TW201536542A - Manufacturing method of support substrate with resin layer, manufacturing method of glass laminated body and manufacturing method of electronic device - Google Patents

Abstract

The present invention relates to a method for manufacturing a support substrate with an attached resin layer which includes a support substrate and a silicon resin layer and is used to manufacture a glass laminate by laminating a glass substrate on the silicon resin layer. The method includes: an application process of forming a curable silicon composition layer on the support substrate by applying a curable silicon composition including curable silicon and a solvent on the support substrate, and then obtaining a curable layer attachment support substrate including the support substrate and the silicon composition layer; an insertion process of inserting the curable layer attachment support substrate into a heat processing apparatus and then stacking the curable layer attachment support substrate on support pins in the heat processing apparatus; a first heating process of arranging a heating plate on an upper side of the curable silicon composition layer of the curable layer attachment support substrate, executing ventilation, performing a heating process on the curable layer attachment support substrate at a first temperate or lower, and removing the solvent remaining on the curable silicon composition layer; a moving process of placing the curable silicon composition layer apart from the heating plate after the first heating process; an extraction process of extracting the curable layer attachment support substrate from the heating process apparatus; and a second heating process of performing a heat process on the curable layer attachment support substrate at a second temperature higher than the first temperature.

Description

Manufacturing method of supporting substrate with resin layer, method for producing glass laminate, and method for manufacturing electronic device

The present invention relates to a method for producing a support substrate with a resin layer, a method for producing a glass laminate, and a method for producing an electronic device.

In recent years, thinner and lighter devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL (Electroluminescence) panels (OLEDs) have been developed, and the glass used in such devices has been progressing. The thinning of the substrate is constantly evolving. If the strength of the glass substrate is insufficient due to thinning, the handleability of the glass substrate is lowered in the manufacturing process of the device.

Recently, in order to cope with the above-mentioned problems, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared, and a member for an electronic device such as a display device is formed on a glass substrate of a glass laminate, and then the reinforcing plate is made of glass. The substrate is separated (for example, refer to Patent Document 1). The reinforcing plate has a supporting substrate and a polyoxyalkylene resin layer fixed to the supporting substrate, and the polyoxyxylene resin layer and the glass substrate are adhered to each other in a peelable manner. The reinforcing plate is peeled off at the interface between the polyoxygen resin layer of the glass laminate and the glass substrate, and the reinforcing plate separated from the glass substrate can be laminated with a new glass substrate to be reused as a glass laminate.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2007/018028

On the other hand, a method in which a support substrate having a coating film on its surface is placed on top of a plurality of support pins and heated and dried is known. Further, as a method of performing heat drying, a method of using a heat treatment apparatus provided with a hot plate is known.

When the inventors of the present invention produced the reinforcing plate according to the method described in Patent Document 1, the supporting substrate on which the coating film of the polyoxyxylene resin layer is heated by the surface is placed on the plurality of heat treatment devices. On the top of each of the support pins, a hot plate is placed on the coating film to perform a prebaking treatment, and then a post-baking treatment is performed to form a polyoxyxylene resin layer, and then a glass substrate is laminated on the polyoxynoxy resin layer to form a glass laminate. body. Then, the obtained glass laminate was subjected to heat treatment, and the peeling property of the glass substrate was evaluated. As a result, it was found that one of the polyoxynitride layers was agglomerated and adhered to the surface of the glass substrate.

If the polyoxyxene resin is attached to the glass substrate, the obtained electronic device is not suitable for use as a product, and thus the yield of the electronic device is lowered, and the productivity is lowered.

The present invention has been made in view of the above problems, and an object of the invention is to provide a method for producing a support substrate having a resin layer supporting a substrate and a polyoxynitride resin layer, wherein the support substrate for the resin layer is used for peeling off the glass substrate. The production of a glass laminate for suppressing aggregation failure of the polyoxyn resin layer.

Moreover, an object of the present invention is to provide a method for producing a glass laminate using a support substrate with a resin layer produced by the method for producing a support substrate with a resin layer, and an electronic device using the glass laminate. method.

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

That is, the first aspect of the present invention is a method of manufacturing a support substrate with a resin layer having a support substrate and a single side disposed on the support substrate. An oxygen resin layer for laminating a glass substrate on a polyoxyxene resin layer to produce a glass laminate, and the method for manufacturing the support substrate of the resin layer includes, in order, a coating step, which comprises containing a curable polysiloxane The curable polyaluminoxy composition with a solvent is applied onto the support substrate to form a hardenable polyoxynitride composition layer on the support substrate, thereby obtaining a hardenable layer including the support substrate and the curable polyoxynitride composition layer. a support substrate; a carry-in step of loading a support substrate having a curable layer into a heat treatment device, and placing a support substrate on which a curable layer is placed on a support pin in the heat treatment device; and the first heating step is performed on the support substrate A heating plate is disposed on the upper portion of the curable polyoxynitride composition layer of the support substrate with the curable layer, and while the exhaust gas is exhausted, the support substrate having the curable layer is heat-treated at a temperature equal to or lower than the first temperature, and remains on the support substrate. a solvent removal step of the curable polydecane oxide composition layer; and a moving step of removing the hardened polyoxyxide composition layer subjected to the heat treatment from the heating plate after the first heating step; a step of carrying out the support substrate with the curable layer from the heat treatment device, and a second heating step of heat-treating the support substrate with the curable layer at a second temperature higher than the first temperature. A polyoxygenated resin layer was obtained.

In the first aspect, the curable polyfluorene oxide is preferably an organic alkenyl polyoxyalkylene having an alkenyl group and an organic hydrogen polyoxyalkylene having a hydrogen atom bonded to a deuterium atom.

In the first aspect, the first temperature preferably satisfies the initial boiling point of the solvent -30 ° C ≦ the first temperature 初 the initial boiling point of the solvent + 30 ° C.

A second aspect of the present invention provides a method for producing a glass laminate having a lamination step of laminating a glass substrate on a polyoxynated resin layer in a support substrate with a resin layer produced in the first aspect. The glass laminate of the support substrate, the polyoxymethylene resin layer, and the glass substrate is sequentially provided.

A third aspect of the present invention provides a method of manufacturing an electronic device, comprising: a member forming step of forming a member for an electronic device on a surface of a glass substrate of a glass laminate manufactured by the second aspect; a laminate having a member for an electronic device; and a separating step of removing the support substrate with the resin layer from the laminate of the member for the electronic device; An electronic device having a member for a glass substrate and an electronic device is obtained.

According to the present invention, it is possible to provide a method of manufacturing a support substrate having a resin layer supporting a substrate and a polyoxyxylene resin layer, the support substrate of the resin layer being used for more suppressing the polyoxyalkylene resin layer when the glass substrate is peeled off. The manufacture of agglomerated glass laminates.

Moreover, according to the present invention, a method for producing a glass laminate using a support substrate with a resin layer produced by the method for producing a support substrate with a resin layer, and an electronic device using the glass laminate can be provided. method.

10‧‧‧Support substrate

12‧‧‧ hardened polysiloxane composition layer

14‧‧‧Support substrate with hardened layer

16‧‧‧Polyoxy resin layer

16a‧‧‧ Surface of the polyoxyl resin layer opposite to the support substrate side

18‧‧‧Support substrate with resin layer

20‧‧‧ glass substrate

20a‧‧‧1st main surface of the glass substrate

20b‧‧‧2nd main surface of the glass substrate

22‧‧‧Members for electronic devices

24‧‧‧Laminated body of components for electronic devices

26‧‧‧Electronic devices

30‧‧‧heat treatment unit

32‧‧‧heating room

34‧‧‧Support pins

36‧‧‧Support Desk

38‧‧‧heating plate

40‧‧‧Exhaust pipe

42‧‧‧ Moving into the exit

100‧‧‧glass laminate

Fig. 1 is a flow chart showing the manufacturing steps of a method for producing a support substrate with a resin layer of the present invention.

2(A) and 2(B) are schematic cross-sectional views showing an embodiment of a method of manufacturing a support substrate with a resin layer of the present invention in the order of steps.

Fig. 3 is a schematic cross-sectional view showing the configuration of a heat treatment apparatus.

Figure 4 is a schematic cross-sectional view showing a glass laminate of the present invention.

5(A) and 5(B) are schematic cross-sectional views showing an embodiment of a method of manufacturing an electronic device according to the present invention in order of steps.

In the following, the preferred embodiments of the present invention are described with reference to the drawings, but the present invention is not limited to the following embodiments, and various embodiments may be applied in the following embodiments without departing from the scope of the invention. Change and replacement.

The inventors of the present invention have studied the above problems and found that when the layer of the curable polydecane oxide composition is dried using a hot plate disposed on the upper portion of the layer of the curable polydecane oxide composition, it remains in the curable polyoxyl combination. The solvent of the layer is volatilized and stays between the hot plate and the layer of the curable polyoxynitride composition, which is one of the causes of the above problems. If such a residual volatile solvent is present in a large amount, it is difficult for the residual solvent to volatilize from the layer of the curable polyoxo composition, and When the support substrate with the curable layer is carried out from the heat treatment device, the solvent returns to the curable polyoxynitride composition layer again, and the hardenability of the curable polyoxynitride composition layer is lowered, and as a result, the aggregation failure is presumed. It becomes easy to carry out.

Therefore, it is presumed that the desired effect can be obtained by, after the end of the heating, the heating plate and the curable polyaluminoxy composition layer are separated to expand the space between the two, thereby promoting the solvent exhaust. Therefore, the concentration of the solvent remaining is lowered, and the influence on the polyoxymethylene resin layer is lowered.

Fig. 1 is a flow chart showing the manufacturing steps in the method for producing a support substrate with a resin layer of the present invention. As shown in FIG. 1, a manufacturing method of a support substrate with a resin layer includes a coating step S102, a loading step S104, a first heating step S106, a moving step S108, a carrying-out step S110, and a second heating step S112.

Hereinafter, the materials used in the respective steps and their procedures will be described in detail. First, the coating step S102 will be described in detail.

<Coating step>

In the coating step S102, a curable polyfluorene oxide composition containing a curable polyfluorene oxide and a solvent is applied onto a support substrate, and a curable polyoxynitride composition layer is formed on the support substrate, thereby obtaining a support substrate and The step of supporting the substrate with the hardenable layer of the hardenable polyoxynitride composition layer. By performing this step S102, the curable polysilicon composition layer 12 can be formed on the support substrate 10 as shown in FIG. 2(A) to obtain the support substrate 14 with the curable layer.

Hereinafter, the materials (support substrate, curable polyfluorene oxide composition) used in the step S102 will be described in detail first, and then the procedure of the step S102 will be described in detail.

(support substrate)

The support substrate 10 has two main surfaces, a front surface and a back surface, and cooperates with the polyoxyxene resin layer 16 described below to support and reinforce the glass substrate 20 described below, and the member forming step (electronic device member) described below Glass-based in the manufacture of components for preventing electronic devices in the manufacturing step) Deformation, damage, damage, etc. of the board 20. Moreover, in the case of using a glass substrate having a thickness smaller than that of the prior art, a glass laminate having the same thickness as the previous glass substrate can be used, and a manufacturing method suitable for the glass substrate of the previous thickness can be used in the member forming step or The manufacturing equipment is also one of the purposes of using the support substrate 10.

As the support substrate 10, for example, a glass plate, a plastic plate, a metal plate such as a SUS (Steel Use Stainless) plate, a ceramic plate, or the like can be used. In the case where the member forming step is accompanied by heat treatment, the support substrate 10 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 20, and more preferably formed of the same material as the glass substrate 20. That is, the support substrate 10 is preferably a glass plate. In particular, the support substrate 10 is preferably a glass plate containing the same glass material as the glass substrate 20.

The thickness of the support substrate 10 may be thicker than the glass substrate 20 or thinner than the glass substrate 20. The thickness of the support substrate 10 is preferably selected based on the thickness of the glass substrate 20, the thickness of the resin layer 16, and the thickness of the glass laminate. For example, the current member forming step is designed to treat a substrate having a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 20 and the thickness of the resin layer 16 is 0.1 mm, the thickness of the support substrate 10 is set to 0.4mm. The thickness of the support substrate 10 is preferably 0.2 to 5.0 mm in the usual case.

When the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons of easy handling and difficulty in damage. In addition, when the thickness of the glass plate is peeled off after the member for electronic device is formed, it is preferably 1.0 mm or less for the reason that the rigidity is moderately bent without being damaged.

The difference between the average linear expansion coefficient (hereinafter, simply referred to as "average linear expansion coefficient") of the support substrate 10 and the glass substrate 20 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or less, more preferably 300 × 10 ^-7 / ° C or less, further preferably 200 × 10 ^-7 / ° C or less. When the difference is too large, the glass laminate is strongly bent during the heating and cooling in the member forming step, or the glass substrate 20 may be peeled off from the support substrate 18 with the resin layer described below. When the material of the glass substrate 20 is the same as the material of the support substrate 10, the above problem can be suppressed.

(curable polyoxyl composition)

The curable polydecene oxide composition contains at least a curable polyfluorene oxide and a solvent. As described below, the curable polyfluorene-containing composition of the curable polyfluorene oxide can be obtained by applying the curable polydecane oxide composition onto the support substrate 10.

Hereinafter, the materials contained in the composition will be described in detail.

The curable polyfluorene is a compound or composition which is cured to form a polyoxyxylene resin. The curable polyfluorene oxide is classified into a condensation reaction type polyoxane, an addition reaction type polyoxane, an ultraviolet curing type polyfluorene oxygen, and an electron beam curing type polyoxane according to the hardening mechanism. Any of the hardened polyfluorenes. Among these, an addition reaction type polyoxane is preferred. The reason for this is that the hardening reaction proceeds easily, and the degree of peeling property when the polyoxynoxy resin layer is formed is good, and the heat resistance is also high.

The addition reaction type polyoxo oxygen-based composition contains a main component and a crosslinking agent, and is hardened by the presence of a catalyst such as a platinum-based catalyst. The hardening of the addition reaction type polyoxygen is promoted by heat treatment. The main component in the addition reaction type polyoxo is preferably an organic polyoxyalkylene having an alkenyl group (vinyl group or the like) bonded to a halogen atom (i.e., an organic alkenyl polyoxyalkylene; further, preferably It is a linear chain), and an alkenyl group etc. become a crosslinking point. The crosslinking agent in the addition reaction type polyoxo is preferably an organic polyoxyalkylene having a hydrogen atom (hydrogenated alkylene group) bonded to a halogen atom (that is, an organic hydrogen polyoxyalkylene; further, preferably It is linear), and a hydrogenated alkylene group or the like becomes a crosslinking point.

The addition reaction type polyoxymethylene is hardened by an addition reaction of a crosslinking point of a main agent and a crosslinking agent. Further, in terms of the more excellent heat resistance derived from the crosslinked structure, the molar ratio of the hydrogen atom of the organohydrogenpolyoxyalkylene bonded to the hydrogen atom of the halogen atom relative to the alkenyl group of the organic alkenyl polyoxyalkylene is further compared. Good for 0.5~2.

The curable polydecyloxy composition comprises a solvent. The solvent is preferably one which can easily dissolve various components and can be easily removed by volatilization. Specifically, for example, butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF (Tetrahydrofuran, tetrahydrofuran), chloroform, and the like. In particular, a saturated hydrocarbon is used, and one or two or more kinds of various saturated hydrocarbons (linear saturated hydrocarbons, branched saturated hydrocarbons, and alicyclic saturated hydrocarbons) can be used as practical various saturated hydrocarbon solvents. For example, Isopar G (manufactured by Exxon Mobil Co., Ltd.), Isopar L (manufactured by Exxon Mobil Co., Ltd.), Isopar H (manufactured by Exxon Mobil Co., Ltd.), Isopar M (manufactured by Exxon Mobil Co., Ltd.), NORPAR 13 (Exxon Mobil Co., Ltd.) Made by the company), NORPAR 15 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D40 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D60 (manufactured by Exxon Mobil Co., Ltd.), Exxsol D80 (manufactured by Exxon Mobil Co., Ltd.), Neothiosol (Centralized Chemicals Co., Ltd.) Made by the company), IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.).

In the above, in the first heating step, it is preferred to use a solvent having an initial boiling point (at atmospheric pressure) of 210 ° C or less.

When the curable polyfluorene oxide contained in the curable polyoxynene composition is an addition reaction type polyoxane, the curable polyoxynoxy composition may further contain a catalyst (especially a platinum group metal contact). Medium), or a reaction inhibitor.

A platinum group metal catalyst (a platinum group metal catalyst for hydrogenation) is used to carry out and promote the hydrogenation of an alkenyl group in the above organic alkenyl polyoxyalkylene and a hydrogen atom in the above organic hydrogen polyoxyalkylene. Catalyst for reaction. Examples of the platinum group-based catalyst include platinum-based, palladium-based, and lanthanide-based catalysts. In terms of economy and reactivity, it is particularly preferable to use a platinum-based catalyst.

The reaction inhibitor (reaction inhibitor for hydrazine hydrogenation) suppresses the catalytic activity of the above-mentioned catalyst (especially a platinum group metal catalyst) at normal temperature, and the life of the hardenable polyfluorene composition becomes long. Applicable period extender (also known as retarder). Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, hydrazine compounds, and organic chlorine compounds. It is especially preferred to be an acetylene compound (for example, a decyl alcohol and a decyl alcohol of an acetylene alcohol).

(order of steps)

The method of applying the curable polyfluorene oxide composition on the support substrate is not particularly limited, and a known method can be employed. Examples of the coating method include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method. From the above methods, it can be appropriately selected depending on the kind of the curable polysiloxane composition.

Further, the thickness of the layer of the curable polydecane oxide composition is not particularly limited, and may be appropriately adjusted so as to obtain a polyoxynitride resin layer having a preferable thickness as described below.

<Moving step>

In the loading step S104, the support substrate having the curable layer is carried into the heat treatment device, and the support substrate on which the curable layer is placed is placed on the support pin in the heat treatment device. By carrying out this step, the support substrate 14 to which the curable layer is attached is placed on the top end (top) of the support pin 34 in the heat treatment device 30 as shown in FIG. Further, the support pin 34 supports the back surface of the support substrate 10 in the support substrate 14 with the curable layer (the side opposite to the side having the curable polyoxynitride composition layer).

Hereinafter, the heat treatment apparatus 30 used in this step will be described in detail first.

Fig. 3 is a cross-sectional view showing an outline of an example of the heat treatment apparatus 30 of the present invention. The heat treatment device 30 is a device for performing heat treatment in the first heating step S106 described below, and is a so-called prebaking device.

The heat treatment device 30 includes a support pin 34 for supporting the support substrate 14 with a curable layer, a support table 36 for supporting the support pin 34, and a plate shape disposed on the upper portion of the support substrate 14 with the curable layer in the heating chamber 32. The plate 38 is heated.

In FIG. 3, only two support pins 34 are shown, but the number of the pins is not particularly limited. Further, the heat treatment device 30 has an elevating mechanism (not shown) for elevating and lowering the heating plate 38, and the heating plate 38 is vertically movable in Fig. 3 .

Further, an exhaust pipe 40 connected to an exhaust mechanism (not shown) is provided in an upper portion of the heat treatment device 30, and air supplied from the gas supply port (not shown) to the heat treatment device 30 is provided. The solvent or the like which is volatilized from the sclerosing polyoxygen composition layer 12 is discharged from the exhaust pipe 40. Further, a loading port 42 for loading and unloading the support substrate 14 with the curable layer on the side of the heat treatment device 30 is provided.

In the procedure of the step S104, the support substrate 14 with the curable layer is carried into the heat treatment device 30 via the carry-in port 42, and the support substrate 14 to which the curable layer is placed is placed on the support pin 34.

<1st heating step>

In the first heating step S106, a heating plate is disposed on the upper portion of the curable polyoxynitride composition layer of the support substrate with the curable layer, and the support substrate having the curable layer is heated at a temperature equal to or lower than the first temperature while exhausting. The step of removing the solvent remaining in the layer of the hardenable polysiloxane composition is carried out. This step S106 is a so-called prebaking step. By performing the step S106, the solvent remaining in the layer of the curable polydecane oxide composition can be removed, and the curable polycondensation can be achieved by heating at a suitable temperature. The surface of the oxygen composition is smoothed. After performing the prebaking treatment in the above manner, the post-baking treatment is performed in the second heating step S112 described below, thereby further removing the solvent remaining in the formed polyoxynoxy resin layer, whereby the surface is changed. It is flatter and has better adhesion to the glass substrate.

In the step S106, as shown in FIG. 3, the heating plate 38 is placed on the upper portion of the support substrate 14 to which the curable layer is attached, and heat treatment is performed. Further, as shown in FIG. 3, the heating plate 38 is opposed to the curable polyoxynitride composition layer 12.

The distance between the heating plate 38 and the curable polyoxynitride composition layer 12 is not particularly limited, and the solvent is efficiently removed from the curable polyoxynitride composition layer 12, and the decomposition of the hardenable polyfluorene oxygen is suppressed. In other words, it is preferably 30 to 120 mm, more preferably 60 to 90 mm.

Further, in the step S106, the heat treatment may be performed while gradually changing the distance between the heating plate 38 and the curable polyoxynitride composition layer 12. For example, the heating plate 38 may be subjected to heat treatment while being gradually separated from the curable polyoxynitride composition layer 12. More specifically, the distance between the heating plate 38 and the curable polyoxynitride composition layer 12 is The heat treatment is carried out under the condition of X, and then the heating plate 38 and the hardenable polyoxynitride composition layer 12 may be further away from each other at a distance X (the heating plate 38 and the curable polyoxynitride composition layer 12). The heat treatment is again performed under the distance Y>distance X).

As a condition of the heat treatment in the step S106, the optimum conditions are appropriately selected depending on the type of the solvent or the curable polyfluorene to be used, and the solvent-removing polyoxynitride composition layer is more excellent in the solvent removal property. The surface is flat and the decomposition of the curable polyfluorene is further suppressed. The first temperature is preferably in the range of from -30 ° C of the initial boiling point of the solvent to the initial boiling point of the solvent + 30 ° C. In other words, the first temperature preferably satisfies the following relational expression.

The initial boiling point of the solvent is -30 ° C ≦ the first temperature ≦ the initial boiling point of the solvent + 30 ° C

Further, the initial boiling point of the solvent means a value measured in accordance with JIS K0066 (1992). The contents of JIS K0066 (1992) are incorporated herein by reference.

Furthermore, the first temperature in the first heating step is preferably 210 ° C or less in terms of flattening the surface of the curable polyfluorene oxide composition layer and further suppressing decomposition of the curable polyfluorene oxide. Among them, in terms of suppressing aggregation failure of the polyoxyxene resin layer, it is preferably 150 to 210 ° C, more preferably 180 to 205 ° C.

The heating time is not particularly limited, and the optimum conditions are appropriately selected depending on the type of the solvent to be used or the type of the curable polyfluorene oxide, and it is preferably 1 to 5 in terms of the removability of the residual solvent and the productivity. Minutes, preferably 2 to 3 minutes.

In the present step S106, heat treatment is performed while exhausting is performed. As shown in FIG. 3, an exhaust pipe 40 is provided in the heat treatment device 30, and is exhausted by the exhaust pipe 40 during the heat treatment. The amount of exhaust gas is not particularly limited, and is preferably 100 L/min or more, and more preferably 900 L/min or more in terms of more efficiently removing the solvent. The upper limit is not particularly limited, and is preferably 2000 L/min or less in terms of performance and economy of the device.

In addition, when the amount of the exhaust gas is 100% when the exhaust gas from the exhaust pipe 40 is fully opened, it is preferably 50% or more, more preferably 75% or more, and further preferably 100%.

When the step S106 is performed, the gas may be supplied from a gas supply port (not shown). The volatile solvent in the heating chamber 32 can be efficiently removed by supplying a gas. The type of the gas to be supplied is not particularly limited, and examples thereof include an inert gas such as air or nitrogen.

The amount of supply of the gas is not particularly limited, and is more preferably 100 L/min or more, and more preferably 900 L/min or more in terms of more efficiently removing the solvent. The upper limit is not particularly limited, and is preferably 2000 L/min or less in terms of performance and economy of the device.

Moreover, as the gas to be supplied, it is preferable to heat the air in terms of the removability of the residual solvent in the curable polyoxynitride composition layer. The temperature of the heated air is not particularly limited, and is preferably 100 to 150 ° C in terms of solvent removal property and surface smoothness of the curable polyoxynitride composition layer.

<moving step>

The moving step S108 is a step of separating the curable polyfluorinated composition layer subjected to the heat treatment from the heating plate after the first heating step S106. More specifically, in FIG. 3, the heating plate 38 is moved in the direction of the arrow, thereby moving the curable polyoxynitride composition layer 12 away from the heating plate 38 to expand the distance therebetween, thereby expanding both. The space between them. By performing the step S108, the concentration of the solvent remaining between the curable polydecane oxide composition layer 12 and the heating plate 38 can be made thin, so that the solvent removal property is improved, and the solvent can be suppressed from being hardened again. The layer of the oxygen-containing composition 12 is attached.

As described above, the heat treatment device 30 includes an elevating mechanism (not shown) for elevating and lowering the heating plate 38, and the elevating mechanism moves the heating plate 38 away from the curable polysilicon composition layer 12.

The distance from the curable polysiloxane composition layer 12 and the heating plate 38 is preferably further separated by a distance of 20 mm or more from the first heating step S106, and more preferably 40 mm or more. The upper limit is not particularly limited, but in terms of the size of the device, it is usually 100 mm or less.

The moving time of the heating plate 38 is not particularly limited, and in terms of productivity, it is preferably within 5 seconds, more preferably within 3 seconds.

Furthermore, in the aspect of FIG. 3, the heating plate 38 is moved, so that the distance between the hardened polyoxynitride composition layer 12 and the heating plate 38 is enlarged, but the procedure of this step S108 is not limited to this aspect. The support substrate 14 including the hardenable layer of the curable polyoxyn composition layer 12 may be moved to keep the two away. For example, when the support pin is a so-called jacking pin, the jacking pin of the support substrate supporting the hardenable layer may be lowered after the first heating step S106, and the hardenable polyoxynitride composition layer and the heating plate may be used. keep away.

<Moving out step>

The carry-out step S110 is a step of carrying out the support substrate with the curable layer from the heat treatment device.

In the step S110, the support substrate 14 with the curable layer is carried out from the heat treatment device 30 via the carry-in port 42 of the heat treatment device 30. That is, the carry-in port 42 is opened, and the support substrate 14 with the curable layer is recovered from the inside of the heat treatment apparatus 30.

<2nd heating step>

The second heating step S112 is a step of obtaining a polysilicon oxide resin layer by heat-treating the support substrate of the curable layer recovered in the carry-out step S110 at a second temperature higher than the first temperature. In this step S112, a so-called post-baking treatment is carried out, and by performing the step S112, the solvent in the layer of the curable polyfluorene oxide composition is further removed, whereby the hardening of the poly-oxygen oxide is carried out to obtain a polyoxynitride resin layer. . By carrying out this step, the support substrate 18 including the resin-attached layer supporting the substrate 10 and the polyoxy-oxygen resin layer 16 as shown in Fig. 2(B) can be obtained.

The method of the heat treatment in the step S112 is not particularly limited, and a known heating device such as an oven can be used.

The temperature condition of the heat treatment in this step S112 is performed at a temperature higher than the first temperature of the first heating step S106 described above. First temperature and second temperature The difference is not particularly limited, and the optimum conditions are appropriately selected depending on the type of the hardening polysiloxane or the solvent to be used, and the aggregation failure of the polyoxyxene resin layer is further suppressed. 100 ° C, more preferably 30 to 70 ° C.

Among them, the second temperature is preferably more than 210 °C. The solvent removal and the hardening reaction in the self-hardening polysiloxane composition layer 12 are preferably more than 210 ° C and not more than 250 ° C. The heating time is appropriately selected depending on the materials to be used, and is preferably from 10 to 120 minutes, more preferably from 20 to 60 minutes, in terms of productivity and solvent removal.

(Support substrate with resin layer)

By the above steps, the support substrate 18 including the support substrate 10 and the resin layer attached to the polyoxyalkylene resin layer 16 fixed on the support substrate 10 can be obtained.

The support substrate 18 with the resin layer is used to laminate the glass substrate 20 on the polyoxynitride layer 16 as shown in FIG. 4 to produce the glass laminate 100.

The polyoxynoxy resin layer 16 in the support substrate 18 with the resin layer is fixed to one side of the support substrate 10 by the hardening reaction of the curable polyoxynitride composition layer 12 on the support substrate 10, The detachable method is in close contact with the glass substrate 20 described below. The polyoxygenated resin layer 16 prevents the misalignment of the glass substrate 20 until the operation of separating the glass substrate 20 from the support substrate 10 is performed, and is prevented from being easily peeled off from the glass substrate 20 due to the separation operation, and the glass substrate 20 or the like is separated by the operation. damaged. Further, the polyoxyxene resin layer 16 is fixed to the support substrate 10, and the polyoxynitride resin layer 16 is not peeled off from the support substrate 10 during the separation operation, and the support substrate 18 with the resin layer can be obtained by a separation operation.

The surface of the polyoxyxene resin layer 16 that is in contact with the glass substrate 20 is detachably adhered to the first main surface of the glass substrate 20. In the present invention, the property of easily peeling off the surface of the polyoxyalkylene resin layer 16 is referred to as easy peelability (peelability).

In the present invention, there is a difference in the peel strength (that is, the stress required for peeling) for the above-mentioned fixed and peelable close contact, and the fixed means the peel strength with respect to the close contact. Larger. Further, the term "peelable" means that it can be peeled off and peeled off without causing peeling of the surface to be fixed. Specifically, in the case where the glass substrate 20 and the support substrate 10 are separated from each other in the glass laminate of the present invention, it means that the surface to be adhered is peeled off, and the surface to be fixed is not peeled off. Therefore, in the operation of separating the glass substrate 20 and the support substrate 10 in the glass laminate, the glass laminate is divided into both the glass substrate 20 and the support substrate 18 with the resin layer.

That is, the bonding strength of the polyoxyxylene resin layer 16 to the surface of the support substrate 10 is relatively higher than the bonding strength of the polyoxynoxy resin layer 16 to the first main surface of the glass substrate 20.

The thickness of the polyoxyxene resin layer 16 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, still more preferably 7 to 20 μm. When the thickness of the polyoxyxene resin layer 16 is in the above range, even if air bubbles or foreign matter are present between the polyoxynoxy resin layer 16 and the glass substrate 20, the occurrence of deformation defects of the glass substrate 20 can be suppressed. Further, when the thickness of the polyoxyxene resin layer 16 is too thick, it takes time and material to form, which is uneconomical and the heat resistance is lowered. Further, when the thickness of the polyoxyxene resin layer 16 is too small, the adhesion between the polyoxynated resin layer 16 and the glass substrate 20 may be lowered.

<Method of Manufacturing Glass Laminate>

As described above, the support substrate with the resin layer obtained through the above steps is used to laminate a glass substrate on the polyoxynitride layer to produce a glass laminate.

The method for producing the glass laminate is not particularly limited, and it is preferable to carry out a lamination step of laminating a glass substrate on the polyoxyalkylene resin layer in the support substrate with the resin layer, thereby obtaining a support substrate and a polylayer in sequence. An oxygen resin layer and a glass laminate of a glass substrate.

Hereinafter, the procedure of the lamination step will be described in detail.

(layering step)

The lamination step is to laminate the glass substrate 20 on the surface of the polyoxynoxy resin layer 16 in the support substrate 18 with the resin layer, and to obtain the support substrate 10 and the polyoxymethylene resin layer in this order. 16. The step of the glass laminate 100 of the glass substrate 20. More specifically, as shown in FIG. 4, the surface 16a of the polyoxy-oxygen resin layer 16 on the side opposite to the support substrate 10 side and the first glass substrate 20 having the first main surface 20a and the second main surface 20b are the first. The main surface 20a is an accumulation layer, and the polysilicon oxide resin layer 16 and the glass substrate 20 are laminated to obtain a glass laminate 100.

The glass substrate 20 to be used will be described in detail below.

The method of laminating the glass substrate 20 on the polyoxynoxy resin layer 16 is not particularly limited, and a known method can be employed.

For example, a method of laminating the glass substrate 20 on the surface of the polyoxyxene resin layer 16 under a normal pressure environment can be cited. Further, if necessary, the glass substrate 20 is placed on the surface of the polyoxyxene resin layer 16, and then the glass substrate 20 is pressure-bonded to the polyoxyalkylene resin layer 16 by using a roll or pressurization. It is preferable to remove bubbles which are mixed between the polyoxynoxy resin layer 16 and the glass substrate 20 by pressure bonding by a roll or pressurization.

When the polyoxyxylene resin layer 16 and the glass substrate 20 are pressure-bonded by a vacuum lamination method or a vacuum press method, it is more preferable to suppress the incorporation of air bubbles or to ensure good adhesion. There is also an advantage that even when fine bubbles remain in the vacuum bonding, the bubbles are not grown by heating, and deformation defects of the glass substrate 20 are hard to occur.

In the case of laminating the glass substrate 20, it is preferable to sufficiently wash the surface of the glass substrate 20 which is in contact with the polyoxynoxy resin layer 16, and to laminate it in an environment having a high degree of cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 20 becomes, which is preferable.

Further, after the laminated glass substrate 20 is laminated, a pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 20 to the polyoxynoxy resin layer 16 is improved, and the peel strength can be suitably obtained, and it becomes difficult to produce an electronic device in the member forming step described below. The dislocation of the components, etc., and the productivity of the electronic device is improved.

The conditions of the pre-annealing treatment are appropriate depending on the type of the polyoxyxene resin layer 16 to be used. The optimum conditions are selected so that the peeling strength between the glass substrate 20 and the polyoxyxene resin layer 16 is more appropriate, preferably at a temperature of 300 ° C or higher (preferably 300 to 400 ° C). The heat treatment is carried out for 5 minutes or more (preferably 5 to 30 minutes).

(glass substrate)

In the glass substrate 20, the first main surface 20a is in contact with the polyoxynitride resin layer 16, and the second main surface 20b on the side opposite to the polyoxynitride resin layer 16 side is provided with an electronic device member.

The type of the glass substrate 20 may be a normal one, and examples thereof include a glass substrate for a display device such as an LCD (liquid crystal display) or an OLED (Organic Light-Emitting Diode). The glass substrate 20 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. As an index of the heat shrinkage rate, the linear expansion coefficient prescribed in JIS R 3102 (1995 Revision) can be used. The contents of JIS R 3102 (amended in 1995) are incorporated herein by reference.

When the linear expansion coefficient of the glass substrate 20 is large, since the member forming step described below is often accompanied by heat treatment, various problems are likely to occur. For example, when a thin film transistor (TFT) is formed on the glass substrate 20, if the glass substrate 20 on which the TFT is formed is cooled under heating, the misalignment of the TFT becomes excessive due to thermal contraction of the glass substrate 20. Hey.

The glass substrate 20 is obtained by melting a glass raw material and shaping the molten glass into a plate shape. Such a molding method may be a usual one, and for example, a float method, a melting method, a flow down method, a rich method, a Luber method, or the like may be used. Further, in particular, the glass substrate 20 having a small thickness can be formed by heating a glass which is temporarily formed into a plate shape to a temperature at which it can be formed, and stretching by a method such as stretching to thin the glass (re-drawing method). And get.

The type of the glass of the glass substrate 20 is not particularly limited, and is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda lime glass, a high cerium oxide glass, or another oxide-based glass containing cerium oxide as a main component. The oxide-based glass is preferably a glass having a content of cerium oxide in an amount of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 20, a glass suitable for the type of the member for an electronic device or a manufacturing step thereof is used. For example, a glass substrate for a liquid crystal panel is likely to have an influence on liquid crystals due to elution of an alkali metal component, and therefore is composed of glass (alkali-free glass) containing substantially no alkali metal component (including a normal alkaline earth metal component). As described above, the glass of the glass substrate 20 is appropriately selected depending on the type of the apparatus to be applied and the manufacturing steps thereof.

The thickness of the glass substrate 20 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and still more preferably 0.10 mm or less from the viewpoint of thickness reduction and/or weight reduction of the glass substrate 20. When the thickness of the glass substrate 20 is 0.3 mm or less, the glass substrate 20 can be provided with good flexibility. When the thickness of the glass substrate 20 is 0.15 mm or less, the glass substrate 20 can be wound into a roll shape.

Moreover, the thickness of the glass substrate 20 is preferably 0.03 mm or more for the reason that the production of the glass substrate 20 is easy and the operation of the glass substrate 20 is easy.

Further, the glass substrate 20 may include two or more layers. In this case, the material forming each layer may be the same material or a different material. Moreover, in this case, "the thickness of the glass substrate 20" means the total thickness of all layers.

(glass laminate)

The glass laminate 100 has a laminate of the support substrate 10, the glass substrate 20, and the polyoxynoxy resin layer 16 present between the layers. The polyoxyxene resin layer 16 is in contact with the support substrate 10 on one surface thereof, and the other surface thereof is in contact with the first main surface 20a of the glass substrate 20.

This glass laminate 100 is used in the member forming step described below. In other words, the glass laminate 100 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 20b of the glass substrate 20. Thereafter, the glass laminate in which the member for electronic device is formed is separated into the support substrate 18 with the resin layer and the electronic device, and the support substrate 18 with the resin layer does not become a part constituting the electronic device. A new glass substrate 20 can be laminated on the support substrate 18 with the resin layer to be reused as a new glass laminate 100.

The interface between the support substrate 10 and the polyoxyxene resin layer 16 has a peel strength (x), if When the stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the substrate 10 and the polyoxynoxy resin layer 16, peeling occurs at the interface between the support substrate 10 and the polyoxyxene resin layer 16. The interface between the polyoxyxene resin layer 16 and the glass substrate 20 has a peeling strength (y). When a stress exceeding the peeling strength (y) in the peeling direction is applied to the interface between the polyoxynoxy resin layer 16 and the glass substrate 20, Peeling occurs at the interface between the oxygen resin layer 16 and the glass substrate 20.

As described above, in the glass laminate 100 (also referred to as a laminate of the member for electronic devices described below), the peel strength (x) is greater than (higher than) the peel strength (y). Therefore, when a stress in a direction in which the support substrate 10 and the glass substrate 20 are peeled off is applied to the glass laminate 100, the glass laminate 100 is peeled off at the interface between the polyoxynitride resin layer 16 and the glass substrate 20 to be separated into a glass substrate. 20 and a support substrate 18 with a resin layer.

That is, the polyoxyxene resin layer 16 is fixed to the support substrate 10 to form a support substrate 18 with a resin layer, and the glass substrate 20 is detachably adhered to the polyoxynoxy resin layer 16.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 16 to the support substrate 10 can be improved, and the relatively high adhesion to the glass substrate 20 after the heat treatment can be maintained.

The improvement of the adhesion of the polyoxyxene resin layer 16 to the support substrate 10 is achieved by forming the curable polyoxyxene composition layer 12 on the support substrate 10 to form a polyfluorinated oxygen as described above. Resin layer 16. The polyoxynitride resin layer 16 bonded to the support substrate 10 with a high bonding force can be formed by the adhesion force at the time of cross-linking hardening.

On the other hand, the bonding strength of the cured product of the curable polyoxynitride composition layer 12 to the glass substrate 20 is generally lower than that at the time of crosslinking hardening described above.

The glass laminate 100 can be used for various purposes, and examples thereof include the use of a panel for a display device, a PV, a film secondary battery, and an electronic component such as a semiconductor wafer on which a circuit is formed. Further, in this application, the glass laminate 100 is often exposed to high temperature conditions (for example, 360 ° C or higher) (for example, 1 hour or longer).

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

<Electronic device (glass substrate with attached members) and method of manufacturing the same>

In the present invention, an electronic device (a glass substrate with a member) including a glass substrate and a member for an electronic device is produced by using the above-described glass laminate.

The method of manufacturing the electronic device is not particularly limited, and in terms of excellent productivity of the electronic device, it is preferable to form an electronic device by forming a member for an electronic device on a glass substrate in the glass laminate. The laminated body of the member is separated into a supporting substrate of the electronic device and the resin-attached layer from the laminated body of the member for electronic device obtained by using the side surface of the glass substrate side of the polyoxyxene resin layer as a peeling surface.

In the following, a step of forming a laminate for a member for an electronic device on a glass substrate in the glass laminate is referred to as a member forming step, and the glass substrate side interface of the polyoxyxene resin layer is peeled off. The step of separating the laminated body of the member for electronic device into the supporting substrate of the electronic device and the resin-attached layer is referred to as a separating step.

Hereinafter, the materials and procedures used in the respective steps will be described in detail.

(component forming step)

The member forming step is a step of forming a member for an electronic device on the glass substrate 20 in the glass laminate 100 obtained in the above laminating step. More specifically, as shown in FIG. 5(A), the electronic device member 22 is formed on the second main surface 20b (exposed surface) of the glass substrate 20, and the laminated body 24 for the electronic device is obtained.

First, the electronic device member 22 used in this step will be described in detail, and the procedure of the step will be described in detail later.

(Mechanical components (functional components))

The electronic device member 22 is formed on the glass substrate 20 in the glass laminate 100 and is a member constituting at least a part of the electronic device. More specifically, as an electronic device The member 22 is a member used for a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, a member for a display device, a member for a solar cell, and a film 2). Sub-battery member, circuit for electronic parts).

For example, as a member for a solar cell, a transparent electrode such as a tin oxide of a positive electrode, a tantalum layer represented by a p layer/i layer/n layer, a metal of a negative electrode, or the like may be used as the member for the solar cell, and the like. Various members and the like corresponding to a compound type, a dye-sensitized type, a quantum dot type, and the like are listed.

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

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

(procedure of steps)

The manufacturing method of the laminated body 24 of the member for electronic devices described above is not particularly limited, and the second main surface of the glass substrate 20 of the glass laminate 100 is formed by a conventionally known method depending on the type of the constituent members of the electronic device member. A member 22 for an electronic device is formed on 20b.

In addition, the electronic device member 22 may not be the entire member (hereinafter referred to as "all members") of the second main surface 20b of the glass substrate 20, and may be one part of all members (hereinafter referred to as "partial member" "). The part from which the polyoxynoxy resin layer 16 is peeled off may also be attached The glass substrate of the sub-members is formed into a glass substrate (corresponding to an electronic device described below) with all the members in the subsequent step.

Moreover, the glass substrate with all the members which are peeled off from the polyoxynoxy resin layer 16 may be formed with other electronic device members on the peeling surface (first main surface 20a). Moreover, the laminated body with all the members may be combined, and thereafter, the laminated body with the resin layer may be peeled off from the laminated body of all the members to manufacture an electronic device. Further, an electronic device can be assembled by using two laminated bodies with all the members, and then the laminated body with the resin layers removed from the laminated body of all the members, and an electronic device having two glass substrates can be manufactured.

For example, in the case of manufacturing an OLED, the surface of the glass substrate 20 of the glass laminate 100 on the side opposite to the side of the polyoxyxene resin layer 16 (corresponding to the second main surface 20b of the glass substrate 20) is formed. The organic EL structure is formed by forming or processing various layers to form a transparent electrode; and further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed; Electrode; and sealing using a sealing plate. Specific examples of the formation or treatment of the layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, in the case of manufacturing a TFT-LCD, the manufacturing method has various steps such as a TFT forming step, a CF forming step, and a bonding step, and the TFT forming step is applied to the second main member of the glass substrate 20 of the glass laminate 100. On the surface 20b, a metal film and a metal oxide film formed by a usual film formation method such as a CVD (Chemical Vapor Deposition) method or a sputtering method are used to form a film by using a resist liquid. a TFT (TFT); the CF forming step is performed on the second main surface 20b of the glass substrate 20 of the other glass laminate 100, and the resist liquid is used for pattern formation to form a color filter (CF); In the step, the laminated body of the TFT obtained in the TFT forming step and the laminated body of the CF obtained in the CF forming step are laminated.

In the TFT forming step or the CF forming step, TFT or CF is formed on the second main surface 20b of the glass substrate 20 by using a known photolithography technique or etching technique. At this point, you can use anti- The etching liquid is used as a coating liquid for pattern formation.

Further, before forming the TFT or the CF, the second main surface 20b of the glass substrate 20 may be washed as needed. As the washing method, a dry cleaning or a wet washing which is well known can be used.

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

(separation step)

In the separation step, as shown in FIG. 5(B), the interface between the polyoxyxene resin layer 16 and the glass substrate 20 is a peeling surface, and the laminated body 24 of the member for electronic device obtained in the above-described member forming step is separated into The glass substrate 20 (electronic device) of the electronic device member 22 and the support substrate 18 with the resin layer are laminated to obtain the electronic device 26 including the electronic device member 22 and the glass substrate 20.

In the case where the electronic device member 22 on the glass substrate 20 at the time of peeling is a part of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 20 after separation.

The method of peeling the glass substrate 20 and the support substrate 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade can be inserted into the interface between the glass substrate 20 and the polyoxyxene resin layer 16, and after the origin of the peeling is given, the mixed fluid of water and compressed air is blown and peeled off. It is preferable that the support substrate 10 of the laminated body 24 for the electronic device-attached member is placed on the upper side, the electronic device member 22 side is placed on the pressure plate, and the electronic device member 22 side is vacuum-adsorbed to the pressure plate. (In the case where the two-layer layer has a supporting substrate, it is sequentially performed), and in this state, the blade is first invaded into the interface of the glass substrate 20-polyoxyalkylene resin layer 16. Then, the support substrate 10 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pad is sequentially raised from the vicinity of the insertion blade. Thereby using the polyoxyalkylene resin layer 16 The interface of the glass substrate 20 or the agglomerated fracture surface of the polyoxyxene resin layer 16 forms an air layer which spreads over the entire surface of the interface or the agglomerated fracture surface, and the support substrate 10 can be easily peeled off.

Further, the support substrate 10 can be laminated with a new glass substrate to produce the glass laminate 100 of the present invention.

Further, when the electronic device 26 is separated from the laminated body 24 of the self-contained electronic device member, it is possible to suppress the electrostatic adsorption of the fragments of the polyoxynoxy resin layer 16 to the electronic device by controlling the blowing or humidity by the ionizer. 26 cases.

The above-described manufacturing method of the electronic device 26 is preferably used for the manufacture of a small display device used by a mobile terminal such as a mobile phone or a PDA (Personal Digital Assistant). Display devices mainly include LCD or OLED, and as LCD, including TN (Twisted Nematic), STN (Super Twisted Nematic), FE (Ferroelectric), TFT (Thin-film) Transistor, thin film transistor type, MIM (Metal-Insulator-Metal), IPS (In-Plane Switching) type, VA (Vertical Aligned) type, and the like. It can also be applied basically in the case of any of the passive driving type and the active driving type.

The electronic device 26 manufactured by the above method includes a panel for a display device having a member for a glass substrate and a display device, a solar cell having a member for a glass substrate and a solar cell, and a member for a glass substrate and a secondary battery. A film secondary battery, an electronic component having a glass substrate and a member for an electronic device, and the like. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

[Examples]

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

In the following examples and comparative examples, a glass plate composed of an alkali-free borosilicate glass (length 880 mm, width 680 mm, thickness 0.2 mm, linear expansion coefficient 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd., was used. The name "AN100" is used as a glass substrate. Further, as the support substrate, the same glass plate (length 920 mm, width 730 mm, plate thickness 0.5 mm, linear expansion coefficient 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd., trade name) was used. AN100").

<Example 1>

First, the surface of the support substrate is washed with an alkaline aqueous solution, and then washed with pure water to be cleaned.

Then, using a die coater (coating speed: 40 mm/s, discharge amount: 8 ml), the following solution S was applied to the first main surface of the support substrate to contain an unhardened crosslinkable organic polyfluorene. The layer of the oxyalkylene (hardenable polyoxynitride composition layer) was provided on the support substrate to obtain a support substrate (coating amount: 20 g/m ² ) having a curable layer.

(solution S)

Linear linear methyl polysiloxane (component A), manufactured by Azmax Co., Ltd., trade name "VDT-127", viscosity at 25 ° C: 700-800 cP (centipoise), organic polyoxymethane The mol% of the vinyl group in 1 mol: 0.325), the linear methyl hydrogen polyoxyalkylene as the component (B) (manufactured by Azmax, trade name "HMS-301", viscosity at 25 ° C: 25-35 cP (centipoise), the number of hydrogen atoms bonded to the deuterium atom in one molecule: 8) The molar ratio (hydrogen atom/vinyl group) of all the hydrogen atoms bonded to all the hydrogen atoms of the deuterium atom becomes 0.9. In this manner, 1 part by mass of the oxime compound having an acetylene-based unsaturated group (boiling point: 120 ° C) represented by the following formula (1) as the component (C) is mixed with 100 parts by weight of the mixture of the oxirane. .

HC≡CC(CH ₃ ) ₂ -O-Si(CH ₃ ) ₃ (1)

Then, a platinum-based catalyst (manufactured by Shin-Etsu Silicones Co., Ltd., trade name) was added to the total amount of the component (A) and the component (B) and the component (C) in a platinum equivalent of platinum. "CAT-PL-56") to obtain an organopolyoxane composition Mixture. Furthermore, 150 parts by weight of IP solvent 2028 (initial boiling point: 200 ° C, manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts by weight of the obtained mixed liquid to obtain a mixed solution.

Then, the support substrate with the curable layer is carried into the heating chamber through the loading and unloading port in the heat treatment device shown in FIG. 3, and the curable layer is placed on the tip end of the plurality of support pins provided at the bottom of the heating chamber. Support the substrate and close the loading and exiting. Further, the tip end of the support pin is in contact with the surface of the back side of the support substrate (the side opposite to the side having the curable polyoxynitride composition layer) in the support substrate with the curable layer.

In the heat treatment apparatus, as shown in FIG. 3, a heating plate is disposed on the upper portion of the curable polyoxynitride composition layer of the support substrate with the curable layer, and the distance between the curable polyoxynitride composition layer and the heating plate is 70mm.

First, the support substrate having the curable layer was heated at 200 ° C for 60 seconds by the heating plate, and then the distance between the curable polysiloxane composition and the heating plate was changed to 80 mm, and further, 90 seconds was performed. heating.

Further, at the time of heat treatment, the exhaust gas was exhausted under conditions of 960 L/min (the amount of exhaust gas from the exhaust pipe was equivalent to full opening), and heated air (temperature: 120 ° C) was supplied under conditions of 1000 L/min.

After the end of the heat treatment, the hot plate was moved 50 mm away from the layer of the curable polyoxynitride composition. Thereafter, the loading/unloading port of the heat treatment device is opened, and the supporting substrate with the curable layer subjected to the heat treatment is carried out from the heat treatment device.

Thereafter, the support substrate with the curable layer after the heat treatment is placed in another heat treatment device, and further subjected to a heat treatment (post-baking treatment) at 250 ° C for 1450 seconds, and the first substrate is supported. The main surface was formed into a polyoxynitride resin layer having a thickness of 8 μm.

Then, the glass substrate and the polyoxymethylene resin layer on the support substrate are bonded together by atmospheric pressure at room temperature to obtain a glass laminate S1.

In the obtained glass laminate S1, the support substrate and the glass substrate are adhered to each other without generating bubbles between the polyoxynated resin layers, and there is no deformation defect and smoothness. Also good. Further, in the glass laminate S1, the peeling strength at the interface between the layer of the polyimide layer and the layer of the support substrate is larger than the peel strength at the interface between the layer of the glass substrate and the layer of the polyimide resin layer.

<Example 2>

The glass laminate was produced according to the same procedure as in Example 1 except that the amount of exhaust gas during the heat treatment was changed from 960 L/min to 500 L/min, and the supply amount of the heated air was changed from 1000 L/min to 600 L/min. Body S2. Further, in the glass laminate S2, the peel strength at the interface between the layer of the polyimide layer and the layer of the support substrate is larger than the peel strength at the interface between the layer of the glass substrate and the layer of the polyimide resin layer.

<Comparative Example 1>

After the completion of the heat treatment, the glass laminate C was produced in the same manner as in Example 1 except that the heat-receiving sheet was moved and the support substrate with the curable layer after the heat treatment was removed from the heat treatment apparatus.

<Cohesive failure evaluation>

The glass laminate obtained in the above Examples and Comparative Examples was cut into 100 mm × 75 mm, and heat-treated at 350 ° C for 60 minutes in a nitrogen atmosphere.

Then, the glass laminate after the heat treatment was cut into 25 mm × 75 mm, and a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the polyoxynoxy resin layer at one of the four corner portions to form a peeling. The notch portion applies an external force to a direction separating the glass substrate from the support substrate, and separates the glass substrate from the support substrate.

The surface of the evaluation object (25 mm × 65 mm) in contact with the polyoxyxylene resin layer of the peeled glass substrate was observed by visual observation, and the adhesion rate (%) of the polyoxynoxy resin layer was determined { (attached to the peeled glass substrate) The area/observation area of the polyoxyalkylene resin layer on the surface of the upper polyoxyethylene resin layer side was ×100}, and was evaluated based on the following criteria. The greater the adhesion rate, the more agglomerated and destroyed one part of the polyoxymethylene resin layer.

"○": the case where the adhesion rate is less than 5%

"△": the case where the adhesion rate is 5% or more and less than 10%

"X": the case where the adhesion rate is 10% or more

In the case of the evaluation of the aggregation failure, the evaluation result of "○" in the first embodiment was the evaluation result of "△" in the second embodiment, and the evaluation result of "x" in the comparative example 1.

From the results, it was confirmed that in the comparative example 1 in which the treatment of the hot plate and the curable polyfluorene oxide composition layer was not carried out, the aggregation failure of the polyoxymethylene resin layer was easily performed.

Further, from the results of Example 1 and Example 2, it was confirmed that the amount of exhaust gas was more suppressed by aggregation failure.

<Example 3>

In this example, an OLED was produced using the glass laminate S1 obtained in Example 1.

First, on the second main surface of the glass substrate of the glass laminate S1, tantalum nitride, ruthenium oxide, and amorphous ruthenium are sequentially formed by a plasma CVD method. Then, boron of a low concentration is injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to carry out dehydrogenation treatment. Then, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing device. Then, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Then, on the second main surface side of the glass substrate, a ruthenium oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering to form a film by using a photolithography method. The etching is performed to form a gate electrode. Then, by using a photolithography method and an ion doping apparatus, a high concentration of boron and phosphorus is implanted into a desired region of each of the N-type and the P-type to form a source region and a drain region. Then, on the second main surface side of the glass substrate, an interlayer insulating film is formed by film formation of cerium oxide by a plasma CVD method, and film formation by aluminum by sputtering method and by photolithography are used. The TFT electrode is formed by etching. Then, after performing a hydrogenation treatment in a hydrogen atmosphere, a passivation layer is formed by film formation of tantalum nitride by a plasma CVD method. Then, coating on the second main surface side of the glass substrate The ultraviolet curable resin is formed into a planarization layer and a contact hole by photolithography. Then, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

Then, on the second main surface side of the glass substrate, 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine as a hole injection layer was sequentially deposited by a vapor deposition method. , as a hole transport layer, bis[(N-naphthyl)-N-phenyl]benzidine, as a light-emitting layer in the 8-hydroxyquinoline aluminum complex (Alq ₃ ) mixed with 2,6-double [4-[N-(4-Methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN) 40% by volume, and as an electron transport layer The Alq _{3 is} formed into a film. Then, aluminum is formed into a film by a sputtering method, and a counter electrode is formed by etching using a photolithography method. Then, on the second main surface side of the glass substrate, an ultraviolet curing type is interposed. The other glass substrate is bonded to the other layer and sealed. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is A laminate of the member for an electronic device of the present invention.

Then, after the sealing body side of the panel A is vacuum-adsorbed to the platen, a stainless steel blade having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the panel A, and the interface between the glass substrate and the resin layer is imparted. The starting point of stripping. Then, the first main surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, and then the adsorption pad is raised. Here, the insertion of the blade is performed by blowing an electrostatic fluid to the interface between the glass substrate and the resin layer from an ionizer (manufactured by KEYENCE Co., Ltd.). Then, the ionizer continues to blow the neutralizing fluid to the formed voids, and injects water into the stripping front while lifting the vacuum adsorbing pad. As a result, only the glass substrate on which the organic EL structure is formed remains on the platen, and the support substrate with the resin layer can be peeled off.

Then, the separated glass substrate is cut by a laser cutting or scribing-breaking method, and divided into a plurality of units, and then the glass substrate on which the organic EL structure is formed is combined with the counter substrate, and the module forming step is performed. And making OLED. The OLED obtained in the above manner has no problem in characteristics.

The present invention has been described in detail with reference to the specific embodiments thereof.

The present application is based on Japanese Patent Application No. 2013-260253, filed on Dec.

10‧‧‧Support substrate

12‧‧‧ hardened polysiloxane composition layer

14‧‧‧Support substrate with hardened layer

30‧‧‧heat treatment unit

32‧‧‧heating room

34‧‧‧Support pins

36‧‧‧Support Desk

38‧‧‧heating plate

40‧‧‧Exhaust pipe

42‧‧‧ Moving into the exit

Claims (5)

A manufacturing method of a support substrate with a resin layer, the support substrate with a resin layer having a support substrate and a polyoxyalkylene resin layer provided on one side of the support substrate, and for laminating a glass substrate on the polysilicon oxide resin layer The method for producing a glass laminate, the support substrate for the resin layer, comprises a coating step of applying a curable polyoxynoxy composition containing a curable polyfluorene oxide and a solvent to the support substrate. Forming a hardenable polyoxynitride composition layer on the support substrate to obtain a support substrate having a curable layer comprising the support substrate and the curable polyoxynitride composition layer; and carrying the step to the heat treatment device Carrying the support substrate with the curable layer therein, and placing the support substrate with the curable layer on the support pin in the heat treatment device; the first heating step is performed on the support substrate of the curable layer A heating plate is disposed on the upper portion of the curable polyoxynitride composition layer, and the supporting substrate of the hardenable layer is placed at a temperature lower than the first temperature while exhausting. The heat treatment is performed to remove the solvent remaining in the curable polyoxynitride composition layer; and the moving step is performed after the first heating step to cause the hardened polysulfonate composition layer subjected to the heat treatment Leaving the heating plate; carrying out the step of carrying out the support substrate with the curable layer from the heat treatment device; and performing a second heating step for the hardening at the second temperature higher than the first temperature The support substrate of the layer is subjected to heat treatment to obtain a polyoxymethylene resin layer. The method for producing a support substrate with a resin layer according to claim 1, wherein the hardenable polyfluorene oxide comprises an organic alkenyl polyoxyalkylene having an alkenyl group, and an organic hydrogen polycondensation having a hydrogen atom bonded to a germanium atom. Oxytomane. The method for producing a support substrate with a resin layer according to claim 1 or 2, wherein the first temperature satisfies an initial boiling point of the solvent of -30 ° C ≦ a first temperature 初 an initial boiling point of the solvent + 30 ° C. A method for producing a glass laminate having a lamination step of laminating a glass substrate on the polyoxyalkylene resin layer in a support substrate with a resin layer manufactured by the production method according to any one of claims 1 to 3, A glass laminate having a support substrate, a polyoxymethylene resin layer, and a glass substrate is obtained in this order. A method of manufacturing an electronic device, comprising: a member forming step of forming an electronic device member on a surface of the glass substrate of the glass laminate produced by the manufacturing method of claim 4, thereby obtaining an electronic device And a separation step of removing the support substrate with the resin layer from the laminate of the member for electronic device, and obtaining an electronic device having the glass substrate and the member for the electronic device.