KR101973826B1 - Laminate, method for producing laminate, and method for producing glass substrate having member for electronic devices attached thereto - Google Patents

Abstract

(상기 식 (1) 중, R¹ 은 수소 원자 또는 탄소 원자수 1 ∼ 4 의 알킬기를 나타낸다. 상기 식 (2) 중, R⁶ 및 R⁷ 은, 각각 독립적으로 탄소 원자수 1 ∼ 4 의 알킬기를 나타낸다.)This invention is equipped with the layer of a support plate, the layer of a resin layer, and a glass substrate in this order, and the peeling strength (y) of the interface of the layer of the said support plate and the said resin layer is the interface of the said resin layer and the said glass substrate. Organosiloxy unit (A) which is higher than the peel strength (x) or the cohesive failure strength (z) of the resin layer, the resin of the resin layer is a crosslinked silicone resin, and the crosslinked silicone resin is represented by formula (1) -1) and the organosiloxy unit (B-1) represented by Formula (2), and the ratio of (A-1) + (B-1) with respect to all organo siloxy units is 70- It is related with the laminated body which is 100 mol% and is a crosslinked silicone resin whose ratio of (A-1) with respect to the sum total of (A-1) and (B-1) is 15-50 mol%:

(In Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In Formula (2), R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms. Is displayed.)

Description

The manufacturing method of a laminated body, a manufacturing method of a laminated body, and a glass substrate with a member for electronic devices {LAMINATE, METHOD FOR PRODUCING LAMINATE, AND METHOD FOR PRODUCING GLASS SUBSTRATE HAVING MEMBER FOR ELECTRONIC DEVICES ATTACHED THERETO}

This invention relates to the manufacturing method of a laminated body, the manufacturing method of a laminated body, and the glass substrate with a member for electronic devices.

In recent years, thinning and weight reduction of devices (electronic devices), such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED), are progressing, and the thinning of the glass substrate used for these devices is progressing. When the strength of the glass substrate becomes insufficient by thinning, the handleability of the glass substrate falls in the manufacturing process of a device.

Therefore, conventionally, after forming a device member (for example, a thin film transistor) on the glass substrate thicker than a final thickness, the method of thinly thinning a glass substrate by a chemical etching process is adopted. However, in this method, for example, when the thickness of one glass substrate is thinned from 0.7 mm to 0.2 mm or 0.1 mm, most of the material of the original glass substrate is scraped off with an etchant, thus improving productivity and use efficiency of raw materials. It is not preferable from the viewpoint.

In addition, in the thinning method of the glass substrate by the said chemical etching, when a fine flaw exists on the surface of a glass substrate, fine flaws (etch pits) are formed by an etching process as a starting point, and it becomes an optical defect. There was a case.

Recently, in order to cope with the above problem, a laminate obtained by laminating a thin glass substrate and a reinforcement plate is prepared, and after forming a member for an electronic device such as a display device on the thin glass substrate of the laminate, a supporting plate is formed from the thin glass substrate. A method of separating these is proposed (for example, refer patent document 1). The reinforcement plate has a support plate and a resin layer fixed on the support plate, and the resin layer and the thin glass substrate are in close contact with each other so as to be peelable. The interface of the resin layer of a laminated body and a thin glass substrate peels, and the reinforcement board isolate | separated from the thin glass substrate can be laminated | stacked with a new thin glass substrate, and can be reused as a laminated body.

On the other hand, the resin layer obtained using the thermosetting resin of patent document 2 is known as a heat resistant resin layer.

International Publication No. 07/018028 Japanese Unexamined Patent Publication No. 2009-215343

Regarding the laminate described in Patent Literature 1, higher heat resistance has recently been demanded. In accordance with the high functionalization and complexity of the electronic device member formed on the glass substrate of the laminated body, the temperature at the time of forming the electronic device member becomes further high, and the time exposed to the high temperature also requires a long time. Not a lot.

The laminated body of patent document 1 can withstand the process of 300 degreeC in air | atmosphere for 1 hour. However, according to the examination of the present inventors, the silicone resin of the resin layer in the laminated body of patent document 1 decomposes in 400 degreeC in a short time, and a large amount of outgas is generated. The generation of such outgas contaminates the electronic device member formed on the glass substrate, resulting in lowering the productivity of the electronic device.

Moreover, a crack etc. generate | occur | produce in the resin layer itself by decomposition | disassembly of a resin layer, adhesiveness with the glass substrate laminated | stacked on it falls, and the position shift of a glass substrate at the time of manufacture of the member for electronic devices by which high temperature processing is performed, etc. It is easy to produce, and there exists a possibility of reducing productivity of an electronic device as a result.

In addition, when separating a glass substrate from a laminated body, a part of heat-deteriorated resin layer may adhere to the peeling surface of the glass substrate which is a product side, and the removal was very difficult.

This inventor examined about the heat resistance improvement of the resin layer of patent document 1. As a silicone resin with high heat resistance, a silicone resin crosslinked by a condensation reaction is known. In addition, the silicone resin of patent document 1 is a silicone resin bridge | crosslinked by the hydrosilylation reaction. Of the silicone resins crosslinked by the condensation reaction, silicone resins having units in which aryl groups such as phenyl groups are bonded to silicon atoms are particularly high in heat resistance. The silicone resin described in patent document 2 etc. is known as such a silicone resin. However, as a result of using the silicone resin of patent document 2 as a material of the resin layer of patent document 1, the surface shape of the surface laminated | stacked with the glass substrate of a resin layer is rough, and adhesiveness with respect to the resin layer of a glass substrate is not necessarily enough. It could not be used as a laminated body of patent document 1.

This invention is made | formed in view of the said subject, The laminated body which can be used also in high temperature heat processing conditions, and can maintain the cleanliness of the peeling surface of the separated glass substrate by performing a cleaning process, and the manufacturing method of the laminated body are It aims to provide.

Moreover, this invention also makes it the objective to provide the manufacturing method of the glass substrate with a member for electronic devices using the laminated body.

MEANS TO SOLVE THE PROBLEM The present inventors completed this invention, as a result of earnestly examining in order to solve the said subject.

That is, the 1st aspect of this invention is equipped with the layer of a support plate, the layer of a resin layer, and a glass substrate in this order, The peeling strength (y) of the interface of the layer of the said support plate, and the said resin layer is the said resin layer, It is higher than the peeling strength (x) of the interface of the said glass substrate or the cohesive fracture strength (z) of the said resin layer, resin of the said resin layer is crosslinked silicone resin, and the said crosslinked silicone resin is represented by Formula (1) mentioned later. (A-1) + to all organosiloxy units, including the organosiloxy unit (A-1) to be mentioned and the organosiloxy unit (B-1) represented by Formula (2) described later Lamination | stacking of the crosslinked silicone resin whose ratio of (B-1) is 70-100 mol%, and the ratio of (A-1) with respect to the sum total of (A-1) and (B-1) is 15-50 mol%. It is a sieve.

In a 1st aspect, the crosslinked silicone resin is further represented by the organosiloxy unit (A-2) represented by Formula (3) mentioned later, and the organo siloxy unit represented by Formula (4) mentioned later (B- [(A-1) + (B-2)] for [(A-1) + (A-2) + (B-1) + (B-2)], including at least one of 2) It is preferable that the ratio of is 15-50 mol%.

Moreover, the phenyl group (X) represented by Formula (9) mentioned later in Formula (1) and Formula (3), and the alkyl group represented by R <^6> and / or R <^7> in Formula (2) and (4) ( It is preferable that ratio of Y) is [(X)] / [(X) + (Y)] = 10-40 mol%.

Moreover, it is preferable that the ratio of [(A-1) + (A-2) + (B-1) + (B-2)]] with respect to all organo siloxy units is 95-100 mol%.

Moreover, it is preferable that all the organo siloxy units represented by Formula (1)-(4) mentioned later are units derived from an organoalkoxysilane compound.

In addition, in 1st aspect, it is preferable that peeling strength (x) is higher than cohesive failure strength (z). Moreover, it is preferable that the thickness of the said resin layer is 1-5 micrometers, and it is preferable that the said support plate is a glass plate. Moreover, it is preferable that the difference of the average linear expansion coefficient in 25-300 degreeC of the said support plate and the said glass substrate is 0-500 * 10 <^-7> / ^degreeC .

The 2nd aspect of this invention is a manufacturing method of the laminated body of 1st aspect of this invention, Comprising: The film | membrane of curable silicone resin used as a crosslinking silicone resin mentioned later by crosslinking hardening is formed on the surface of a support plate, and is curable on the surface of the said support plate It is a manufacturing method of the laminated body which crosslinks-cures a silicone resin, forms the film of crosslinked silicone resin, and then laminates a glass substrate on the surface of the film of the said crosslinked silicone resin.

In the second aspect, the curable silicone resin consists of a partial hydrolysis condensate of a mixture of an organoalkoxysilane compound, and a solution containing the curable silicone resin and a solvent is applied to the surface of the support plate to remove the solvent. It is preferable to form the film of curable silicone resin. Moreover, it is preferable that the weight average molecular weights of the said partial hydrolysis-condensation products are 10,000-200,000. Moreover, as for the weight average molecular weight of the said partial hydrolysis-condensation thing, it is more preferable that it is 10,000-100,000.

The 3rd aspect of this invention forms the member for electronic devices on the glass substrate in the laminated body of the 1st aspect of this invention, manufactures the laminated body with a member for electronic devices, and attaches the member for electronic devices. The glass substrate with an electronic device member and the support plate with a resin layer were isolate | separated from the laminated body which made the glass substrate side interface of the resin layer, or the inside of a resin layer into a peeling surface, and the member for electronic devices then adheres It is a manufacturing method of the glass substrate with an electronic device member which cleans the peeling surface of the made glass substrate.

Moreover, it is preferable that the said cleaning is washing | cleaning using a solvent, and it is preferable that washing | cleaning is washing | cleaning using the solvent whose solubility parameter is 7-15.

In addition, the glass substrate with a member for said electronic device is called "the glass substrate with a member" hereafter.

According to this invention, it can use even under high temperature heat processing conditions, and can provide the laminated body which can maintain the cleanliness of the peeling surface of the separated glass substrate by performing a cleaning process, and the manufacturing method of this laminated body can be provided.

Moreover, according to this invention, the manufacturing method of the glass substrate with a member using this laminated body can also be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing of one Embodiment of the laminated body which concerns on this invention.
2 is a schematic cross-sectional view showing one embodiment of a method for manufacturing an electronic device according to the present invention in the order of steps.

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention is demonstrated with reference to drawings, this invention is not limited to the following embodiment, A various deformation | transformation and substitution are given to the following embodiment, without deviating from the range of this invention. Can be added.

The laminated body of this invention is equipped with the layer of a support plate, the resin layer, and the layer of a glass substrate in this order. That is, the resin layer is provided between the layer of a support plate and the layer of a glass substrate. Therefore, one side of a resin layer is in contact with the layer of a support plate, and the other side is in contact with the layer of a glass substrate.

The interface between the resin layer and the glass substrate has a peel strength (x), and when the stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the resin layer and the glass substrate, the interface between the resin layer and the glass substrate is peeled off. . The interface of a resin layer and a support plate has peeling strength y, and when the stress of the peeling direction exceeding peeling strength y is applied to the interface of a resin layer and a support plate, the interface of a resin layer and a support plate will peel. On the other hand, the resin of the resin layer has strength against its own destruction, and when a stress in the direction in which the glass substrate and the support plate are peeled off is applied to the resin layer, it does not break up to a certain degree of stress and withstands the stress. However, when a stress exceeding the strength of the resin itself is applied, the resin layer is broken, and the strength of the limit that the resin layer endures is referred to as the cohesive failure strength (z).

In the laminated body of this invention (it also means the laminated body with an electronic device member mentioned later), the said peeling strength (y) is higher than the said peeling strength (x) or the said cohesive fracture strength (z). Therefore, when the stress of the direction which peels a glass substrate and a support plate is applied to the laminated body of this invention, the laminated body of this invention peels at the interface of a resin layer and a glass substrate, and isolate | separates into the support plate with a glass substrate and a resin layer. Or by the cohesive failure of a resin layer, it isolate | separates into the glass substrate with resin and the support plate with resin. Either of these aspects depends on the size of the peel strength (x) and the cohesive failure strength (z). When the peel strength (x) is higher than the cohesive failure strength (z), cohesive failure of the resin layer occurs, and the peel strength When (x) is lower than the cohesive failure strength z, it is thought that interface peeling occurs.

As described above, when the peeling strength (x) in the laminate of the present invention is higher than the cohesive failure strength (z), when the glass substrate and the supporting plate of the laminate are peeled off, the glass substrate with resin and the resin are attached. A support plate is created. As mentioned later, in the laminated body after forming the member for electronic devices on the glass substrate in a laminated body, the separated glass substrate is a glass substrate with a member. Since it is not preferable that resin adheres to the peeling surface (surface in which the member for electronic devices of a glass substrate is not formed) of a glass substrate with a member, it is preferable to remove resin adhered to a peeling surface.

In addition, even if the attached resin is removed, the smaller the amount thereof, the easier it is to remove, so that the smaller the resin attached to the peeling surface immediately after separation is preferable. The closer the peeling strength (x) to the cohesive failure strength (z), the higher the possibility of partial interfacial peeling, and the amount of resin attached to the peeling surface of the glass substrate is considered to be smaller than the amount of resin attached to the supporting plate.

In addition, since peeling strength (x) and the cohesive fracture strength (z) are substantially the same as below, since it is thought that the glass substrate with resin adhered to a peeling surface, it is easy to produce, and in this invention, peeling strength (x) is cohesive failure. It shall be included when it is higher than intensity | strength (z).

As mentioned above, when the peeling strength (x) in the laminated body of this invention is lower than the cohesive fracture strength (z), when the glass substrate and support plate of a laminated body are peeled off, the support plate with a glass substrate and a resin layer will arise. . The closer the peeling strength (x) is to the cohesive failure strength (z), the more easily the cohesive failure of the resin layer occurs, and the glass substrate with the resin is likely to be formed on the peeling surface. When the peeling strength (x) and the cohesive failure strength (z) are close to each other, there is a possibility that a glass substrate with a resin and a glass substrate without a resin are formed for each laminate. Therefore, even if it is considered that there is no adhesion of resin, it is preferable to consider the possibility of adhering a trace amount of resin to the peeling surface of the glass substrate after separation, and to perform operation which removes resin.

It is preferable that peeling strength (y) is sufficiently higher than both compared with peeling strength (x) and cohesive failure strength (z). Thereby, the amount of resin adhering to the support plate after separation can be made relatively large compared with a glass substrate. Increasing the peel strength (y) means that the adhesive force of the resin layer to the support plate can be increased, and the adhesive force relatively higher than that of the glass substrate can be maintained after the heat treatment.

In order to raise the adhesive force of the resin layer with respect to a support plate, it is preferable to crosslink-cure hardenable silicone resin on a support plate, and to form a resin layer. By the adhesive force at the time of crosslinking hardening, the resin layer couple | bonded with the high bonding force with respect to the support plate can be formed.

On the other hand, it is usual for the bonding force of the crosslinked silicone resin after crosslinking hardening to a glass substrate to be lower than the bonding force which arises at the time of the said crosslinking hardening. Therefore, it is preferable to crosslink-cure hardenable silicone resin on a support plate, to form a resin layer, and to laminate | stack a glass substrate on the surface of the resin layer which consists of crosslinking-hardened silicone resin, and to manufacture a laminated body.

The adhesion of the layer surface of the crosslinked silicone resin crosslinked by the condensation reaction is higher than the layer surface of the crosslinked silicone resin crosslinked by the hydrosilylation reaction described in Patent Document 1. Therefore, in this invention, when the glass substrate is laminated | stacked on the surface of the silicone resin layer fully crosslinked and hardened on the support plate, it is thought that the adhesiveness of the resin layer surface and the glass substrate surface is higher than the case in the laminated body of patent document 1 do. Therefore, it is thought that the peeling strength (x) of the laminated body of this invention becomes high compared with the peeling strength of the interface of the resin layer and glass substrate layer in the laminated body of patent document 1.

Moreover, it is thought that the reactivity of the curable silicone resin crosslinking-curing by condensation reaction is lower than the reactivity of the curable silicone resin crosslinking-curing by hydrosilylation reaction. Therefore, it is not easy to complete | finish the crosslinking reaction of resin of the resin layer formed on the support plate before laminating | stacking with a glass substrate. When a glass substrate is laminated | stacked on the resin layer which consists of crosslinked silicone which the unreacted crosslinking point remained, after completion | finish, it is thought that an unreacted crosslinking point bridge | crosslinks and resin adheres to a glass substrate, and peeling strength (x) becomes high. In particular, when forming a member for an electronic device on the glass substrate surface of the laminate, heat treatment is often performed. Therefore, bonding of the interface between the glass substrate and the resin layer proceeds, thereby laminating the electronic device member after formation. The peeling strength (x) in a sieve (laminated body with a member for electronic devices) tends to be higher.

Therefore, in the present invention, at the time of peeling, it is considered that the peeling strength (x) is often higher than the cohesive failure strength (z).

Moreover, curable silicone resin crosslinked and hardened by condensation reaction can fully advance a crosslinking reaction by heating, without using a curing catalyst. In the crosslinked silicone resin in which the curing catalyst remains, there is a possibility that low molecular weight silicon is generated by the depolymerization of the crosslinked silicone resin by the action of the curing catalyst. Therefore, the production of low molecular weight silicone is prevented by not using the curing catalyst. You can do less.

When the low molecular weight silicon is small, there is little gas generation resulting from low molecular weight silicon under the high temperature conditions at the time of forming a member for electronic devices on the glass substrate surface of a laminated body, It is characterized by a low risk of contamination.

Moreover, in the range below the allowable amount of gas generation, you may perform the easy peeling process with respect to the interface to laminate | stack using a silicon compound, a fluorine compound, etc. before lamination for the purpose of adjusting peeling strength.

In the present invention, since the separation of the glass substrate and the supporting plate is conventionally performed on the laminate after forming the electronic device member (the laminate with the electronic device member attached), the separated glass substrate (glass with the member attached) It is thought that resin adheres to the peeling surface of the board | substrate). As mentioned above, it is not preferable that resin adheres to the peeling surface of the glass substrate with a member, and resin attached to the peeling surface of the glass substrate with a member normally requires the removal. Resin in this invention has solvent solubility, Therefore, it is preferable to remove resin by the removal operation using a solvent.

1 is a schematic sectional view of an example of a laminate according to the present invention.

As shown in FIG. 1, the laminated body 10 is a laminated body in which the resin layer 14 exists between the layer of the support plate 12, the layer of the glass substrate 16, and them. One side of the resin layer 14 is in contact with the layer of the support plate 12, and the other side thereof is in contact with the first main surface 16a of the glass substrate 16. In other words, the resin layer 14 is in contact with the first main surface 16a of the glass substrate 16.

The two-layer part which consists of the layer of the support plate 12 and the resin layer 14 reinforces the glass substrate 16 in the member formation process which manufactures components for electronic devices, such as a liquid crystal panel. In addition, the two-layer part which consists of the layer of the support plate 12 previously manufactured for manufacture of the laminated body 10, and the resin layer 14 is called the support plate 18 with a resin layer.

This laminated body 10 is used up to a member formation process. That is, this laminated body 10 is used until the member for electronic devices, such as a liquid crystal display device, is formed on the surface of the 2nd main surface 16b of the glass substrate 16. FIG. Then, the laminated body in which the electronic device member was formed is isolate | separated into the support plate 12 and the glass substrate with a member, and when the resin is affixed to the peeling surface of the glass substrate with a member, the attached resin is Removed. The support plate 12 with resin (or the support plate 12 having the resin layer 14) does not become a part constituting the electronic device. The separated support plate 12 is laminated with a new glass substrate 16 after removing the attached resin and the resin layer 14 as needed, and can be reused as the laminate 10.

Below, each layer (glass substrate, support plate, resin layer) and resin material which comprise a laminated body are explained in full detail first, and the laminated body and the manufacturing method of an electronic device are explained in full detail after that.

(Glass substrate)

In the glass substrate 16, the 1st main surface 16a is in contact with 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.

The kind of glass substrate 16 should just be a general thing, For example, the glass substrate for display apparatuses, such as LCD and OLED, etc. are mentioned. The glass substrate 16 is excellent in chemical resistance, moisture permeability, and low in heat shrinkage. As an index of thermal contraction rate, the linear expansion coefficient prescribed | regulated to JISR3102 (Rev. 1995) is used.

When the coefficient of linear expansion of the glass substrate 16 is large, since a member formation process often involves heat processing, various problems tend to arise. For example, when forming a TFT on the glass substrate 16, when the glass substrate 16 in which TFT was formed was cooled under heating, there exists a possibility that the position shift of TFT may become large largely by the heat shrink of the glass substrate 16. FIG.

The glass substrate 16 is obtained by melting a glass raw material and shaping 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 laverse method and the like are used. Moreover, especially the glass substrate 16 with a thin thickness is obtained by shape | molding the glass once shape | molded at plate shape by the method (stretch method) which stretches and thins by means, such as extending | stretching, by means of extending | stretching temperature.

Although the glass of the glass substrate 16 is not specifically limited, Oxide type glass which has alkali-borosilicate glass, borosilicate glass, soda-lime glass, high silica glass, and other silicon oxide as a main component is preferable. As oxide type glass, glass with a content of 40-90 mass% of the silicon oxide by oxide conversion is preferable.

As glass of the glass substrate 16, the glass suitable for the kind of electronic device member or its manufacturing process is employ | adopted. For example, the glass substrate for a liquid crystal panel consists of glass (alkali free glass) which does not substantially contain an alkali metal component, since the elution of an alkali metal component tends to affect a liquid crystal (however, an alkali earth metal component is normally Is included). Thus, the glass of the glass substrate 16 is suitably selected based on the kind of device applied, and its manufacturing process.

It is preferable that the thickness of the glass substrate 16 is 0.3 mm or less from a viewpoint of thinning and / or lightening of the glass substrate 16, More preferably, it is 0.15 mm or less. In the case of 0.3 mm or less, it is possible to give favorable flexibility to the glass substrate 16. When it is 0.15 mm or less, it is possible to wind up the glass substrate 16 in roll shape.

Moreover, it is preferable that the thickness of the glass substrate 16 is 0.03 mm or more for the reason that manufacture of the glass substrate 16 is easy, and the handling of the glass substrate 16 is easy.

In addition, the glass substrate 16 may consist of two or more layers, In this case, the material which forms each layer may be a homogeneous material, or a heterogeneous material may be sufficient as it. In this case, "thickness of the glass substrate 16" shall mean the thickness of the sum total of all the layers.

[Support plate]

The support plate 12 supports and reinforces the glass substrate 16, and in the member formation process (step of manufacturing a member for an electronic device) which will be described later, deformation of the glass substrate and generation of scratches, Prevent damage.

As the support plate 12, metal plates, such as a glass plate, a plastic plate, and a SUS board, etc. are used, for example. Usually, since the member formation process involves heat treatment, the support plate 12 is preferably formed of a material having a small difference in coefficient of linear expansion with the glass substrate 16, and more preferably formed of the same material as the glass substrate 16. It is preferable that the support plate 12 is a glass plate. In particular, the support plate 12 is preferably a glass plate made of the same glass material as that of the glass substrate 16.

The thickness of the support plate 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support plate 12 is selected based on the thickness of the glass substrate 16, the thickness of the resin layer 14, and the thickness of the laminated body 10. For example, the current member formation process is designed to process a substrate having a thickness of 0.5 mm, and when the sum of the thickness of the glass substrate 16 and the thickness of the resin layer 14 is 0.1 mm, the thickness of the support plate 12 is 0.4. Let it be mm. It is preferable that the thickness of the support plate 12 is 0.2-5.0 mm normally.

When the support plate 12 is a glass plate, it is preferable that the thickness of a glass plate is 0.08 mm or more for the reason of being easy to handle and hard to break. Moreover, when the thickness of a glass plate peels after formation of the member for electronic devices, it is preferable that it is 1.0 mm or less, for the reason that rigidity which is bent moderately without breaking is calculated | required.

The difference between the average linear expansion coefficient (hereinafter, simply referred to as "average linear expansion coefficient") at 25 to 300 ° C of the support plate 12 and the glass substrate 16 is preferably 500 × 10 ^-7 / ° C or less, and more Preferably it is 300x10 <^-7> / degrees C or less, More preferably, it is 200x10 <^-7> / degrees C or less. When the difference is too large, there is a possibility that the laminate 10 is severely warped or the support plate 12 and the glass substrate 16 are peeled off at the time of heating and cooling in the member forming step. When the material of the support plate 12 is the same as the material of the glass substrate 16, it can suppress that this problem arises.

[Resin layer]

While the resin layer 14 prevents the position shift of the glass substrate 16 until the operation which isolate | separates the glass substrate 16 and the support plate 12 is performed, the glass substrate 16 etc. are removed by a separation operation. To prevent breakage. The surface 14a in contact with the glass substrate 16 of the resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16. The resin layer 14 is bonded by the weak bond force to the 1st main surface 16a of the glass substrate 16, and the peeling strength (x) of the interface is a thing of the interface between the resin layer 14 and the support plate 12. It is often lower than peel strength (y). The bonding force of the interface of the resin layer 14 and the glass substrate 16 changes before and after forming the member for electronic devices on the surface (second main surface 16b) of the glass substrate 16 of the laminated body 10. You may change (that is, peeling strength (x) may change). However, even after forming the member for electronic devices, it is preferable that peeling strength (x) is lower than peeling strength (y).

It is thought that the layers of the resin layer 14 and the glass substrate 16 are bonded by the bonding force resulting from a weak adhesive force and van der Waals force. In the case where the glass substrate 16 is laminated on the surface after the resin layer 14 is formed, when the crosslinked silicone resin of the resin layer 14 is sufficiently crosslinked so as not to exhibit adhesive force, it is caused by van der Waals force. It is thought that it is combined by the bonding force. However, as mentioned above, the crosslinked silicone resin of the resin layer 14 does not have some weak adhesive force in some cases. For example, even when the adhesiveness is very low, when forming a member for an electronic device on the laminate after manufacture of the laminate, the crosslinked silicone resin of the resin layer 14 adheres to the glass substrate surface by heating operation or the like. It is thought that the bonding force between the layer 14 and the layer of the glass substrate 16 rises.

In some cases, a treatment may be applied to the surface of the resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination to weaken the bonding force between the two. By carrying out non-adhesive treatment or the like on the surface to be laminated, and laminating thereafter, the bonding strength of the interface between the resin layer 14 and the layer of the glass substrate 16 can be weakened, and the peeling strength (x) can be made low.

The resin layer 14 is bonded to the surface of the support plate 12 with strong bonding force such as adhesive force and adhesive force. For example, by crosslinking-curing the curable silicone resin mentioned later on the support plate 12 surface, the crosslinked resin can be adhered to the support plate 12 surface to obtain a high bonding force. In addition, a treatment for generating a strong bonding force between the surface of the support plate 12 and the resin layer 14 (for example, a treatment using a coupling agent) may be performed to increase the bonding force between the surface of the support plate 12 and the resin layer 14. have.

The bonding of the layers of the resin layer 14 and the support plate 12 with high bonding force means that the peeling strength (y) of both interfaces is high.

Although the thickness of the resin layer 14 is not specifically limited, It is preferable that it is 1-5 micrometers, It is more preferable that it is 1-4 micrometers, It is further more preferable that it is 1-3 micrometers. If the thickness of the resin layer 14 is such a range, even if air bubbles or foreign substances may intervene between the resin layer 14 and the glass substrate 16, generation | occurrence | production of the deformation | transformation defect of the glass substrate 16 can be suppressed. have. Moreover, when the thickness of the resin layer 14 is too thick, since it requires time and a material to form, it is not economical.

In addition, the resin layer 14 may consist of two or more layers. In this case, "thickness of the resin layer 14" shall mean the thickness of the sum total of all the layers.

Moreover, when the resin layer 14 consists of two or more layers, resin which forms each layer may consist of different crosslinked silicone resins.

The resin of the resin layer 14 has its own strength as a property of the material, and the resin is destroyed when a stress equal to or higher than the cohesive failure strength z is received. Therefore, when the resin layer 14 is subjected to a stress in the thickness direction and the stretching direction thereof, and the stress is equal to or higher than the cohesive failure strength z, the resin layer 14 is destroyed inside the layer. As a result, the resin layer on the glass substrate side is attached to the glass substrate surface from the fracture surface, and the resin layer 14 on the support plate 12 side is attached to the support plate 12 surface from the fracture surface. Therefore, when the resin of the resin layer 14 agglomerates and breaks in the laminated body with an electronic device member, one side will become the glass substrate with a member with resin attached to the 1st main surface 16a, and the other It becomes the support plate 12 with resin on the surface.

The cohesive failure strength (z) of the crosslinked silicone resin is higher than the peel strength (y) unless the bond strength between the resin layer 14 and the layer of the support plate 12 is particularly low as a property thereof. little. On the other hand, compared with the said peeling strength (x), the cohesive failure strength (z) may become lower than peeling strength (x), and may increase. As mentioned above, peeling strength (x) can be adjusted and may change. In particular, when the member for an electronic device is formed on the second main surface 16b of the glass substrate 16, the peel strength x easily rises, whereby the cohesive failure strength z is higher than the peel strength x. Easy to be lowered

When the resin layer 14 is cohesive-broken, resin may not necessarily adhere to the whole surface of the 1st main surface 16a of the glass substrate 16. As shown in FIG. When the difference between the cohesive failure strength z and the peeling strength x is small, the layer of the resin layer 14 and the glass substrate 16 is partially interfacially peeled off, and a part of the first main surface 16a on the surface of the glass substrate is The surface on which resin does not adhere may arise.

[Crosslinked Silicone Resin]

The resin layer 14 consists of crosslinked silicone resin. Crosslinked silicone resin is obtained by crosslinking-hardening curable silicone resin. Curable silicone resin in this invention is a mixture (monomer mixture) of the hydrolyzable organosilane compound which is a monomer, or the partial hydrolysis-condensation product obtained by carrying out partial hydrolysis condensation reaction of a monomer mixture. Moreover, the mixture of a partial hydrolysis-condensation product and a monomer may be sufficient. As curable silicone resin in this invention, the partial hydrolysis-condensation product of a monomer mixture is preferable.

In order to crosslink and harden curable silicone resin, a crosslinking reaction is normally advanced by hardening, and it hardens | cures (that is, thermosets). A crosslinked silicone resin is obtained by thermosetting curable silicone resin. However, hardening does not necessarily require heating, and it can also harden at room temperature.

Usually, a crosslinked silicone resin consists of a trifunctional organo siloxy unit called a T unit, and a bifunctional organo siloxy unit called a D unit. In some cases, a monofunctional organosiloxy unit called an M unit or a tetrafunctional organosiloxy unit called a Q unit may be included. In addition, although a Q unit is a unit which does not have the organic group (organic group which has the carbon atom couple | bonded with the silicon atom) couple | bonded with the silicon atom, it considers as organo siloxy unit in this invention. The organosiloxy unit (A-1) mentioned later and the organosiloxy unit (B-2) mentioned later in this invention are T units, and the organosiloxy unit (B-1) mentioned later and later mentioned The organosiloxy unit (A-2) is a D unit. In addition, hereinafter, the organosiloxy unit (A-1) is simply referred to as the (A-1) unit, and the organosiloxy unit (B-1) is also referred to simply as the (B-1) unit. The same applies to other organosiloxy units.

Usually, M unit in crosslinked silicone resin is used in order to adjust the molecular weight of crosslinked silicone resin or curable silicone resin, and Q unit is used in order to increase a crosslinking point. The crosslinked silicone resin in the present invention does not require neither M unit nor Q unit, preferably contains neither M unit nor Q unit, and even if it is included, the number thereof is preferably small.

90-100 mol% is preferable and, as for the ratio of the sum total of T unit and D unit with respect to the total organosiloxy unit of the crosslinked silicone resin in this invention, the effect of this invention is more preferable, 95- 100 mol% is more preferable. In the case where the crosslinked silicone resin in the present invention contains M units and / or Q units, the ratio of the M units and the Q units is preferably less than 10 mol% (but the sum of both is less than 10 mol%), Less than 5 mol% each (but the sum total is less than 5 mol%) is preferable. It is especially preferable that the crosslinked silicone resin in this invention does not contain both M unit and Q unit.

When crosslinked silicone resin contains many M units, the heat resistance of resin will fall easily, and when it contains many Q units, the brittleness of resin will become large easily, and all are not suitable as a material of the resin layer in this invention. Occurs.

The crosslinked silicone resin in the present invention is an organosiloxy unit (A-1) represented by formula (1) described later and an organosiloxy unit (B-1) represented by formula (2) described later. It includes. The ratio of the total amount (represented by (A-1) + (B-1)) of the (A-1) unit and the (B-1) unit to all the organosiloxy units is 70 to 100 mol%, 30 mol Less than% is the total amount of T units other than (A-1) units, D units other than (B-1) units, M units, and Q units. It is preferable not to include M unit and Q unit, and in that case, less than 30 mol% is the total amount of T unit other than (A-1) unit, and D unit other than (B-1) unit. It is preferable that it is 85-100 mol%, and, as for the ratio of (A-1) + (B-1) with respect to all organo siloxy units, it is more preferable that it is 90-100 mol%. The remaining units are T units (particularly preferred organosiloxy unit (B-2) described later) other than the (A-1) unit and / or D units other than the (B-1) unit (organo described in particular later) Siloxy unit (A-2) is preferred).

In the crosslinked silicone resin in the present invention, the ratio of the (A-1) unit to the total of the (A-1) unit and the (B-1) unit, that is, (A-1) / [(A-1) + (B-1)] is 15-50 mol%. More preferably, this ratio is 20-40 mol%.

In the case where the unit (A-1) is less than 15 mol%, the heat resistance of the crosslinked silicone resin is poor and voids are likely to occur in the resin layer, while in the case where the unit (A-1) is more than 50 mol%, the brittleness of the resin becomes large. A crack etc. tend to arise in a resin layer, and the flatness of a surface falls easily at the time of resin layer formation, and it is easy to laminate | stack a glass substrate on the resin layer surface.

When the crosslinked silicone resin contains T units other than the (A-1) unit or D units other than the (B-1) unit, the total T units including the (A-1) unit and the (B-1) unit are included. It is preferable that it is 15-50 mol%, and, as for the ratio of all T units, ie T / [T + D], with respect to the total amount of all D units, it is more preferable that it is 20-40 mol%. When the ratio of the T unit is less than 15 mol%, the heat resistance of the crosslinked silicone resin tends to be lowered. When the ratio of the T unit is more than 50 mol%, the brittleness of the crosslinked silicone resin tends to increase.

The organosiloxy unit (A-1) in this invention is a unit represented by following formula (1), and an organo siloxy unit (B-1) is a unit represented by following formula (2). However, in following formula (1) and formula (2), R <^1> represents a hydrogen atom or a C1-C4 alkyl group. R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms.

[Formula 1]

As represented by Formula (1), the unit (A-1) is a T unit having a phenyl group, and the phenyl group may have an alkyl group having 1 to 4 carbon atoms. R ¹ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, particularly preferably a hydrogen atom. As represented by Formula (2), the unit (B-1) is a D unit having two alkyl groups. It is preferable that it is a methyl group or an ethyl group, respectively, and, as for two alkyl groups, it is more preferable that all are methyl groups.

The crosslinked silicone resin having an organosiloxy unit in which the aromatic ring is bonded to the silicon atom has a higher heat resistance than the crosslinked silicone resin having an organosiloxy unit in which the alkyl group is bonded to the silicon atom. Although the crosslinked silicone resin having a large ratio of T units has a good heat resistance, brittleness tends to increase, but the crosslinked silicone resin in the present invention has a T unit having an aromatic ring, so that even if the ratio of the T units is somewhat small, This high crosslinking silicone resin is low.

As an organo siloxy unit which the aromatic ring other than the (A-1) unit couple | bonded with the silicon atom, the organo siloxy unit (A-2) represented by following formula (3) is preferable, and the organo siloxy unit ( As an organo siloxy unit which alkyl group other than B-1) couple | bonded with the silicon atom, the organo siloxy unit (B-2) represented by following formula (4) is preferable. The unit (A-2) is a D unit, and the unit (B-2) is a T unit. In following formula (3) and formula (4), R <^1> represents a hydrogen atom or a C1-C4 alkyl group, and R <^2> represents a C1-C4 alkyl group. R ⁶ represents an alkyl group having 1 to 4 carbon atoms.

[Formula 2]

As an organosiloxy unit which the aromatic ring other than the (A-1) unit and the (A-2) unit couple | bonded with the silicon atom, there exists a D unit which has two aromatic rings. Moreover, as an organo siloxy unit which alkyl groups other than (B-1) unit and (B-2) unit couple | bonded with the silicon atom, there exist a D unit and T unit which has a C5 or more alkyl group. However, the crosslinked silicone resin having these units may have insufficient properties such as mechanical properties, and the crosslinked silicone resin in the present invention preferably does not include such organosiloxy units.

The crosslinked silicone resin in the present invention may include at least either one of the (A-2) unit and the (B-2) unit. When the crosslinked silicone resin in the present invention is composed of at least one of (A-1) units, (B-1) units, and (A-2) units and (B-2) units, the T units and D The ratio of T units to the sum of units is [(A-1) + (B-2)] for [(A-1) + (A-2) + (B-1) + (B-2)] It is a ratio of 15-50 mol% is preferable, and it is more preferable that it is 20-40 mol%.

Moreover, the ratio of the organosiloxy unit which has an aromatic ring with respect to all organo siloxy units, ie, with respect to [(A-1) + (A-2) + (B-1) + (B-2)] As for the ratio of [(A-1) + (A-2)], 20-40 mol% is preferable. More preferably, this ratio is 20-30 mol%.

In addition, as described above, the ratio of the sum of the (A-1) units and the (B-1) units to the total organosiloxy units, that is, [(A-1) + (A-2) + (B-1) The ratio of [(A-1) + (B-1)] to + (B-2)] is 70 to 100 mol%, preferably 85 to 100 mol%, more preferably 95 to 100 mol%. desirable.

The crosslinked silicone resin in the present invention is a phenyl group (X) represented by the following formula (9) in the formulas (1) and (3), and R ⁶ in the formulas (2) and (4). And / or the ratio of the alkyl group (Y) represented by R ⁷ is [(X)] / [(X) + (Y)] = 10-40 (mol%), and it is 10-20 (mol%) It is more preferable. If it is 10 (mol%) or more, heat resistance is favorable and since the smoothness of the formed resin layer is maintained, it can laminate | stack favorably. If it is 40 (mol%) or less, it has the adhesiveness of the grade which can be laminated | stacked favorably.

[Formula 3]

In formula (9), R <^1> represents a hydrogen atom or a C1-C4 alkyl group.

Curable Silicone Resin

Each organosiloxy unit in the crosslinked silicone resin in the present invention is formed from a hydrolyzable organosilane compound which is a monomer. Although an alkoxy group is preferable, the hydrolyzable group in a hydrolyzable organosilane compound is not limited to this, Halogen atoms, such as a chlorine atom, an acyl group, an amino group, an alkoxyalkoxy group, etc. may be sufficient.

As curable silicone resin used as a crosslinked silicone resin, although the mixture of the hydrolyzable organosilane compound which is a monomer may be sufficient, the partial hydrolysis-condensation product obtained from the mixture of a hydrolyzable organosilane compound is preferable. The partially hydrolyzed condensate has a silanol group and crosslinks by dehydration condensation of the silanol groups to form a crosslinked silicone resin. The partially hydrolyzed condensate may include a hydrolyzable group, or may be crosslinked and cured by a condensation reaction of a hydrolyzable group and a silanol group or a condensation reaction between hydrolyzable groups.

As a hydrolyzable organosilane compound which is a monomer, the alkoxysilane compound which has an alkoxy group as a hydrolyzable group is preferable. As an alkoxysilane compound used as a (A-1) unit, the compound represented by following formula (5) is preferable, and as an alkoxysilane compound used as a (B-1) unit, the compound represented by following formula (6) is preferable. Do.

[Formula 4]

In the formula (5), equation (6), R ^1, R ^6, R ⁷ is as defined in the formula (1), formula (2) R ^1, R ^6, R ⁷ in each. R ³ , R ⁴ , R ⁵ , R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms.

^{R 3, R 4, R 5} , R 8, R 9 are each independently preferably a methyl group or an ethyl group, and particularly R ^3, R ^4, R ⁵ are both a methyl group is preferred, R ^8, R ⁹ is It is preferable that all are ethyl groups.

As an alkoxysilane compound used as a (A-2) unit, the compound represented by following formula (7) is preferable, and as an alkoxysilane compound used as a (B-2) unit, the compound represented by following formula (8) is preferable. Do.

[Formula 5]

In the formula (7), equation (8), R ^1, R ^2, R ⁶ is as defined in the formula (3), R ^1, R ^2, R ⁶ in the formula (4), respectively. R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 4 carbon atoms.

R ^3, R ^4, R ^8, R ^9, R ¹⁰ are each independently preferably a methyl group or an ethyl group, and particularly R ^3, R ⁴ are both a methyl group is preferred, R ^8, R ^9, R ¹⁰ is It is preferable that all are ethyl groups.

As shown in said Formula (5)-(8) and said Formula (1)-(4), each molecule | numerator of each hydrolysable organosilane compound and each organosiloxy unit correspond to one to one. That is, the ratio of each said organosiloxy unit in a crosslinked silicone resin corresponds to the ratio of said each hydrolysable organosilane compound (monomer). Therefore, by using as a curable silicone resin the monomer mixture mixed in the ratio same as the ratio of each said organo siloxy unit, or the partial hydrolysis-condensation product obtained from this monomer mixture, crosslinked silicone which has the organo siloxy unit of the said ratio Resin is obtained.

Moreover, as a hydrolysable organosilane compound used as M unit, trialkyl alkoxysilane compounds, such as trimethylethoxysilane, are preferable, and the hydrolyzable silane compound used as Q unit (However, in this specification, as a hydrolyzable organosilane compound, Considered), tetraalkoxysilane compounds such as tetraethoxysilane are preferable.

As curable silicone resin, the monomer mixture which mixed the said hydrolyzable organosilane compound so that it may become the ratio of each said organo siloxy unit may be sufficient. However, it is preferable that it is a partial hydrolysis-condensation thing from the viewpoint of control, handling, etc. of reaction. Hereinafter, the partial hydrolysis-condensation product is also called curable oligomer.

The partially hydrolyzed condensate is obtained by partially hydrolyzing and condensing a monomer mixture obtained by mixing a hydrolyzable organosilane compound so as to be a ratio of the respective organosiloxy units. The method of partially hydrolytic condensation is not particularly limited. Usually, a mixture of hydrolyzable organosilane compounds is prepared by reacting in the presence of a catalyst in a solvent. As the catalyst, an acid catalyst or an alkali catalyst can be used. However, in order to control the reaction to obtain a partial hydrolysis condensate having an appropriate molecular weight, the use of an alkali catalyst is preferable. Moreover, it is preferable to use water normally for a hydrolysis reaction. It is preferable that the partial hydrolysis-condensation product used for this invention was manufactured by making the mixture of a hydrolysable organosilane compound react in presence of aqueous alkali solution in a solvent. As a manufacturing method of a specific partial hydrolysis-condensation product, the method of the said patent document 2 (in particular, the method of the Example) is preferable.

In the case where the curable silicone resin in the present invention is the curable oligomer (that is, partially hydrolyzed condensate), the weight average molecular weight of polystyrene in terms of GPC (gel permeation chromatography) measurement is preferably 5,000 or more. . More preferable weight average molecular weight is 10,000 or more. When this molecular weight is too low, the quantity of water and alkanol by-produced in a crosslinking reaction will increase, and there exists a possibility that a void may arise in a crosslinked silicone resin. In addition, when the weight average molecular weight is too high, the viscosity may be too high or the solvent solubility may be deteriorated. Therefore, the weight average molecular weight of the curable oligomer is preferably 200,000 or less, more preferably 100,000 or less. .

Adjustment of the molecular weight of a curable oligomer can be performed by controlling reaction conditions. For example, by adjusting the amount of solvent when preparing the curable oligomer, increasing the concentration of the hydrolyzable organosilane compound yields a high molecular weight product, while lowering the concentration yields a low molecular weight product.

As mentioned above, a curable oligomer has a silanol group mainly as a reactive group, crosslinks by reaction of silanol groups, and it becomes a crosslinked silicone resin. In order to perform this crosslinking reaction, it is preferable to heat curable silicone resin. Although the crosslinking reaction of a silanol group is a dehydration condensation reaction, water is a by-product, but by the thin resin layer of the laminated body of this invention, the water by-produced when hardening the film of a curable oligomer on a support plate can be fully removed, for example. .

The temperature conditions for crosslinking are not particularly limited within the range of maintaining the heat resistance of the crosslinked silicone resin and the adhesiveness with the support plate, but are preferably from 300 to 475 ° C, more preferably from 350 to 450 ° C. Moreover, 30 to 300 minutes are preferable normally, and 60 to 120 minutes are more preferable. When the temperature is too low, the crosslinking is insufficient, and the heat resistance of the resin decreases or the flatness of the resin layer tends to decrease. On the other hand, when the temperature is too high, the adhesive force with the supporting plate of the resin layer tends to decrease.

In crosslinking hardening of curable silicone resins other than the said curable oligomer, alkanol etc. may also be by-produced besides water by a crosslinking reaction, but it can remove easily from resin similarly to water. Thereby, the quantity of volatile components, such as water, in the resin layer of a laminated body can be made into a very small quantity, and water, such as water, under the high temperature conditions at the time of forming an electronic device member on the glass substrate surface of a laminated body. The gas generation resulting from a low molecular weight compound can be reduced.

In order to form the resin layer 14 on the support plate 12, it is preferable to form the layer of curable silicone resin on the support plate 12, and to make the resin layer 14 crosslink-harden this curable silicone resin. In order to form the layer of curable silicone resin on the support plate 12, the solution which melt | dissolved curable silicone resin in the solvent is used, this solution is apply | coated on the support plate 12, and a layer of a solution is formed, and then a solvent is It is preferable to remove and set it as the layer of curable silicone resin. The thickness of the layer of curable silicone resin can be controlled by adjusting the density | concentration of a solution.

It will not specifically limit, if it is a solvent which can melt | dissolve curable silicone resin easily in a working environment, and can volatilize easily under a working environment. Specifically, butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate, etc. can be illustrated, for example. 1-methoxy-2-propanol acetate is preferable at the point which the resin layer obtained by a crosslinking reaction becomes flat easily.

As solid content concentration of the solution containing curable silicone resin and curable oligomer, 30-70 mass% is preferable, and 40-60 mass% is more preferable.

Laminated Body and Manufacturing Method Thereof

As mentioned above, the laminated body 10 of this invention is a laminated body in which the resin layer 14 exists between the support plate 12 and the glass substrate 16, and these.

Although the manufacturing method of the laminated body 10 of this invention is not specifically limited, In order to obtain a laminated body whose peeling strength (y) is higher than peeling strength (x) or cohesive fracture strength (z), curable silicone resin is used on the support plate surface. The method of crosslinking hardening and forming a resin layer is preferable. That is, a film of curable silicone resin is formed on the surface of the support plate, the curable silicone resin is crosslinked and cured to form a film of crosslinked silicone resin on the surface of the support plate, and then a glass substrate is laminated on the surface of the film of crosslinked silicone resin to produce a laminate. That's how.

Hereinafter, a step of forming a film of the curable silicone resin on the surface of the support plate, crosslinking and curing the curable silicone resin on the support plate surface to form a film of the crosslinked silicone resin, and laminating a glass substrate on the surface of the resin layer forming step and the film of the crosslinked silicone resin The process made into a laminated body is called lamination process, and the procedure of each process is explained in full detail.

 (Resin layer forming step)

In the resin layer formation process, the solution containing the above-mentioned curable silicone resin and a solvent is apply | coated on the surface of the support plate 12, a solvent is removed, and the film of curable silicone resin is formed on the surface of the support plate 12. Next, the film of curable silicone resin on the support plate 12 is thermosetted, and the resin layer 14 is formed. More specifically, as shown to FIG. 2 (A), in the said process, the resin layer 14 is formed on the surface of the at least single side | surface of the support plate 12. FIG.

The method of apply | coating the solution of curable silicone resin on the support plate 12 surface is not specifically limited, A well-known method can be used. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, a gravure coating method, etc. are mentioned.

It is preferable to perform hardening (main hardening), and to harden curable silicone resin after performing precure (preliminary hardening). The resin layer excellent in heat resistance can be obtained by performing precure. It is preferable to perform a precure following removal of a solvent, In that case, the process of removing a solvent from the film | membrane of a solution and forming a film of curable silicone resin, and the process of performing a precure are not specifically distinguished. It is preferable to carry out by heating at 100 degreeC or more, and the removal of a solvent can perform precure subsequently by heating to 150 degreeC or more. 100-300 degreeC and 5-60 minutes are preferable, and, as for the temperature and heating time which remove a solvent and precure, 150-250 degreeC and 10-30 minutes are more preferable.

The temperature condition for thermosetting the curable silicone resin is not particularly limited within the range in which the heat resistance of the resin layer can be improved and the peel strength (x) after lamination with the glass substrate can be controlled as described above, but preferably 300 to 475 ° C. And 350-450 degreeC is more preferable. Moreover, 30-300 minutes are preferable normally and, as for heat time, 60-120 minutes are more preferable. When the temperature of thermosetting is too low, heat resistance and flatness of a resin layer will fall, while when temperature is too high, peeling strength (x) will become low too much and it may become difficult to laminate a glass substrate in all.

(Lamination process)

Lamination | stacking process laminate | stacks the glass substrate 16 on the layer of the resin layer 14 obtained by the said resin layer formation process, and forms the layer of the support plate 12, the resin layer 14, and the layer of the glass substrate 16. It is a process of obtaining the laminated body provided in this order. More specifically, as shown in FIG. 2 (B), the surface 14a on the side opposite to the support plate 12 side of the resin layer 14, the first main surface 16a and the second main surface 16b are separated. The 1st main surface 16a of the glass substrate 16 which has is made into a laminated surface, the resin layer 14 and the glass substrate 16 are laminated | stacked, and the laminated body 10 is obtained.

The method of laminating the glass substrate 16 on the resin layer 14 is not particularly limited, and a known method can be adopted.

For example, the method of overlapping the glass substrate 16 on the surface of the resin layer 14 in an atmospheric pressure environment is mentioned. In addition, after laminating | stacking the glass substrate 16 on the surface of the resin layer 14 as needed, you may crimp the glass substrate 16 to the resin layer 14 using a roll or a press. Since the bubble mixed in between the resin layer 14 and the layer of the glass substrate 16 is removed comparatively easily by the press of a roll or a press, it is preferable.

Pressing by the vacuum lamination method or the vacuum press method is more preferable because suppression of mixing of bubbles and securing of good adhesion are performed. By pressing under vacuum, even when a minute bubble remains, there is also an advantage that the bubble does not grow due to heating and is hard to lead to deformation defects of the glass substrate 16.

When laminating | stacking the glass substrate 16, it is preferable to fully wash | clean the surface of the glass substrate 16 which contacts the resin layer 14, and to laminate | stack in the environment with high cleanness. The higher the cleanliness, the better the flatness of the glass substrate 16 is, which is preferable.

In addition, after laminating | stacking the glass substrate 16, you may perform a pre-annealing process (heating process) as needed. By performing the said pre-annealing process, the adhesiveness with respect to the resin layer 14 of the laminated glass substrate 16 improves, it can be set as appropriate peeling strength (x), and is used for an electronic device at the time of the member formation process mentioned later. Position shift of a member becomes hard to occur, and productivity of an electronic device improves.

Although the conditions of a pre-annealing process are selected suitably according to the kind of resin layer used, 300 is preferable from the point which makes peeling strength (x) between the glass substrate 16 and the resin layer 14 more suitable. It is preferable to heat-process at least 5 degreeC (preferably 300-400 degreeC) for 5 minutes or more (preferably 5 to 30 minutes).

(Laminated body)

The laminated body 10 of this invention can be used for various uses, For example, the manufacture of electronic components, such as a panel for display apparatuses mentioned later, PV, a thin film secondary battery, and a semiconductor wafer with a circuit formed in the surface, etc. are mentioned. Can be. In addition, in the said use, the laminated body 10 is exposed (for example, 1 hour or more) in high temperature conditions (for example, 400 degreeC or more) in many cases.

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.

[Glass Substrate with Member and Manufacturing Method Thereof]

In this invention, the glass substrate (glass substrate with a member) with which the electronic device member containing a glass substrate and the electronic device member is manufactured using the laminated body mentioned above.

Although the manufacturing method of the glass substrate with a said member is not specifically limited, From the point which is excellent in the productivity of an electronic device, the laminated body with which the electronic device member was formed by forming the member for electronic devices on the glass substrate in the said laminated body is attached. Was prepared, and the glass substrate with the member and the support plate with the resin layer were separated from the obtained laminate with an electronic device member with the glass substrate side interface of the resin layer or the inside of the resin layer as a peeling surface, and then, The method of cleaning the peeling surface of the glass substrate with a member is preferable.

Hereinafter, the process of forming the electronic device member on the glass substrate in the said laminated body, and manufacturing the laminated body with an electronic device member is carried out from the member formation process and the laminated body with an electronic device member glass substrate of a resin layer. The process of separating the glass substrate with the member and the support plate with the resin layer with the side interface or the inside of the resin layer as the peeling surface is called a separation process, and the process of cleaning the peeling surface of the glass substrate with the member is called a cleaning process. do.

Below, the material and procedure used in each process are explained in full detail.

(Member formation process)

A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the laminated body 10 obtained by the said lamination process. More specifically, as shown to FIG. 2 (C), the electronic device member 20 is formed on the 2nd main surface 16b (exposure surface) of the glass substrate 16, and the electronic device member adheres. The obtained laminated body 22 is obtained.

First, the electronic device member 20 used at this process is explained in full detail, and the procedure of a process is explained in full detail after that.

(Member for electronic device (functional element))

The member 20 for electronic devices is a member formed on the glass substrate 16 in the laminated body 10, and comprises at least one part of an electronic device. More specifically, the electronic device member 20 is a member (for example, a display device member) used for an electronic component such as a display device panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on its surface. , A member for a solar cell, a member for a thin film secondary battery, and a circuit for an electronic component).

For example, as a solar cell member, in a silicon type | mold, a transparent electrode, such as a tin oxide of a positive electrode, the silicon layer represented by p layer / i layer / n layer, the metal of a negative electrode, etc. are mentioned, In addition, a compound type, Various members etc. corresponding to a dye sensitization type, a quantum dot type, etc. are mentioned.

Moreover, in a lithium ion type | mold, as a member for thin film secondary batteries, transparent electrodes, such as a metal or a metal oxide of a positive electrode and a negative electrode, the lithium compound of an electrolyte layer, the metal of a current collector layer, resin as a sealing layer, etc. are mentioned, In addition, various members etc. which correspond to nickel-hydrogen type | mold, a polymer type, a ceramic electrolyte type, etc. are mentioned.

Examples of circuits for electronic components include metals in the conductive portion, silicon oxide and silicon nitride in the insulating portion, and various sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, flexible printed circuit boards, and rigid circuits. Various members etc. corresponding to a flexible printed board etc. are mentioned.

(Order of process)

The manufacturing method of the laminated body 22 with a member for electronic devices mentioned above is not specifically limited, The glass substrate of the laminated body 10 is conventionally well-known according to the kind of structural member of the member for electronic devices. The member 20 for electronic devices is formed on the surface of the 2nd main surface 16b of 16).

In addition, the member 20 for electronic devices is not all of the member finally formed in the 2nd main surface 16b of the glass substrate 16 (henceforth a "whole member"), but a part of the whole member (following) , "Partial member"). The glass substrate with the partial member peeled off from the resin layer 14 can also be made into the glass substrate with the whole member (corresponding to the electronic device mentioned later) in the subsequent process.

Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with a whole member peeled from the resin layer 14. Moreover, the laminated body with a whole member is assembled, and after that, the support plate 12 can be peeled from the laminated body with a whole member, and an electronic device can be manufactured. In addition, it assembles using the laminated body with two whole members, and after that, the two support plates 12 are peeled from the laminated body with all the members, and the glass substrate with a member which has two glass substrates was attached. It may also be prepared.

For example, when manufacturing OLED, for example, on the surface on the opposite side to the resin layer 14 side of the glass substrate 16 of the laminated body 10 (on the 2nd main surface 16b of the glass substrate 16). In order to form an organic EL structure in the above), a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and a sealing plate is formed. Various layer formation and processing, such as sealing using, are performed. As these layer formation and processing, a film-forming process, vapor deposition process, the adhesion process of a sealing plate, etc. are mentioned specifically ,.

For example, when manufacturing a TFT-LCD, it uses the resist liquid on the 2nd main surface 16b of the glass substrate 16 of the laminated body 10 for general film-forming methods, such as a CVD method and a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning a metal film, a metal oxide film, or the like formed thereon, and a resist liquid on the second main surface 16b of the glass substrate 16 of the other laminate 10. Is used to form a color filter (CF) using pattern formation, and a laminate is formed by laminating the laminate with TFT obtained in the TFT forming step and the laminate with CF obtained in the CF forming step. It has various processes, such as a process.

In a TFT formation process and a CF formation process, TFT and CF are formed in the 2nd main surface 16b of the glass substrate 16 using well-known photolithography technique, an etching technique, etc. At this time, a resist liquid is used as the coating liquid for pattern formation.

In addition, before forming TFT or CF, you may wash the 2nd main surface 16b of the glass substrate 16 as needed. As a washing method, well-known dry washing and wet washing can be used.

In the bonding step, the thin film transistor formation surface of the laminate with TFT and the color filter formation surface of the laminate with CF are faced to each other and bonded using a sealing agent (for example, an ultraviolet curable sealing agent for cell formation). . Thereafter, the liquid crystal material is injected into the cell formed of the laminate with TFT and the laminate with CF. As a method of inject | pouring a liquid crystal material, there exist a vacuum injection method and the dropping injection method, for example.

Separation Process

Separation process makes the interface of the resin layer 14 and the glass substrate 16 or the resin layer 14 into a peeling surface from the laminated body 22 with an electronic device member obtained by the said member formation process, A member including the electronic device member 20 and the glass substrate 16 is attached to the glass substrate 16 (the glass substrate with the member) and the support plate 12 on which the device member 20 is laminated. It is a process of obtaining the obtained glass substrate 24.

When the member 20 for electronic devices on the glass substrate 16 at the time of peeling is a part of formation of the required whole structural member, the remaining structural member may be formed on the glass substrate 16 after separation.

The resin may or may not be attached to the first main surface 16a of the glass substrate 24 with the separated member. As mentioned above, when a peeling surface is an interface of the 1st main surface 16a of the glass substrate 16 and the resin layer 14, resin is in the 1st main surface 16a of the glass substrate 24 with a member. It is not attached. When the peeling surface is inside of the resin layer 14 (that is, when peeling has arisen by cohesive failure of the resin layer), resin is affixed to the 1st main surface 16a of the glass substrate 24 with a member. . In the case where the interfacial peeling and the cohesive fracture peeling occur in part, a portion where the resin is attached to the first main surface 16a of the glass substrate 24 with the member and a portion where the resin is not attached are generated.

Resin is affixed on the surface where the resin layer 14 of the separated support plate 12 existed. When the peeling surface is an interface of the 1st main surface 16a of the glass substrate 16 and the resin layer 14, the support plate 12 with resin of substantially the same structure as the support plate 18 with the said resin layer was affixed. Becomes In the case of the support plate with resin produced by the cohesive failure of the resin layer 14, it becomes a support plate with resin on almost the entire surface of the surface which contacted the resin layer 14, and there are few surfaces with no resin.

2 (D) shows a case where the resin layer 14 is cohesively broken, and a part of the resin of the resin layer 14 is attached to the surface in contact with the resin layer 14 of the glass substrate 16.

The method of peeling the glass substrate 16 and the support plate 12 is not specifically limited. Specifically, for example, a sharp blade-shaped object is inserted into the interface between the glass substrate 16 and the resin layer 14 to give a trigger for peeling, and then sprayed or sprayed with a mixed fluid of water and compressed air. Preferably, it is provided on the surface plate so that the support plate 12 of the laminated body 22 with an electronic device member attached may be an upper side, and the electronic device member 20 side may become a lower side, and the electronic device member 20 side Is vacuum adsorbed on the surface plate (sequentially performed when the supporting plates are stacked on both surfaces), and the blade is first introduced into the glass substrate 16-resin layer 14 interface in this state. Then, the support plate 12 side is adsorbed with a plurality of vacuum adsorption pads, and the vacuum adsorption pads are raised in order from the vicinity of the point where the blade is inserted. Then, an air layer is formed in the interface of the resin layer 14 and the glass substrate 16, and the cohesive failure surface of the resin layer 14, and the air layer spreads to the whole surface of an interface or the cohesive failure surface, and the support plate 12 It can peel easily.

Moreover, the support plate 12 can be laminated | stacked with the new glass substrate, and the laminated body 10 of this invention can be manufactured. When the resin layer 14 adheres to the surface of the separated support plate 12 without being destroyed, the support plate 12 to which the resin layer is attached is used as the support plate 18 with the resin layer, The laminated body 10 can be manufactured similarly to the above. Moreover, in the case of the support plate 12 separated by the cohesive failure of the resin layer, the attached resin is removed and the support plate 12 to which the resin is not attached is used, and the support plate 12 to which this resin is not attached is used. In the same manner as above, the laminate 10 can be manufactured. As a manufacturing method of this new laminated body 10, the manufacturing method of this invention mentioned above is preferable.

In addition, when separating the glass substrate with a member from a laminated body, by controlling the spraying and humidity by an ionizer, it is further suppressed that electrostatic adsorption | suction of the fragment of a resin layer to the glass substrate with a member is carried out. can do.

[Cleaning Process]

A cleaning process is a process of performing a cleaning process to the peeling surface (1st main surface 16a) of the glass substrate 16 in the glass substrate 24 with a member obtained by the said separation process. By performing this process, impurities, such as a resin and a resin layer adhering to a peeling surface, the metal piece and dust generate | occur | produced in the said member formation process attached to a peeling surface, can be removed, and the cleanliness of a peeling surface can be maintained. As a result, the adhesiveness of retardation film, polarizing film, etc. affixed on the peeling surface of the glass substrate 16 improves.

More specifically, by performing this process, as shown to FIG. 2 (E), a part of resin layer adhering on the surface of the glass substrate 16 in FIG. 2 (D) is removed.

The method of the cleaning treatment is not particularly limited as long as the resin, dust or the like attached to the peeling surface can be removed. For example, the method of thermally decomposing a deposit, the method of removing the impurity on a peeling surface by plasma irradiation or light irradiation (for example, UV irradiation process), the method of wash | cleaning process using a solvent, etc. are mentioned. In particular, the washing | cleaning process method using a solvent is preferable at the point which is excellent in the removal property of an impurity.

The kind of solvent used in the washing process method using a solvent is suitably selected according to the kind of resin which comprises the resin layer used.

For example, sp value, namely the solubility parameter is 7-15: it is preferable to perform a cleaning process using a chemical solution containing the solvent (in cal ^1/2 cm ^-3/2). More specifically, it is preferable to use a chemical liquid containing methanol, ethanol, propanol, acetone, xylene, hexane, isoparaffin and the like. Moreover, it is preferable to use the washing | cleaning liquid containing alcohol-type washing | cleaning liquid (for example, methanol, ethanol, propanol) from a viewpoint of environmental load. These solvents are used alone or in combination.

In addition, you may perform a sealing and masking process so that the member for electronic devices 20 may not contact with a solvent as needed. Moreover, it is preferable to perform solvent removal processing, such as air blow or heat drying together.

The manufacturing method of the glass substrate 24 with a member mentioned above is suitable for manufacture of the small display apparatus used for mobile terminals, such as a mobile telephone and a PDA. The display device is mainly LCD or OLED, and the LCD includes 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 any of a passive driving type and an active driving type display device.

As the glass substrate 24 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 member for a glass substrate and a thin film secondary battery The thin film secondary battery which has the thing, the electronic component which has a glass substrate, and the member for electronic devices, etc. are mentioned. 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.

Example

Although an Example etc. demonstrate this invention concretely below, this invention is not limited by these examples.

In the following Examples 1-6 and Comparative Examples 1-3, the glass board which consists of alkali-free borosilicate glass (200 mm in length, 200 mm in width, 0.3 mm in thickness, linear expansion coefficient 38x10 <^-7> / degreeC), Asahi Glass Co., Ltd. brand name "AN100") was used. As the support plate, a glass plate made of alkali-free borosilicate glass (240 mm long, 240 mm wide, 0.4 mm thick, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., and Asahi Glass Co., Ltd. product name “AN100”) was used. .

Production Example 1 Preparation of Liquids Containing Curable Silicone Resin (S1)

100 parts by mass of phenyltrimethoxysilane as the compound constituting the organosiloxy unit (A-1) and 225 parts by mass of dimethyldiethoxysilane as the compound constituting the organosiloxy unit (B-1), 230 parts by mass of toluene was added. Subsequently, 140 mass parts of 0.5 mass% sodium hydroxide aqueous solution was dripped and added to this mixture, maintaining at 10 degrees C or less, and it stirred at 10 degreeC for 3 hours, and 50 degreeC for 3 hours. Thereafter, the mixture was kept at 70 ° C for 2 hours to remove alcohol, and then stirred at 75 ° C for 10 hours.

150 mass parts of toluene was added and diluted to the obtained reaction liquid, and it isolate | separated into two layers. The lower sodium hydroxide aqueous solution layer was removed with a separating funnel. After washing with water until pH of the toluene layer which is an upper layer became 7 or less, it filtered with the membrane filter of 0.5 micrometer of pore diameters. The organic solvent was removed by heating and depressurizing the obtained liquid at 70 degreeC, and curable silicone resin (S1) was obtained.

As for obtained curable silicone resin (S1), the weight average molecular weight (polystyrene conversion) by GPC (gel permeation chromatography) was 55000. Moreover, absorption of 3200-3600 cm <^-1> derived from Si-OH group was confirmed by FT-IR (infrared spectrophotometer).

Next, 100 mass parts of curable silicone resin (S1) was dissolved in 200 mass parts of 1-methoxy-2-propanol acetate, and the liquid substance containing curable silicone resin (S1) was manufactured.

<Manufacture example 2-5> Preparation of curable silicone resin (S2)-(S5) and each liquid substance

About curable silicone resin (S2)-(S5), it carried out similarly to manufacture example 1, and manufactured by the composition ratio shown in Table 1. Subsequently, the obtained curable silicone resin (S2)-(S5) was dissolved in 1-methoxy-2-propanol acetate, and the liquid substance containing curable silicone resin (S2)-(S5), respectively was manufactured.

In addition, the "silanol group" column of the following Table 1 means whether a silanol group is contained in curable silicone resin (S1)-(S5). In addition, in Table 1, mol% of the unit (B-2) was calculated as "0".

<Example 1>

Initially, the support plate of 0.4 mm of plate | board thickness was wash | cleaned purely, and also UV wash | cleaned and it cleaned.

Next, the liquid substance containing curable silicone resin (S1) was coated by the spin coater on the 1st main surface of a support plate (coating amount 30g / m <2>).

Next, this was heat-hardened in air | atmosphere for 10 minutes at 180 degreeC, and the solvent in the layer of the composition on a support plate was removed. Then, it heat-hardened in air | atmosphere for 60 minutes at 450 degreeC, and the resin layer of thickness 2micrometer was formed in the 1st main surface of a support plate.

Then, the resin layer surface of a glass substrate and a support plate is bonded together by vacuum press at room temperature, and then heat-processed at 350 degreeC for 10 minutes, the edge part of a support plate is cut and removed to the same dimension as a glass substrate, and the laminated body A is carried out. Got.

In the obtained laminated body A, the support plate and the glass substrate were closely_contact | adhered without generating a resin layer and foam | bubble, there was no deformation | transformation fault and the smoothness was also favorable.

Next, when the laminated body A was heat-processed for 450 degreeC for 60 minutes in air | atmosphere, and cooled to room temperature, the external appearance change, such as the separation of the support plate and glass substrate of laminated body A, foaming and whitening of the resin layer, was not confirmed.

And a glass substrate and a peeling notch part are formed, inserting the stainless steel cutlery of thickness 0.1mm in the interface of the glass substrate and the resin layer of a support plate in the corner part of four points of laminated body A, and forming a peeling notch. A vacuum suction pad was adsorbed on the surface other than the peeling surface of each support plate, the external force was applied in the direction which isolate | separates a glass substrate and a support plate, and it isolate | separated without damaging a glass substrate and a support plate. Insertion of a cutlery was performed here by spraying an antistatic fluid to the said interface from an ionizer (made by Keyence). Specifically, the vacuum adsorption pad was pulled up while continuously spraying an antistatic fluid from the ionizer toward the formed voids.

Moreover, the main part of a resin layer is isolate | separated from a glass substrate with a support plate, and as a result, the peeling strength (y) of the interface of a layer of a support plate and a resin layer is the peeling strength (x) of the interface of a resin layer and a glass substrate, or It was confirmed that it was higher than the cohesive fracture strength (z) of a resin layer.

Subsequently, after performing the brush washing | cleaning by alcohol solution (Nipol Alcohol Sales Co., Neo-Call R7) for 1 minute on the peeling surface of the separated glass substrate, it air-cleaned and cleaned.

The alcohol solution contains 86.6% by mass of ethanol, 9.5% by mass of normal propyl alcohol (NPA), 2.6% by mass of methanol and 1.5% by mass of isopropyl alcohol (IPA).

As a result of observing the surface of the glass plate after cleaning with a microscope, foreign substances, such as an oxide and resin, and a flaw were not seen.

<Example 2>

In the same manner as in Example 1, a resin layer having a thickness of 1.5 μm made of a heat cured product of the curable silicone resin (S2) was formed on the first main surface of the support plate.

Then, the laminated body B was obtained by the method similar to Example 1.

In the obtained laminated body B, the support plate and the glass substrate were closely_contact | adhered without generating a resin layer and foam | bubble, there was no deformation | transformation fault and the smoothness was also favorable.

Next, when the laminated body B was heat-treated similarly to Example 1, the change in external appearance, such as the separation of the support plate and glass substrate of laminated body B, and foaming and whitening of the resin layer, was not confirmed.

And the laminated body B was isolate | separated without damaging a glass substrate and a support plate by the method similar to Example 1.

Then, the peeling surface of the separated glass substrate was cleaned by the method similar to Example 1.

As a result of observing the surface of the glass plate after cleaning with a microscope, foreign substances, such as an oxide and resin, and a flaw were not seen.

<Example 3>

In the same manner as in Example 1, a resin layer having a thickness of 2 μm made of a heat cured product of the curable silicone resin (S3) was formed on the first main surface of the support plate.

Then, the laminated body C was obtained by the method similar to Example 1.

In the obtained laminated body C, the support plate and the glass substrate were closely_contact | adhered without generating a resin layer and foam | bubble, there was no deformation | transformation fault and the smoothness was also favorable.

Next, when the laminated body C was heat-treated similarly to Example 1, the change in external appearance, such as the separation of the support plate and glass substrate of laminated body C, foaming and whitening of the resin layer, was not confirmed.

And the laminated body C was isolate | separated without damaging a glass substrate and a support plate by the method similar to Example 1.

Then, the peeling surface of the separated glass substrate was cleaned by the method similar to Example 1.

As a result of observing the surface of the glass plate after cleaning with a microscope, foreign substances, such as an oxide and resin, and a flaw were not seen.

<Example 4>

In this example, an OLED is manufactured using the laminate A obtained in Example 1.

First, a film is formed on the second main surface of the glass substrate in the laminate A in the order of silicon nitride, silicon oxide, and amorphous silicon by the plasma CVD method. Next, a low concentration of boron is injected into the amorphous silicon layer by an ion doping apparatus, followed by heat treatment at 450 ° C. for 60 minutes in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, from the etching and ion doping apparatus using the photolithographic method, low concentration phosphorus is inject | poured into an amorphous silicon layer, and N type and P type TFT area is formed. Next, on the second main surface side of the glass substrate, a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering, and a gate electrode is formed by etching using a photolithography method. do. Next, high concentrations of boron and phosphorus are injected into the desired areas of the N type and the P type by the photolithography method and the ion doping apparatus to form a source area and a drain area. Next, on the second main surface side of the glass substrate, an interlayer insulating film is formed by the deposition of silicon oxide by the plasma CVD method, and a TFT electrode is formed by the deposition of aluminum by the sputtering method and the etching using the photolithography method. Next, after performing a heat treatment by performing heat treatment at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by forming nitrogen silicon by plasma CVD method. Next, an ultraviolet curable resin is apply | coated to the 2nd main surface side of a glass substrate, and a planarization layer and a contact hole are formed by the photolithographic method. Next, indium tin oxide is formed into a film by sputtering method, and a pixel electrode is formed by the etching using the photolithographic method.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [(N-naphthyl) as a hole injection layer were formed on the 2nd main surface side of a glass substrate by the vapor deposition method. ) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene to 8-quinolinol aluminum complex (Alq ₃ ) as light emitting layer 40 vol% of -1,5-dicarbonitrile (BSN-BCN) was mixed, and Alq ₃ was formed in this order as an electron transporting layer. Next, aluminum was formed by sputtering, and photolithography was performed. The counter electrode is formed by etching Next, another glass substrate is bonded and sealed to the second main surface side of the glass substrate via an ultraviolet curable adhesive layer. A laminate A having an organic EL structure on a glass substrate (hereinafter referred to as panel A). It is a laminated body (panel for display apparatus with a support plate) with which the electronic device member of this invention was attached.

Subsequently, after vacuum-adsorbing the sealing body side of panel A to a surface plate, the stainless steel cutlery of thickness 0.1mm is inserted in the interface of the glass substrate and the resin layer of the corner part of panel A, and peeling is carried out at the interface of a glass substrate and the resin layer. Give an opportunity. And the surface of the support plate of panel A is made to adsorb | suck with a vacuum suction pad, and then a suction pad is raised. Insertion of a cutlery is performed here by spraying an antistatic fluid to the said interface from an ionizer (made by Keyence). Next, the vacuum suction pad is pulled up while continuously spraying the antistatic fluid from the ionizer toward the formed voids. As a result, only the glass substrate in which the organic electroluminescent structure was formed on the surface plate can be left, and the support plate with a resin layer can be peeled off.

Subsequently, the peeling surface of the glass substrate separated by the method similar to Example 1 was cleaned, the separated glass substrate was cut | disconnected using a laser cutter or the scribe-break method, and it divided | segmented into several cells, and the organic EL structure was formed. The glass substrate and the counter substrate are assembled, and a module forming step is performed to produce an OLED. The OLED obtained in this way does not produce a problem in characteristic.

Example 5

In this example, an LCD is manufactured using the laminate A obtained in Example 1.

First, two laminates A are prepared and formed on the second main surface of the glass substrate in one laminate A1 in the order of silicon nitride, silicon oxide, and amorphous silicon by the plasma CVD method. Next, a low concentration of boron is injected into the amorphous silicon layer by an ion doping apparatus, followed by heat treatment at 450 ° C. for 60 minutes in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing device. Next, a low concentration of phosphorus is injected into the amorphous silicon layer from the etching and ion doping apparatus using the photolithography method to form N-type and P-type TFT areas. Next, on the second main surface side of the glass substrate, a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering, and a gate electrode is formed by etching using a photolithography method. do. Next, high concentrations of boron and phosphorus are injected into the desired areas of the N type and the P type by the photolithography method and the ion doping apparatus to form a source area and a drain area. Next, on the second main surface side of the glass substrate, an interlayer insulating film is formed by the deposition of silicon oxide by the plasma CVD method, and a TFT electrode is formed by the deposition of aluminum by the sputtering method and the etching using the photolithography method. Next, after performing a heat treatment by performing heat treatment at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by forming nitrogen silicon by plasma CVD method. Next, an ultraviolet curable resin is apply | coated to the 2nd main surface side of a glass substrate, and a planarization layer and a contact hole are formed by the photolithographic method. Next, indium tin oxide is formed into a film by sputtering method, and a pixel electrode is formed by the etching using the photolithographic method.

Next, the other laminated body A2 is heat-processed at 450 degreeC for 60 minutes in air | atmosphere atmosphere. Next, chromium is formed into a film by the sputtering method on the 2nd main surface of the glass substrate in the laminated body A, and a light shielding layer is formed by the etching using the photolithographic method. Next, a color resist is apply | coated to the 2nd main surface side of a glass substrate by the die-coat method, and a color filter layer is formed by the photolithographic method and thermosetting. Next, indium tin oxide is formed into a film by sputtering method, and a counter electrode is formed. Next, the ultraviolet curable resin liquid is apply | coated to the 2nd main surface side of a glass substrate by a diecoat method, and columnar spacer is formed by the photolithographic method and thermosetting. Next, a polyimide resin liquid is apply | coated by the roll coat method, an orientation layer is formed by thermosetting, and rubbing is performed.

Next, after drawing the resin liquid for sealing in a frame shape by the dispenser method, and dropping liquid crystal by the dispenser method in a frame, the glass of two laminated bodies A was used using the laminated body A1 in which the pixel electrode was formed above. The 2nd main surface side of a board | substrate is bonded together, and an LCD panel is obtained by ultraviolet curing and thermosetting.

Subsequently, the second main surface of the laminated body A1 was vacuum-adsorbed to the surface plate, and a stainless steel cutlery having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner portion of the laminated body A2, and the first main surface of the glass substrate and the number thereof. It gives an opportunity of peeling of the peelable surface of a strata layer. Insertion of a cutlery is performed here by spraying an antistatic fluid to the said interface from an ionizer (made by Keyence). Next, the vacuum suction pad is pulled up while continuously spraying the antistatic fluid from the ionizer toward the formed voids. And the 2nd main surface of the support plate of laminated body A2 is made to adsorb | suck with a vacuum suction pad, and then a suction pad is raised. As a result, on the surface plate, only the empty cell of the LCD with a support plate of the laminate A1 is left, and the support plate can be peeled off.

Next, the 2nd main surface of the glass substrate in which the color filter was formed in the 1st main surface is vacuum-suctioned to a surface plate, the stainless steel cutlery of thickness 0.1mm is inserted in the interface of the glass substrate and the resin layer of the corner part of laminated body A1, and glass The opportunity of peeling of the peelable surface of a 1st main surface of a board | substrate and a resin layer is given. Then, the second main surface of the support substrate of the laminate A1 is adsorbed with the vacuum adsorption pad, and then the adsorption pad is raised. As a result, only the LCD cell is left on the surface plate, and the support plate on which the resin layer is fixed can be peeled off. Subsequently, the peeling surface is cleaned in the same manner as in Example 1. In this way, the cell of several LCD comprised from the glass substrate of thickness 0.1mm is obtained.

Subsequently, the cell is divided into cells of a plurality of LCDs by a step of cutting. The process of sticking a polarizing plate to each completed LCD cell is performed, and a module formation process is performed subsequently, and an LCD is obtained. LCD obtained in this way does not produce a problem in characteristic.

<Example 6>

In this example, an OLED is manufactured using the laminate A obtained in Example 1.

First, molybdenum is formed into a film by the sputtering method on the 2nd main surface of the glass substrate in the laminated body A, and a gate electrode is formed by the etching using the photolithographic method. Next, silicon nitride is further formed on the second main surface side of the glass substrate by the plasma CVD method to form a gate insulating film, and then indium gallium zinc oxide is formed by the sputtering method, followed by etching using a photolithography method. An oxide semiconductor layer is formed. Next, silicon nitride is further formed on the second main surface side of the glass substrate by plasma CVD to form a channel protective layer, and then molybdenum is formed by sputtering, followed by etching using a photolithography method. And a drain electrode. Next, heat processing is performed for 60 minutes at 450 degreeC in air | atmosphere. Next, on the second main surface side of the glass substrate, silicon nitride is further formed by plasma CVD to form a passivation layer. Subsequently, indium tin oxide is deposited by sputtering to form a pixel electrode by etching using photolithography. To form.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [(N-naphthyl) as a hole injection layer were formed on the 2nd main surface side of a glass substrate by the vapor deposition method. ) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene to 8-quinolinol aluminum complex (Alq ₃ ) as light emitting layer 40 vol% of -1,5-dicarbonitrile (BSN-BCN) was mixed, and Alq ₃ was formed in this order as an electron transporting layer. Next, aluminum was formed by sputtering, and photolithography was performed. The counter electrode is formed by etching Next, another glass substrate is bonded and sealed to the second main surface side of the glass substrate via an ultraviolet curable adhesive layer. A laminate A having an organic EL structure on a glass substrate (hereinafter referred to as panel A). It is a laminated body (panel for display apparatus with a support plate) with which the electronic device member of this invention was attached.

Subsequently, after vacuum-adsorbing the sealing body side of panel A to a surface plate, the stainless steel cutlery of thickness 0.1mm is inserted in the interface of the glass substrate and the resin layer of the corner part of panel A, and peeling is carried out at the interface of a glass substrate and the resin layer. Give an opportunity. And the surface of the support plate of panel A is made to adsorb | suck with a vacuum suction pad, and then a suction pad is raised. Insertion of a cutlery is performed here by spraying an antistatic fluid to the said interface from an ionizer (made by Keyence). Next, the vacuum suction pad is pulled up while continuously spraying the antistatic fluid from the ionizer toward the formed voids. As a result, only the glass substrate in which the organic electroluminescent structure was formed on the surface plate can be left, and the support plate with a resin layer can be peeled off.

Subsequently, the peeling surface of the glass substrate separated by the method similar to Example 1 was cleaned, the separated glass substrate was cut | disconnected using a laser cutter or the scribe-break method, and it divided | segmented into several cells, and the organic EL structure was formed. The glass substrate and the counter substrate are assembled, and a module forming step is performed to produce an OLED. The OLED obtained in this way does not produce a problem in characteristic.

Comparative Example 1

In the same manner as in Example 1, a resin layer having a thickness of 1 μm made of a heat cured product of the curable silicone resin (S4) was formed on the first main surface of the support plate.

Subsequently, as a result of vacuum-pressing the resin layer surfaces of the glass substrate and the support plate at room temperature in the same manner as in Example 1, the resin layer was hard and a part of the resin layer surface of the glass substrate and the support plate was not laminated. Then, as a result of heat-processing for 10 minutes at 350 degreeC, it isolate | separated from the resin layer surface whole surface of a glass substrate and a support plate, and the laminated body was not formed.

Comparative Example 2

In the same manner as in Example 1, a resin layer having a thickness of 1 μm made of a heat cured product of the curable silicone resin (S5) was formed on the first main surface of the support plate. The surface of the resin layer was the flatness of the degree to which a nonuniformity was confirmed by visual observation.

Subsequently, as a result of vacuum pressing the resin layer surfaces of the glass substrate and the support plate at room temperature in the same manner as in Example 1, they were separated from the resin layer surface entire surface of the glass substrate and the support plate, whereby no laminate was formed.

Comparative Example 3

In the same manner as in Example 1, a resin layer having a thickness of 1 μm made of a heat cured product of the curable silicone resin (S6) was formed on the first main surface of the support plate.

Subsequently, as a result of vacuum-pressing the resin layer surfaces of the glass substrate and the support plate at room temperature in the same manner as in Example 1, the resin layer was hard and a part of the resin layer surface of the glass substrate and the support plate was not laminated. Then, as a result of heat-processing for 10 minutes at 350 degreeC, it isolate | separated from the resin layer surface whole surface of a glass substrate and a support plate, and the laminated body was not formed.

<Comparative Example 4>

100 mass parts of silicone for solvent-free addition reaction type release paper (KNS-320A by Shin-Etsu Silicone Co., Ltd.) on the support plate after purifying a support plate (200 mm in length, 200 mm in width, 0.4 mm in thickness) by pure washing | cleaning, UV washing, etc. And a mixture of 2 parts by mass of a platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) with a spin coater (coated amount of 10 g / m 2) and heat-cured at 180 ° C. for 30 minutes in the air to form a silicon having a thickness of 16 μm. The resin layer was obtained.

After cleaning the surface on the side of the glass substrate (200 mm long, 200 mm wide, 0.3 mm thick) in contact with the silicon resin layer by pure water cleaning, UV cleaning, or the like, the silicon resin layer forming surface of the support plate and the glass substrate were kept at room temperature. It bonded together by the vacuum press and obtained the glass laminated body (P) which has an addition polymerization type silicone resin layer.

First, the film was formed on the second main surface of the glass substrate in the laminate P in the order of silicon nitride, silicon oxide, and amorphous silicon by the plasma CVD method. Next, it heat-processed at 450 degreeC for 60 minutes in nitrogen atmosphere, and dehydrogenation was performed. When the laminated body P after dehydrogenation was visually observed, the foam part by volatilization of resin is seen in a part of surface inside, and the edge part of a laminated body, and it is one of four points of laminated body A by the method similar to Example 1. Vacuum adsorption pads on the surface of the glass substrate and the support plate, not the peeling surface of each of the glass substrate and the support plate, while inserting a cutlery of 0.1 mm in thickness into the interface between the glass substrate at the corner portion of the point and the resin layer of the support plate to form a cutout. Was adsorbed, and external force was applied in a direction in which the glass substrate and the support plate were separated from each other to separate the glass substrate and the support plate.

Next, although the brush cleaning by the alcohol solution (Nippon Alcohol company make, Neocol R7) performed in Example 1 was performed with respect to the peeling surface of the glass substrate with resin, adhesion of resin was not able to be removed.

In Examples 4-6, even if an electronic device is formed at high temperature for the laminated body which has a resin layer of this invention, the influence on a device characteristic is not seen. It is inferred that this is because there was no influence by the volatile component in the resin layer of a laminated body.

On the other hand, in the comparative example 4 which is not the resin layer of this invention, foaming is seen when an electronic device is formed at high temperature, and it is thought that volatile component generate | occur | produced. Moreover, resin adhered to a glass substrate cannot be removed.

This application is based on the JP Patent application 2011-228792 of an application on October 18, 2011, The content is taken in here as a reference.

10: laminate
12: support plate
14: resin layer
14a: first principal plane of resin layer
16: glass substrate
16a: first principal surface of glass substrate
16b: second main surface of the glass substrate
18: support plate with a resin layer
20: member for electronic device
22: laminated body with member for electronic devices
24: glass substrate with member

Claims (15)

The layer of a support plate, the resin layer, and the layer of a glass substrate are provided in this order,
The peeling strength (y) of the interface of the layer of the said support plate and the said resin layer is higher than the peeling strength (x) of the interface of the said resin layer and the said glass substrate, or the cohesive fracture strength (z) of the said resin layer,
The resin of the resin layer is a crosslinked silicone resin,
The crosslinked silicone resin includes an organosiloxy unit (A-1) represented by formula (1) and an organosiloxy unit (B-1) represented by formula (2),
The ratio of (A-1) + (B-1) to all the organosiloxy units is 70 to 100 mol%, and (A-1) to the sum of (A-1) and (B-1) The laminated body which is a crosslinked silicone resin whose ratio is 15-50 mol%.

(In Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In Formula (2), R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms. Is displayed.) The method of claim 1,
The crosslinked silicone resin further contains at least one of an organosiloxy unit (A-2) represented by formula (3) and an organosiloxy unit (B-2) represented by formula (4), And the ratio of [(A-1) + (B-2)] to [(A-1) + (A-2) + (B-1) + (B-2)] is from 15 to 50 mol% , Laminate.

(In said formula (3), R <^1> represents a hydrogen atom or a C1-C4 alkyl group, and R <^2> represents a C1-C4 alkyl group. In said formula (4), R <^6> is carbon An alkyl group having 1 to 4 atoms is represented.) The method of claim 2,
In the formulas (1) and (3), the phenyl group (X) represented by formula (9) and the alkyl group (Y) represented by R ⁶ and / or R ⁷ in formulas (2) and (4). The laminated body whose ratio is [(X)] / [(X) + (Y)] = 10-40 mol%.

(In formula (9), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The method of claim 2 or 3,
The laminated body whose ratio of [(A-1) + (A-2) + (B-1) + (B-2)]] with respect to all the organo siloxy units is 95-100 mol%. The method of claim 2 or 3,
The laminated body whose all organo siloxy units represented by said formula (1)-(4) are a unit derived from an organoalkoxysilane compound. The method according to any one of claims 1 to 3,
The laminated body whose thickness of the said resin layer is 1-5 micrometers. The method according to any one of claims 1 to 3,
The laminated body whose said support plate is a glass plate. The method according to any one of claims 1 to 3,
The laminated body whose difference of the average linear expansion coefficient in 25-300 degreeC of the said support plate and said glass substrate is 0-500 * 10 <^-7> / degreeC. A film of curable silicone resin, which is crosslinked and cured to become a crosslinked silicone resin, is formed on the surface of the support plate,
The curable silicone resin is crosslinked and cured on the surface of the support plate to form a film of crosslinked silicone resin, and then
As a manufacturing method of a laminated body which laminates a glass substrate on the surface of the film | membrane of the said crosslinked silicone resin, and manufactures the laminated body provided with the layer of a support plate, the resin layer, and the glass substrate in this order,
The said crosslinked silicone resin contains the organo siloxy unit (A-1) represented by Formula (1), and the organo siloxy unit (B-1) represented by Formula (2), and is all organo siloxy The ratio of (A-1) + (B-1) to the unit is 70 to 100 mol%, and the ratio of (A-1) to the total of (A-1) and (B-1) is 15 to 50 mol% of a method for producing a laminate.

(In Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In Formula (2), R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms. Is displayed.) The method of claim 9,
The curable silicone resin comprises a partially hydrolyzed condensate of a mixture of an organoalkoxysilane compound, and a solution containing the curable silicone resin and a solvent is applied to the surface of the support plate to remove the solvent, thereby removing the solvent. The manufacturing method of a laminated body which forms a film | membrane. The method of claim 10,
The manufacturing method of the laminated body whose weight average molecular weights of the said partial hydrolysis-condensation products are 10,000-200,000. The method of claim 10,
The manufacturing method of the laminated body whose weight average molecular weights of the said partial hydrolysis-condensation product are 10,000-100,000. An electronic device member is formed on the said glass substrate in the laminated body in any one of Claims 1-3, the laminated body with an electronic device member is manufactured,
From the laminated body with an electronic device member, the glass substrate side interface of the said resin layer or the inside of the said resin layer was used as a peeling surface, and it isolate | separates into the glass substrate with an electronic device member, and the support plate with a resin layer, , next,
The manufacturing method of the glass substrate with a member for electronic devices which cleans the peeling surface of the glass substrate with a member for said electronic devices. The method of claim 13,
The manufacturing method of the glass substrate with a member for electronic devices whose said cleaning is washing | cleaning using a solvent. The method of claim 14,
The manufacturing method of the glass substrate with an electronic device member whose said washing | cleaning is washing | cleaning using the solvent whose solubility parameters are 7-15.

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