrate with a resin layer concerning this invention and the glass laminated body containing this glass substrate with a resin layer is explained in full detail.
FIG. 4 is a schematic cross-sectional view of an example of a glass substrate with a resin layer according to the present invention.
As shown in FIG. 4, the glass substrate 20 with a resin layer is a laminate having a layer of the glass substrate 16 and a resin layer 14 formed on the glass substrate 16. The resin layer 14 has a surface 14a in contact with the first main surface of the glass substrate 16 and no other material in contact with the surface 14b.
As shown in FIG. 5, the glass substrate 20 with a resin layer is usually laminated so that the surface 14b of the resin layer and the support base 12 are in contact with each other, whereby a member for an electronic device such as a liquid crystal panel is formed on the glass substrate 16. It is used for the member formation process which manufactures.
FIG. 5 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 5, the glass laminated body 100 is a laminated body in which the layer of the supporting base 12 and the layer of the glass substrate 16 and the resin layer 14 exist between them. The resin layer 14 has one surface in contact with the layer of the support base 12 and the other surface in contact with the first main surface 16 a of the glass substrate 16.

In addition, in the glass laminated body 100 of FIG. 5, the resin layer 14 is being fixed on the glass substrate 16, and the resin layer 14 in the glass substrate 20 with a resin layer is the support base material 12 in the glass substrate 20 with a resin layer. Is laminated (adhered) to the support substrate 12 so as to be in direct contact with each other. As described above, 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 resin layer 14 and the glass substrate 16 is greater than the peel strength at the interface between the resin layer 14 and the support base 12.
More specifically, the interface between the glass substrate 16 and the resin layer 14 has a peel strength (z), and a stress in the peeling direction exceeding the peel strength (z) is applied to the interface between the glass substrate 16 and the resin layer 14. Then, the interface between the glass substrate 16 and the resin layer 14 is peeled off. The interface between the resin layer 14 and the support base 12 has a peel strength (w), and when a stress in the peeling direction exceeding the peel strength (w) is applied to the interface between the resin layer 14 and the support base 12, the resin layer 14 and the support base 12 peel.
In the glass laminate 100, the peel strength (z) is higher than the peel strength (w). Therefore, when a stress is applied to the glass laminate 100 in the direction of peeling the support substrate 12 and the glass substrate 16, the glass laminate 100 of the present invention peels off at the interface between the resin layer 14 and the support substrate 12. The glass substrate 20 with a resin layer and the support base 12 are separated.

The peel strength (z) is preferably sufficiently higher than the peel strength (w). Increasing the peel strength (z) means that the adhesion of the resin layer 14 to the glass substrate 16 can be increased, and a relatively higher adhesion can be maintained after the heat treatment than to the support base 12.
Increasing the adhesion of the resin layer 14 to the glass substrate 16 is a method of forming the resin layer 14 on the glass substrate 16 (preferably a polyimide resin composed of repeating units represented by the formula (1) by thermosetting. The curable resin is cured on the glass substrate 16 to form a predetermined resin layer 14). The resin layer 14 bonded to the glass substrate 16 with a high bonding force can be formed by the adhesive force at the time of curing.
On the other hand, the bonding force of the cured resin layer 14 to the support substrate 12 is generally lower than the bonding force generated during the formation. Therefore, by forming the resin layer 14 on the glass substrate 16 and then laminating the support base 12 on the surface of the resin layer 14, the glass laminate 100 satisfying a desired peeling relationship can be manufactured.

  The above-mentioned indentation elastic modulus and elastic power of the resin layer 14 in the glass substrate with resin layer 20 and the glass laminate 100 show the above-described ranges.

  Each layer (support base material 12, glass substrate 16, resin layer 14) which constitutes glass substrate 20 with a resin layer and glass laminate 100 is composed of each of the above-described support substrate 18 with a resin layer and each layer which constitutes glass laminate 10. This is synonymous and will not be described here.

In the glass laminate 100, the resin layer 14 is fixed to the glass substrate 16, and the surface 14b of the resin layer 14 in contact with the support base 12 is laminated (adhered) to the support base 12 in a peelable manner. As described above, the resin layer 14 is bonded to the support base 12 with a weak bonding force, and the peel strength (w) at the interface is the peel strength (z) at the interface between the resin layer 14 and the glass substrate 16. Lower).
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the support base material 12 and the resin layer 14, and is hardly peeled off at the interface between the glass substrate 16 and the resin layer 14. For this reason, although the resin layer 14 adheres to the glass substrate 16, it has the surface characteristic which can peel the support base material 12 easily. That is, the resin layer 14 is bonded to the support base 12 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off, the glass substrate 16 The resin layer 14 is bonded to the resin layer 14 with a bonding force that can be easily peeled without breaking the film. In this invention, the property which can peel this resin layer 14 surface easily is called peelability. On the other hand, the glass substrate 16 and the resin layer 14 are bonded with a bonding force that is relatively difficult to peel.

It is considered that the resin layer 14 and the layer of the support base 12 are bonded with a bonding force caused by a weak adhesive force or van der Waals force. For example, when the resin layer 14 is a polyimide resin layer, when the support substrate 12 is laminated on the surface after the resin layer 14 is formed, the polyimide resin in the resin layer 14 is sufficiently imide so as not to exhibit an adhesive force. If it is, it is considered that they are connected with a binding force caused by van der Waals force. However, the polyimide resin in the resin layer 14 often has a certain weak adhesive force. Even when the adhesiveness is extremely low, when the electronic device member is formed on the laminated body after the glass laminated body 100 is manufactured, the polyimide resin in the resin layer 14 is supported by a heating operation or the like. It is considered that the bonding force between the resin layer 14 and the support substrate 12 is increased by bonding to the 12th surface.
In some cases, the surface of the resin layer 14 before lamination or the surface of the support substrate 12 before lamination can be laminated by performing a treatment for weakening the bonding force between them. By performing non-adhesive treatment or the like on the surface to be laminated, and then laminating, the bonding strength at the interface between the resin layer 14 and the support substrate 12 can be weakened, and the peel strength (w) can be lowered.

The resin layer 14 is bonded to the surface of the glass substrate 16 with a strong bonding force such as an adhesive force or an adhesive force. As described above, the method for increasing the adhesion is achieved by forming the resin layer 14 on the glass substrate 16. For example, by curing a curable resin that becomes a polyimide resin composed of the repeating unit represented by the above formula (1) by thermosetting on the surface of the glass substrate 16, the polyimide resin is adhered to the surface of the glass substrate 16 and is high. A binding force can be obtained. Moreover, a high bond strength can also be obtained by bringing a composition containing a polyimide resin into contact with the surface of the glass substrate 16 and performing a heat treatment as necessary to form a resin layer. Furthermore, the process (for example, process using a coupling agent) which produces strong bond strength between the glass substrate 16 surface and the resin layer 14 is given, and the bond force between the glass substrate 16 surface and the resin layer 14 is given. Can be increased.
The fact that the resin layer 14 and the glass substrate 16 are bonded with a high bonding force means that the peel strength (z) at the interface between them is high.

  Although the manufacturing method in particular of the glass substrate 20 with a resin layer and the glass laminated body 100 is not restrict | limited, in the manufacturing method of the support base material 18 with a resin layer and the glass laminated body 10 mentioned above, it replaces with the support base material 12, and the glass substrate 16 is used. By using the support substrate 12 instead of the glass substrate 16, the desired glass substrate 20 with a resin layer and the glass laminate 100 can be manufactured. For example, the glass layer 100 can be manufactured by forming the resin layer 14 on the glass substrate 16 and then laminating the support base 12 on the resin layer 14.

[Cutting process (cleaving process)]
The glass laminate 10 and the glass laminate 100 described above can be easily cut (cleaved) by bending.
The cutting method is not particularly limited, but a glass laminate is easily cut at a predetermined position. A scribe line (cut line) is put on the surface of the glass laminate, and the glass laminate is bent along the scribe line and cut. The method of doing is mentioned.
Below, in FIG. 6, an example of the cutting method of the glass laminated body 10 is shown.

First, as shown in FIG. 6A, scribe lines (cut lines) 30 are formed at predetermined positions on the surface of the glass laminate 10.
The method for forming the scribe line is not particularly limited, and a known method such as a method using a cutter or a method using laser light is employed.
In FIG. 6A, both surfaces of the glass laminate 10 (the surface on the side opposite to the resin layer 14 side of the support base 12 and the surface on the side opposite to the resin layer 14 side of the glass substrate 16). Although the scribe line 30 is formed on the surface of the glass laminate 10, the scribe line 30 may be formed only on one surface of the glass laminate 10.
In addition, when a scribe line is formed on both surfaces of the glass laminated body 10, it is preferable to arrange | position the scribe line in the position which opposes on both sides of the resin layer 14. FIG.
Moreover, depending on the kind of member which comprises the glass laminated body 10, you may bend and cut the glass laminated body 10 without forming a scribe line.

Next, as shown in FIG. 6B, the glass laminate 10 is bent along the scribe line 30 and cut. More specifically, by bending one end of the glass laminate 10 along the scribe line 30 toward the glass substrate 16, cracks extend in the thickness direction starting from the scribe line 30, and as a result, along the scribe line. The glass laminate 10 is cut.
In FIG. 6B, the glass laminate 10 is cut by bending one end of the glass laminate 10 to the glass substrate 16 side, but the glass laminate is obtained by bending one end of the glass laminate 10 to the support substrate 12 side. The body 10 may be cut. Alternatively, one end of the glass laminate 10 may be bent toward the glass substrate 16 and then bent toward the support base 12.
In addition, you may cleave the glass laminated body 10 by pulling, bending as needed at the time of bending.

  The said cutting process can be implemented suitably after producing a glass laminated body, for example, may be implemented before the member formation process mentioned later, or may be implemented after a member formation process.

[Glass substrate with member and method for producing the same]
In the present invention, an electronic device can be manufactured using the glass laminate (glass laminate 10 or glass laminate 100) described above.
Below, the aspect using the glass laminated body 10 mentioned above is explained in full detail.
By using the glass laminated body 10, the glass substrate with a member (glass substrate with a member for electronic devices) containing a glass substrate and the member for electronic devices is manufactured.
Although the manufacturing method of this glass substrate with a member is not specifically limited, From the point which is excellent in productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the said glass laminated body, and the laminated body with an electronic device member is used. A method is preferred in which the produced and obtained laminate with a member for electronic devices is separated into a glass substrate with a member and a supporting substrate with a resin layer by using the glass substrate side interface of the resin layer as a release surface.
Hereinafter, the step of forming a member for an electronic device on the glass substrate in the glass laminate and manufacturing the laminate with the member for an electronic device is a member forming step, from the laminate with the member for an electronic device to the glass substrate side of the resin layer A process of separating the glass substrate with a member and the support base with a resin layer using the interface as a release surface is called a separation process.
The materials and procedures used in each process are described in detail below.

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 10 obtained in the said lamination process. More specifically, as shown in FIG. 3C, the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain the laminate 24 with the electronic device member. .
First, the electronic device member 22 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member 22 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 22, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or 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 laminated body 22 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 16 of the glass laminated body 10 is used. The electronic device member 22 is formed on the surface 16b surface.
The electronic device member 22 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (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 peeled from the resin layer 14 can be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.

  For example, taking the case of manufacturing an OLED as an example, an organic EL structure on the surface of the glass laminate 10 opposite to the resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form a body, a transparent electrode is formed, 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 a sealing plate Various layers are formed and processed, such as sealing with the use of. 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 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 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 16b of the glass substrate 16 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 16b of the glass substrate 16 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.

(Separation process)
As shown in FIG. 3D, the separation step is for an electronic device from the laminate 24 with a member for electronic devices obtained in the member forming step, with the interface between the resin layer 14 and the glass substrate 16 as a release surface. In the process of separating the glass substrate 16 (the glass substrate with a member) on which the member 22 is laminated, the resin layer 14 and the supporting base material 12 to obtain the glass substrate 26 with a member including the electronic device member 22 and the glass substrate 16. is there.
When the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 26 with a member and the support base material 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the resin layer 14 and given a trigger for peeling, and then the peeling is performed by spraying a mixed fluid of water and compressed air. can do. Preferably, the electronic device member-attached laminate 24 is placed on the surface plate so that the support base material 12 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 side is vacuumed on the surface plate. Adsorbed (sequentially performed when the supporting base material is laminated on both surfaces). In this state, the blade is first allowed to enter the interface between the glass substrate 16 and the resin layer 14. Then, the support substrate 12 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 resin layer 14 and the glass substrate 16, and the air layer spreads over the entire interface, so that the support substrate 18 with the resin layer can be easily peeled off.
Moreover, the support base material 18 with a resin layer can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.
In addition, when peeling the glass substrate 26 with a member and the support base material 18 with a resin layer, it is preferable to peel while spraying a peeling aid on the interface between the glass substrate 16 and the resin layer 14. The peeling aid intends a solvent such as water described above. Examples of the peeling aid used include water, an organic solvent (for example, ethanol), and a mixture thereof.

  When the glass substrate 26 with a member is separated from the laminated body 24 with a member for electronic devices, the fragments of the resin layer 14 are electrostatically adsorbed to the glass substrate 26 with a member by controlling the spraying and humidity with an ionizer. This can be further suppressed.

  The manufacturing method of the glass substrate 26 with a member mentioned above is suitable for manufacture of the small display apparatus used for mobile terminals, such as a mobile telephone and 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 glass substrate 26 with a member manufactured by the above method, a panel for a display device having a glass substrate and a member for a display device, a solar cell having a glass substrate and a member for a solar cell, a glass substrate and a member for a thin film secondary battery. Examples thereof include a thin film 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.

In the above, although the aspect using the glass laminated body 10 was explained in full detail, an electronic device can also be manufactured using the glass laminated body 100 according to the procedure similar to the above.
When the glass laminate 100 is used, in the separation step, the support base 12, the resin layer 14, the glass substrate 16, and the interface between the support base 12 and the resin layer 14 are used as a release surface. And an electronic device including the electronic device member 22.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Examples 1, 2, and 7-9 are Examples, and Examples 3-6 are Comparative Examples.
In the following example, as a glass substrate, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.2 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) )It was used. Further, as a supporting base material, a glass plate made of an alkali-free 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 Example 1: Production of polyamic acid solution (P1)>
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 (BPDA) (29.4 g, 0.1 mol) was added over 1 minute, and the mixture was stirred at room temperature for 30 minutes. ) And / or a polyamic acid solution (P1) 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 160 centipoise at 20 ° C.
The viscosity is obtained by measuring the rotational viscosity at 20 ° C. using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd. In the production examples described later, the viscosity was measured under the same conditions.
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.

<Production Example 2: Production of polyamic acid solution (P2)>
Paraphenylenediamine (10.8 g, 0.1 mol) was dissolved in 1-methyl-2-pyrrolidone (226.0 g) and stirred at room temperature. To this, BPDA (29.4 g, 0.1 mol) was added in 1 minute, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (P2) having an acid-containing solid content concentration of 20% by mass was obtained. When the viscosity of this solution was measured, it was 5000 centipoise at 20 ° C.
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.

<Production Example 3: Production of polyamic acid solution (P3)>
Paraphenylenediamine (10.8 g, 0.1 mol) was dissolved in 1-methyl-2-pyrrolidone (226.0 g) and stirred at room temperature. To this was added BPDA (29.4 g, 0.1 mol) over 1 minute, and the mixture was stirred at room temperature for 5 hours, and a polyamic having a repeating unit represented by the above formula (2-1) and / or formula (2-2) A polyamic acid solution (P3) having an acid-containing solid concentration of 20% by mass was obtained. When the viscosity of this solution was measured, it was 100,000 centipoise at 20 ° C.
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.

<Production Example 4: Production of polyamic acid solution (P4)>
Diaminodiphenyl ether (20.0 g, 0.1 mol) was dissolved in N, N-dimethylacetamide (206.8 g) and stirred at room temperature. To this was added pyromellitic dianhydride (21.8 g, 0.1 mol) over 1 minute, and the mixture was stirred at room temperature for 2 hours, and represented by the above formula (2-1) and / or formula (2-2). A polyamic acid solution (P4) having a solid content concentration of 20% by mass containing a polyamic acid having a repeating unit was obtained. When the viscosity of this solution was measured, it was 2000 centipoise at 20 ° C.
X in the repeating unit represented by the formula (2-1) and / or formula (2-2) contained in the polyamic acid is a group represented by the formula (X2), and A is a formula (A5). The group represented.

<Production Example 5: Production of polyamic acid solution (P5)>
Diaminodiphenyl ether (20.0 g, 0.1 mol) was dissolved in N, N-dimethylacetamide (206.8 g) and stirred at room temperature. To this, BPDA (29.4 g, 0.1 mol) was added in 1 minute, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (P5) having an acid-containing solid concentration of 20% by mass was obtained. When the viscosity of this solution was measured, it was 5000 centipoise at 20 ° C.
X in the repeating unit represented by the formula (2-1) and / or formula (2-2) contained in the polyamic acid is a group represented by the formula (X1), and A is a formula (A5). The group represented.

<Production Example 6: Production of alicyclic polyimide resin solution (P6)>
9,9-bis (4-aminophenyl) fluorene (35 g, 0.1 mol) and γ-butyrolactone (69.3 g) as a solvent and N, N-dimethylacetamide (140 g) were mixed and dissolved, Stir at room temperature. To this, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (22.5 g, 0.1 mol) was added over 1 minute, stirred at room temperature for 2 hours, and a polyamic acid having a solid content concentration of 20% by mass. An acid solution was obtained. When the viscosity of this solution was measured, it was 3000 centipoise at 20 ° C.
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 the formula (X4), A is a formula (A6) and It was group represented by the said formula (A7).

  Next, triethylamine (0.51 g, 0.005 mol) was added all at once as an imidization catalyst. After completion of the dropwise addition, the temperature was raised to 180 ° C., and the reaction was terminated by distilling off the distillate as needed to complete the reaction. Amide (130.7 g) was added and cooled with stirring to obtain an alicyclic polyimide resin solution (P6) having a solid content concentration of 20% by mass.

<Example 1>
First, a supporting substrate having a thickness of 0.5 mm was cleaned with pure water, and further cleaned by UV cleaning.
Next, the polyamic acid solution (P1) is applied onto the first main surface of the supporting substrate with a spin coater (rotation speed: 500 rpm, 15 seconds), and a coating film containing polyamic acid is provided on the supporting substrate. (Coating amount 2 g / m ² ).
The polyamic acid is a resin obtained by reacting the compound represented by the formula (Y1) with the compound represented by the formula (B1).

  Next, after heating the coating film in the atmosphere at 60 ° C. for 15 minutes and then at 120 ° C. for 15 minutes, the coating film was further heated at 350 ° C. for 60 minutes to form a resin layer. In the formed resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by (X1), A is represented by formula (A1) Was made up of).

The imidation ratio was 99.7%. The surface roughness Ra of the formed resin layer surface was 0.2 nm. The thickness of the resin layer was 5 μm. In Examples 1 to 6 described later, the thickness of the resin layer was 5 μm.
In addition, the measuring method of imidation rate and the measuring method of surface roughness Ra were implemented by the above-mentioned method.

Thereafter, the glass substrate and the resin layer on the supporting substrate were bonded together by a vacuum press at room temperature to obtain a glass laminate S1.
In the obtained glass laminate S1, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there were no distortion defects, and the smoothness was good. In addition, in glass laminated body S1, the peeling strength (x) of the interface of a support base material layer and a resin layer was higher than the peeling strength (y) of the interface of a resin layer and a glass substrate.

<Example 2>
A glass laminate S2 was obtained in the same manner as in Example 1 except that the polyamic acid solution (P2) was used instead of the polyamic acid solution (P1) and the spin rotation speed was changed to 2000 rpm.
The polyamic acid is a resin obtained by reacting the compound represented by the above formula (Y1) with the compound represented by the formula (B1). In the formed resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by formula (X1), A is represented by formula (A1) Consisting of a group).

  The imidation ratio was 99.5%. The surface roughness Ra of the formed resin layer surface was 0.2 nm.

  In the obtained glass laminate S2, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there were no distortion defects, and the smoothness was good. In addition, in glass laminated body S2, the peeling strength (x) of the interface of a support base material layer and a resin layer was higher than the peeling strength (y) of the interface of a resin layer and a glass substrate.

<Example 3>
A glass laminate S3 was obtained in the same manner as in Example 1 except that the polyamic acid solution (P3) was used in place of the polyamic acid solution (P1) and the spin speed was changed to 3000 rpm.
The polyamic acid is a resin obtained by reacting the compound represented by the above formula (Y1) with the compound represented by the formula (B1). In the formed resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by formula (X1), A is represented by formula (A1) Consisting of a group).

  The imidation ratio was 99.5%. The surface roughness Ra of the formed resin layer surface was 0.2 nm.

  In the obtained glass laminate S3, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there was no distortion defect, and the smoothness was good. In the glass laminate S3, the peel strength (x) at the interface between the support substrate layer and the resin layer was higher than the peel strength (y) at the interface between the resin layer and the glass substrate.

<Example 4>
A glass laminate S4 was obtained in the same manner as in Example 1 except that the polyamic acid solution (P4) was used instead of the polyamic acid solution (P1), and the spin rotation speed was changed to 3000 rpm.
The polyamic acid is a resin obtained by reacting the compound represented by the above formula (Y2) with the compound represented by the formula (B5). In the formed resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by formula (X2), A is represented by formula (A5) Consisting of a group).

  The imidation ratio was 99.5%. The surface roughness Ra of the formed resin layer surface was 0.2 nm.

  In the obtained glass laminate S4, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there were no distortion defects, and the smoothness was good. In the glass laminate S4, the peel strength (x) at the interface between the support substrate layer and the resin layer was higher than the peel strength (y) at the interface between the resin layer and the glass substrate.

<Example 5>
A glass laminate S5 was obtained in the same manner as in Example 1 except that the polyamic acid solution (P5) was used instead of the polyamic acid solution (P1).
The polyamic acid is a resin obtained by reacting the compound represented by the above formula (Y1) with the compound represented by the formula (B5). In the formed resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by formula (X1), A is represented by formula (A5)). Consisting of a group).

  The imidation ratio was 99.5%. The surface roughness Ra of the formed resin layer surface was 0.2 nm.

  In the obtained glass laminate S5, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there was no distortion defect, and the smoothness was good. In addition, in glass laminated body S5, the peeling strength (x) of the interface of a support base material layer and a resin layer was higher than the peeling strength (y) of the interface of a resin layer and a glass substrate.

<Example 6>
A glass laminate S6 was obtained in the same manner as in Example 1 except that the alicyclic polyimide resin solution (P6) was used instead of the polyamic acid solution (P1).

  The imidation ratio was 99.5%. The surface roughness Ra of the formed resin layer surface was 0.2 nm.

  In the obtained glass laminate S6, the supporting base material and the glass substrate were in close contact with the resin layer without generating bubbles, there were no distortion defects, and the smoothness was good. In the glass laminate S6, the peel strength (x) at the interface between the support substrate layer and the resin layer was higher than the peel strength (y) at the interface between the resin layer and the glass substrate.

(Measurement of indentation elastic modulus and elastic power)
According to the following method, the indentation elastic modulus of the resin layer on the supporting base material before the glass substrate was laminated was measured.
A Vickers pyramid indenter was attached to a microhardness tester (Fischer Instruments, Picodenter HM500), a load-unload test was performed on the resin layer (thickness: 5 μm), and a load displacement curve was measured. Here, the indentation speed (load speed) F is a condition where the resin layer is loaded at a load speed of F = 0.1 mN / sec, the maximum load is kept at 0.5 mN for 5 seconds, and then the load is unloaded at the same load speed. And the indentation elastic modulus and elastic power were measured.

(Evaluation of film formability)
The polyamic acid solution (P1) to the alicyclic polyimide resin solution (P6) are applied onto the first main surface of the supporting substrate with a spin coater, and it is determined whether or not the coating film can be formed on the supporting substrate. did.
The case where a coating film was obtained was designated as “◯”, and the case where a coating film was not obtained was designated as “x”.

(Cutting evaluation of glass laminate)
A scribe line (cut line) was put on a glass substrate and a supporting base material of the obtained glass laminate S1 using a wheel blade (diameter 1 mm) having an APIO Type C blade angle of 115 ° manufactured by Mitsuboshi Diamond Co., Ltd. In addition, when observing from the normal line direction of the glass substrate surface of glass laminated body S1, the scribe line was formed so that the position of the scribe line on a glass substrate and the position of the scribe line on a support base material might correspond. In other words, the scribe line on the glass substrate and the scribe line on the support base were arranged at opposing positions.
Next, along the scribe line on the glass substrate, the glass laminate S1 is bent in a U shape so that the support base materials come close to each other, and then the glass substrate is cut. Then, along the scribe line on the support base material 12 Then, the glass laminate S1 was pulled while being bent in a dogleg shape on the opposite side to cut the entire glass laminate S1.
The case where the glass laminate S1 could be cut by the above procedure was “◯”, and the case where the glass laminate S1 could not be cut was “x”.
The glass laminates S2 to S6 were also evaluated by the same method.

(Heat resistance evaluation)
Next, when the glass laminates S1 to S2 are heat-treated at 400 ° C. for 60 minutes in the atmosphere and cooled to room temperature, the glass substrate S1 to S2 is separated from the supporting base material and the glass substrate, and the resin layer There were no changes in appearance such as foaming or whitening.
And while forming the notch part of peeling by inserting the stainless steel blade 0.1mm in thickness into the interface of the glass substrate and resin layer in the corner part of one place among four places of glass laminated body S1-S2, glass The vacuum suction pad is adsorbed on the non-peeling surface of the substrate and the supporting substrate, and water is sprayed on the interface between the glass substrate and the resin layer while applying an external force in the direction in which the glass substrate and the supporting substrate separate from each other The substrate and the supporting substrate were separated without damage. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
The resin layer was separated from the glass substrate together with the supporting base material. The above results also confirmed that the peel strength (x) at the interface between the support substrate and the resin layer was higher than the peel strength (y) at the interface between the resin layer and the glass substrate.

As shown in Table 1, the glass laminates S1 and S2 described in Examples 1 and 2 satisfying the predetermined requirements could be easily cut by bending.
On the other hand, the glass laminates of Examples 3 to 6 that did not satisfy the predetermined requirements could not be cut by bending.

<Example 7>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate S1 by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming 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 is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after performing a heat treatment in a hydrogen atmosphere and performing a hydrogenation treatment, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is 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 are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel A) is an electron of the present invention. It is a laminated body with a member for devices.
Subsequently, after the panel A sealing body side is vacuum-adsorbed on the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of panel A, and the glass substrate Gives the interface between the resin layer and the resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
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 is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

<Example 8>
In this example, an LCD is manufactured using the glass laminate S1 obtained in Example 1.
First, two glass laminates S1 are prepared, and silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in one glass laminate S1-1 by plasma CVD. . Next, low concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, after a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after a heat treatment and a hydrogenation treatment are performed in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Next, the other glass laminate S1-2 is heat-treated in an air atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate S1 by a sputtering method, and a light shielding layer is formed by etching using a photolithography method. Next, a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing. Next, a film of indium tin oxide is formed by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
Next, the sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass sheets S1-1 on which the pixel electrodes are formed are used. The second main surface sides of the glass substrates of the glass laminate S1 are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.

  Subsequently, the second main surface of the support base material of the glass laminate S1-1 is vacuum-adsorbed on a surface plate, and a thickness of 0. A 1 mm stainless steel blade is inserted to give a trigger for peeling between the first main surface of the glass substrate and the peelable surface of the resin layer. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while water is being supplied to the separation front while spraying a static elimination fluid from the ionizer toward the formed gap. And after adsorb | sucking the 2nd main surface of the support base material of glass laminated body S1-2 with a vacuum suction pad, a suction pad is raised. As a result, only the empty cell of the LCD with the support substrate of the glass laminate S1-1 is left on the surface plate, and the support substrate with the resin layer can be peeled off.

  Next, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed on the surface plate, and the thickness of the glass substrate S1-1 at the interface between the glass substrate and the resin layer at the corner portion is increased. A stainless steel knife having a thickness of 0.1 mm is inserted to give an opportunity for peeling between the first main surface of the glass substrate and the peelable surface of the resin layer. And after adsorb | sucking the 2nd main surface of the support base material of glass laminated body S1-1 with a vacuum suction pad, a suction pad is raised, spraying water between a glass substrate and a resin layer. As a result, only the LCD cell is left on the surface plate, and the supporting base material on which the resin layer is fixed can be peeled off. Thus, a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm are obtained.

  Subsequently, it is divided into a plurality of LCD cells by a cutting step. A step of attaching a polarizing plate to each completed LCD cell is performed, and then a module forming step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

<Example 9>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, molybdenum was formed into a film by sputtering method on the 2nd main surface of the glass substrate in glass laminated body S1, and the gate electrode was formed by the etching using the photolithographic method. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film, and subsequently an indium gallium zinc oxide film is formed by a sputtering method. An oxide semiconductor layer was formed by etching. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protective layer. Subsequently, a molybdenum film is formed by a sputtering method, and etching is performed using a photolithography method. A source electrode and a drain electrode were formed.
Next, heat treatment is performed in the atmosphere. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a passivation layer. Subsequently, indium tin oxide is formed by a sputtering method, and etching is performed using a photolithography method. A pixel electrode is formed.
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 are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel B) is an electronic device according to the present invention. It is a laminated body with a member for devices (panel for display devices with a supporting substrate).
Subsequently, after the panel B sealing body side is vacuum-sucked to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of panel B, and the glass substrate Gives the interface between the resin layer and the resin layer. And after adsorb | sucking the support base material surface of the panel B with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
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 is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

DESCRIPTION OF SYMBOLS 10,100 Glass laminated body 12 Support base material 14 Resin layer 16 Glass substrate 18 Support base material with resin layer 20 Glass substrate with resin layer 22 Electronic device member 24 Laminated body with electronic device member 26 Glass substrate with member 30 Scribe line

Claims (10)

A glass laminate having a supporting substrate, a resin layer, and a glass substrate in this order,
The glass laminated body whose indentation elastic modulus of the said resin layer is 5.5 GPa or more, and whose elastic work modulus of the said resin layer is less than 70%.   The glass laminate according to claim 1, wherein the resin layer is a polyimide resin layer. The polyimide resin is composed of a repeating unit having a tetracarboxylic acid residue (X) and a diamine residue (A) represented by the following formula (1), and the tetracarboxylic acid residue: 50 mol% or more of the total number of (X) consists of groups represented by the following formula (X1), and 50 mol% or more of the total number of residues (A) of the diamines is represented by the following formula (A1). The glass laminate according to claim 2, comprising a base.

(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.)
  The glass laminated body of any one of Claims 1-3 whose said support base material is a glass plate. A glass substrate with a resin layer having a glass substrate and a resin layer formed on the glass substrate, wherein the glass substrate with a resin layer is manufactured by laminating a support base material on the resin layer. Is used to
A glass substrate with a resin layer, wherein the indentation elastic modulus of the resin layer is 5.5 GPa or more, and the elastic power of the resin layer is less than 70%.   The glass substrate with a resin layer according to claim 5, wherein the resin layer is a polyimide resin layer. The polyimide resin is composed of a repeating unit having a tetracarboxylic acid residue (X) and a diamine residue (A) represented by the following formula (1), and the tetracarboxylic acid residue: 50 mol% or more of the total number of (X) consists of groups represented by the following formula (X1), and 50 mol% or more of the total number of residues (A) of the diamines is represented by the following formula (A1). The glass substrate with a resin layer according to claim 6, comprising a base.

(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.)
A support substrate with a resin layer having a support substrate and a resin layer formed on the support substrate, wherein the support substrate with a resin layer is formed by laminating a glass substrate on the resin layer. Used to manufacture the body,
The support base material with a resin layer whose indentation elastic modulus of the said resin layer is 5.5 GPa or more, and whose elastic work modulus of the said resin layer is less than 70%.   The support substrate with a resin layer according to claim 8, wherein the resin layer is a polyimide resin layer. The polyimide resin is composed of a repeating unit having a tetracarboxylic acid residue (X) and a diamine residue (A) represented by the following formula (1), and the tetracarboxylic acid residue: 50 mol% or more of the total number of (X) consists of groups represented by the following formula (X1), and 50 mol% or more of the total number of residues (A) of the diamines is represented by the following formula (A1). The support substrate with a resin layer according to claim 9, comprising a base.

(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.)