KR20160102429A - Glass laminate and method for manufacturing same - Google Patents

Abstract

식 중, R^a 및 R^b는 각각 독립적으로 탄소수 4 이하의 알킬기 또는 치환기를 갖고 있어도 되는 페닐기를 나타낸다.The present invention relates to a glass laminate comprising a support substrate layer, a silicone resin layer and a glass substrate layer in this order, wherein the silicone resin of the silicone resin layer has a D unit represented by the following formula (D) ), Wherein the peel strength of the interface between the silicon resin layer and the glass substrate layer is different from the peel strength of the interface between the silicon resin layer and the support substrate layer, Lt; / RTI >

In the formulas, R ^a and R ^b each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent.

Description

Technical Field [0001] The present invention relates to a glass laminate,

The present invention relates to a glass laminate and a method of manufacturing the same, and more particularly to a glass laminate having a predetermined silicone resin layer and a method of manufacturing the same.

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

In recent years, in order to cope with the above problem, a glass laminate in which a glass substrate and a supporting glass plate are laminated is prepared, an electronic device member such as a display device is formed on a glass substrate of the glass laminate, (See, for example, Patent Document 1). More specifically, in the embodiment of Patent Document 1, there is disclosed a glass laminate obtained by subjecting one surface of a glass substrate and a supporting glass plate to surface treatment using dimethyl silicone oil (SH200) and laminating them.

International Publication No. 2011/048979

In recent years, with respect to the glass laminate, the ease of handling thereof becomes difficult due to the thinning of a single layer of the glass substrate, and it is required to more easily peel off the glass substrate after the heat treatment. In other words, it is required that the peeling strength of the glass substrate from the glass laminate is smaller.

The glass laminate obtained using the SH200 described in Patent Document 1 can be peeled off even after heating treatment at 450 ° C for 1 hour in the atmosphere. However, as described above, it is required that the glass substrate be easily peeled off from the present, and the form of Patent Document 1 does not satisfy the required level, and further improvement is required.

In the case of forming a layer by surface treatment using SH200 as described in Patent Document 1, even if the surface treatment conditions are the same for each production lot, depending on the conditions of the liquid used and the environmental conditions such as temperature, The thickness of the layer may be changed depending on the production lot. In the case of using SH200 as described in Patent Document 1, when the thickness of the layer to be formed becomes thick, the layer is foamed and a large amount of outgas is generated. Such generation of outgas causes contamination of a member for an electronic device formed on a glass substrate, which results in deterioration of the productivity of the electronic device.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and provides a glass laminate having a silicon resin layer which can easily peel off a glass substrate even after high temperature heating treatment and has a small difference in degree of foaming with respect to thickness, .

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

That is, the first embodiment of the present invention is a glass laminate comprising a support substrate layer, a silicone resin layer, and a glass substrate layer in this order, wherein the silicone resin of the silicone resin layer is a D Unit and a Q unit expressed by the following formula (Q), wherein the peel strength of the interface with respect to the glass substrate layer of the silicon resin layer is different from the peel strength of the interface between the silicon resin layer and the support substrate layer Glass laminate.

In the first aspect, it is preferable that the molar ratio (D unit / Q unit) of the D unit and the Q unit in the axial polymerizate is 0.02 to 2.

In the first aspect, it is preferable that R ^a and R ^b in formula (D) are all methyl groups.

In the first aspect, it is preferable that the thickness of the silicone resin layer is 5 to 2000 nm.

In the first aspect, it is preferable that the axial polymer is a mixture of the silicon compound (X) represented by the formula (X) to be described later or a large amount thereof and the silicon compound (Y) represented by the formula (Y) It is preferable that the curable compound containing the partial-axis condensation polymer of the mixture is a condensation polymerization polymer.

In the first aspect, it is preferable that R ^a and R ^b in formula (X) are all methyl groups and the hydrolyzable group is an alkoxy group having 4 or less carbon atoms.

In the first aspect, it is preferable that the peel strength of the interface with respect to the layer of the glass substrate of the silicon resin layer is lower than the peel strength of the interface of the silicon resin layer to the support substrate layer.

In the first aspect, it is also preferable that the peel strength at the interface of the silicon resin layer with respect to the glass substrate layer is higher than the peel strength at the interface with the support substrate layer of the silicon resin layer.

In the first aspect, it is preferable that the layer of the supporting substrate is a laminated supporting substrate having a layer of the supporting glass plate and the second silicon resin layer, and the second silicon resin layer is in contact with the silicon resin layer.

In the first aspect, it is preferable that the silicone resin of the second silicone resin layer contains a cured organopolysiloxane having a curing property, and the curable organopolysiloxane has a siloxane unit (A) represented by the formula (1) (B) represented by the following general formula (2).

In the first aspect, it is preferable that the thickness of the second silicon resin layer is thicker than the thickness of the silicon resin layer, and is 50 mu m or less.

A second mode of the present invention is a method for producing a glass laminate of the first mode, wherein a curable compound is applied onto the surface of either the glass substrate or the supporting substrate, And a step of laminating the other of the glass substrate and the supporting substrate on the silicon resin layer.

According to the present invention, it is possible to provide a glass laminate having a silicon resin layer which can easily peel off a glass substrate even after a high-temperature heating treatment and has a small difference in degree of foaming with respect to a thickness, and a method of manufacturing the same.

1 is a schematic cross-sectional view of a first form of a glass laminate according to the present invention.
2 (A) to 2 (D) are schematic cross-sectional views showing one embodiment of a manufacturing method of a glass substrate with a member according to the present invention in the order of process.
3 is a schematic cross-sectional view of a second form of the glass laminate according to the present invention.
4 is a schematic cross-sectional view of a modification of the second form of the glass laminate according to the present invention.

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications and substitutions may be made without departing from the scope of the present invention. .

The feature of the glass laminate of the present invention is that the silicone resin in the silicone resin layer is a chain polymer having a D unit represented by the formula (D) to be described later and a Q unit represented by the formula (Q) described later. When the Q polymer is included in the polymer, the three-dimensional crosslinked structure is formed in the silicone resin layer to improve the heat resistance. When the thickness is increased, foaming of the silicone resin layer is suppressed, Is excellent in peelability. Further, it is presumed that the lamination property of each layer constituting the glass laminate is improved by including the D unit. Here, the improvement in lamination property means a state in which the peeling of the obtained glass laminate is reduced and the lifting of the end portion is reduced.

Further, in the glass laminate, the peel strength at the interface with respect to the glass substrate layer of the silicon resin layer is different from the peel strength at the interface between the silicon resin layer and the support substrate layer. For example, in the first embodiment, the peel strength at the interface of the silicon resin layer to the glass substrate layer is lower than the peel strength at the interface of the silicon resin layer to the support substrate layer, so that the silicon resin layer and the glass substrate layer are peeled And separated into a laminate of a layer of a silicone resin layer and a support substrate and a layer of a glass substrate. In the second embodiment, the peel strength at the interface with respect to the glass substrate layer of the silicon resin layer is higher than the peel strength at the interface with the support substrate layer of the silicone resin layer, so that the silicone resin layer and the support substrate layer are peeled off And is separated into a layer of a glass substrate and a layer of a silicon resin layer and a layer of a supporting substrate.

 Hereinafter, the first embodiment and the second embodiment will be described separately.

≪ First Embodiment >

1 is a schematic cross-sectional view of a first embodiment of a glass laminate according to the present invention.

1, the glass laminate 10 includes a layer of a supporting substrate 12, a layer of a glass substrate 16, and a layer of a silicone resin layer 14 (hereinafter referred to as " (14) ") is present. One side of the silicone resin layer 14 is in contact with the layer of the supporting substrate 12 and the other side of the silicon resin layer 14 is in contact with the first main surface 16a of the glass substrate 16. [

The two-layer portion including the layer of the supporting substrate 12 and the silicon resin layer 14 reinforces the glass substrate 16 in the member forming process for manufacturing the electronic device member such as the liquid crystal panel. The two-layer portion including the layer of the supporting substrate 12 and the silicon resin layer 14 previously prepared for the production of the glass laminate 10 is referred to as a supporting substrate 18 with a resin layer.

This glass laminate 10 is used until the member forming process described later. That is, this glass laminate 10 is used on the surface of the second main surface 16b of the glass substrate 16 until a member for an electronic device such as a liquid crystal display device is formed. Thereafter, the glass laminate on which the electronic device member is formed is separated into the supporting substrate 18 with the resin layer and the glass substrate with the member, and the supporting substrate 18 with the resin layer does not constitute a part constituting the electronic device. The resin supporting base material 18 with the resin layer can be laminated with the new glass substrate 16 and reused as a new glass laminate 10.

The interface between the supporting substrate 12 and the silicone resin layer 14 has a peeling strength x and a stress in the peeling direction exceeding the peeling strength x is applied to the interface between the supporting substrate 12 and the silicon resin layer 14 The interface between the supporting substrate 12 and the silicone resin layer 14 is peeled off. The interface between the silicon resin layer 14 and the glass substrate 16 has a peel strength y and a stress in the peeling direction exceeding the peel strength y is exerted on the interface between the silicon resin layer 14 and the glass substrate 16 The interface between the silicon resin layer 14 and the glass substrate 16 is peeled off.

In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, when the stress in the direction in which the supporting substrate 12 and the glass substrate 16 are separated from each other is applied to the glass laminate 10, the glass laminate 10 is bonded to the interface between the silicon resin layer 14 and the glass substrate 16 And separated into the glass substrate 16 and the supporting substrate 18 with the resin layer.

The peel strength (x) is preferably sufficiently high as compared with the peel strength (y). Raising the peel strength x means that the adhesion force of the silicone resin layer 14 to the support substrate 12 can be increased and a relatively high adhesion force to the glass substrate 16 can be maintained after the heat treatment .

In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, for example, a method of forming the silicone resin layer 14 on the support substrate 12 (for example, a method in which a curable compound ) To form the silicone resin layer 14). The silicone resin layer 14 bonded to the supporting substrate 12 with high bonding force can be formed by the adhesive force at the time of curing at the time of forming the silicone resin layer 14. [

On the other hand, the bonding force of the silicone resin to the glass substrate 16 after curing is generally lower than the bonding force generated at the time of curing. The glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the supporting substrate 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14. [

Hereinafter, each of the layers (supporting substrate 12, glass substrate 16, and silicone resin layer 14) constituting the glass laminate 10 will be described in detail, and then the glass laminate body 10 Will be described in detail.

[Supporting substrate]

The supporting substrate 12 supports and reinforces the glass substrate 16 and is capable of deforming and deforming the glass substrate 16 at the time of manufacturing the electronic device member in the member forming process (the process for manufacturing the electronic device member) It prevents scratches, breakage, and the like.

As the supporting substrate 12, for example, a metal plate such as a glass plate, a plastic plate, an SUS plate, or the like is used. It is preferable that the supporting substrate 12 is formed of a material having a small difference in coefficient of linear expansion from the glass substrate 16 and is formed of the same material as that of the glass substrate 16 And the supporting substrate 12 is preferably a glass plate. In particular, the supporting substrate 12 is preferably a glass plate containing the same glass material as the glass substrate 16.

Further, as described later, the supporting substrate 12 may be a laminate including two or more layers.

The thickness of the supporting substrate 12 may be thicker or thinner than that of the glass substrate 16. The thickness of the supporting substrate 12 is preferably selected based on the thickness of the glass substrate 16, the thickness of the silicon resin layer 14, and the thickness of the glass laminate 10. [ For example, the present member forming process is designed to process a substrate having a thickness of 0.5 mm. When the sum of the thickness of the glass substrate 16 and the thickness of the silicon resin layer 14 is 0.1 mm, The thickness is 0.4 mm. The thickness of the supporting substrate 12 is usually 0.2 to 5.0 mm. Further, in the case where the supporting substrate 12 is a laminate including two or more kinds of layers, the " thickness of the supporting substrate 12 " means the total thickness of all the layers.

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for ease of handling and difficulty in breaking. The thickness of the glass plate is preferably not more than 1.0 mm from the viewpoint of the rigidity required to warp properly without breaking when peeling off after formation of the electronic device member.

The difference in average coefficient of linear expansion between the support substrate 12 and the glass substrate 16 at 25 to 300 占 폚 is preferably 500 占^10-7 / 占 폚 or less, more preferably 300 占^10-7 / 占 폚 or less, More preferably 200 x 10 < ^-7 > / DEG C or less. When the difference is too large, there is a possibility that the glass laminate 10 is severely bent and the supporting substrate 12 and the glass substrate 16 are peeled off during the heating and cooling in the member forming process. When the material of the supporting substrate 12 is the same as the material of the glass substrate 16, occurrence of such a problem can be suppressed.

[Glass Substrate]

The glass substrate 16 is provided with the electronic device member on the second main surface 16b on the side opposite to the side of the silicon resin layer 14 with the first main surface 16a contacting with the silicon resin layer 14. [

The type of the glass substrate 16 may be a general one, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 16 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. The coefficient of thermal expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio. The contents of JIS R 3102 (revised in 1995) are also incorporated herein by reference.

If the coefficient of linear expansion of the glass substrate 16 is large, the member forming process often involves heat treatment, and thus various problems are likely to occur. For example, when the TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed under heating is cooled, the positional deviation of the TFT may be excessive due to heat shrinkage of the glass substrate 16. [

The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate. Such a forming method may be a general one, and for example, a float method, a fusion method, a slot down-draw method, a fur co-ling method, a lub bus method, and the like are used. In particular, the glass substrate 16 having a small thickness can be obtained by heating the glass molded into a plate shape at one time to a moldable temperature, stretching it by means of drawing or the like and thinning it (lead-through method).

The kind of glass of the glass substrate 16 is not particularly limited, but is preferably an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, glass having a silicon oxide content of 40 to 90 mass% in terms of an oxide is preferable.

As the glass for the glass substrate 16, glass suitable for the kind of the electronic device member and its manufacturing process is adopted. For example, a glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free of an alkali metal component from the viewpoint that elution of an alkali metal component easily affects the liquid crystal . Thus, the glass of the glass substrate 16 is appropriately selected based on the kind of the applied device and the manufacturing process thereof.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. [ When the thickness is 0.3 mm or less, it is possible to impart good flexibility to the glass substrate 16. When the thickness is 0.15 mm or less, the glass substrate 16 can be rolled up.

The thickness of the glass substrate 16 is preferably 0.03 mm or more for ease of manufacture of the glass substrate 16 and ease of handling of the glass substrate 16. [

Further, the glass substrate 16 may include two or more layers. In this case, the materials for forming the respective layers may be the same or different materials. In this case, " the thickness of the glass substrate 16 " means the total thickness of all the layers.

[Silicone resin layer]

The silicon resin layer 14 in the glass laminate 10 prevents the positional deviation of the glass substrate 16 until the operation of separating the glass substrate 16 and the supporting substrate 12 is performed, (16) is prevented from being damaged by the separating operation. The surface 14a of the silicon resin layer 14 in contact with the glass substrate 16 is in close contact with the main surface 16a of the glass substrate 16 in a peelable manner. On the other hand, the silicone resin layer 14 is fixed on the supporting substrate 12. [ That is, the silicon resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength y of the interface is higher than the peeling strength y of the silicon resin layer 14 and the support substrate 12. [ Is less than the peel strength (x) of the interface.

That is, when separating the glass substrate 16 and the supporting substrate 12, the glass substrate 16 is separated from the interface between the first main surface 16a of the glass substrate 16 and the silicone resin layer 14, It is difficult to peel off from the interface of the layer 14. Therefore, although the silicon resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, it has a surface characteristic capable of easily separating the glass substrate 16. That is, the silicon resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain degree of bonding force to prevent displacement of the glass substrate 16, and the glass substrate 16 The glass substrate 16 is bonded to the glass substrate 16 with a bonding force to such an extent that the glass substrate 16 can easily be peeled off. In the present invention, the property of easily peeling off the surface of the silicone resin layer 14 is referred to as peelability. On the other hand, the first main surface of the supporting substrate 12 and the silicon resin layer 14 are bonded with a bonding force that is relatively difficult to peel off.

The bonding force of the interface between the silicon resin layer 14 and the glass substrate 16 is formed by forming the electronic device member on the surface (the second main surface 16b) of the glass substrate 16 of the glass laminate 10 (I.e., the peel strength (x) or the peel strength (y) may be changed). However, even after forming the member for electronic devices, the peel strength (y) is lower than the peel strength (x).

It is considered that the layers of the silicone resin layer 14 and the glass substrate 16 are bonded with a bonding force due to weak adhesive force or Van der Waals force. In the case where the glass substrate 16 is laminated on the surface of the silicon resin layer 14 after it is formed, if the silicone resin of the silicone resin layer 14 is sufficiently crosslinked so as not to exhibit the adhesive force, As shown in Fig. However, the silicone resin of the silicone resin layer 14 often has a weak adhesive strength to some extent. Even in the case where the adhesive property is very low, when the electronic device member is formed on the laminated body after the production of the glass laminate 10, the silicone resin of the silicone resin layer 14 is heated on the glass substrate 16 surface And it is considered that the bonding force between the silicon resin layer 14 and the layer of the glass substrate 16 is increased.

The bonding strength between the surface of the silicon resin layer 14 before lamination and the first main surface 16a of the glass substrate 16 before lamination may be weakened as the case may be. The bonding strength between the interface of the silicon resin layer 14 and the layer of the glass substrate 16 can be weakened and the peeling strength y can be lowered by performing non-adhesive treatment or the like on the surface to be laminated and then laminating it.

Further, the silicone resin layer 14 is bonded to the surface of the supporting substrate 12 with a strong bonding force such as an adhesive force and an adhesive force, and a known method can be adopted as a method for enhancing the adhesion of the both. For example, by curing the curable compound described below on the surface of the supporting substrate 12, a high bonding force can be obtained by adhering the silicone resin as the axis polymer to the surface of the supporting substrate 12. The surface of the supporting substrate 12 and the surface of the silicon resin layer 14 are subjected to a treatment (for example, a treatment using a coupling agent) that generates a strong bonding force between the surface of the supporting substrate 12 and the silicone resin layer 14, Can be increased.

The reason why the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peel strength x of the interface is high.

The thickness of the silicone resin layer 14 is not particularly limited, but is preferably 5 to 5000 nm, more preferably 5 to 2000 nm, further preferably 50 to 2000 nm, particularly preferably 100 to 1000 nm. When the thickness of the silicon resin layer 14 is within this range, the occurrence of distortion defects in the glass substrate 16 can be suppressed even when bubbles or foreign matter intervene between the silicon resin layer 14 and the glass substrate 16 .

The thickness is intended to mean the average thickness, and the thickness of the silicone resin layer 14 is measured at arbitrary positions of 5 points or more, and these are arithmetically averaged.

The surface roughness Ra of the surface of the silicon resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably 0.1 to 20 nm, more preferably 0.1 to 20 nm, in view of better lamination and releasability of the glass substrate 16. [ More preferably 10 nm.

The surface roughness Ra is measured according to JIS B 0601-2001, and the value obtained by arithmetically averaging the Ra measured at any five or more points corresponds to the surface roughness Ra. The contents of JIS B 0601-2001 are also incorporated herein by reference.

The water contact angle of the surface of the silicon resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably 70 degrees or more and 105 degrees or less from the viewpoint of better lamination property and peelability of the glass substrate 16 Do.

As a method of measuring the water contact angle, a water contact angle is measured by placing 1 mu L of water droplet on the surface of one glass plate using a contact angle meter (DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2 manufactured by Krus).

(Silicone resin in the silicone resin layer)

The silicone resin of the silicone resin layer 14 is a condensation polymer having a D unit represented by the following formula (D) and a Q unit represented by the following formula (Q).

In the formula (D), R ^a and R ^b each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent.

The number of carbon atoms contained in the alkyl group is preferably 1 to 3 since the heat resistance of the silicone resin layer 14 or the peelability of the glass substrate 16 is more excellent. More specifically, examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.

In the condensate, the molar ratio (D unit / Q unit) of the D unit to the Q unit is preferably 0.02 to 2, more preferably 0.1 to 1.8. Within this range, heat resistance and peelability are good.

The content of the sum of the D unit and the Q unit in the condensed polymer is not particularly limited, but is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%, based on the total siloxane units. Examples of the siloxane unit include M units and T units in addition to the D units and Q units.

The condensation polymer is obtained by reacting a silicon compound (X) represented by the following formula (X) or a multimer thereof (hydrolyzed condensate) described below with a silicon compound (Y) represented by the formula (Y) Water), or a cured compound containing a partial condensate of the mixture.

When the R ^x group of the silicon compound (X) is a hydroxy group, molecules of the silicon compound (X) are intensively polymerized to form a multimer. When the R ^x group of the silicon compound (X) is a hydrogen atom and a hydrolyzable group, the hydrogen atom and the hydrolyzable group are hydrolyzed to generate a hydroxyl group, and then the molecules of the silicon compound (X) are intensively polymerized to become a multimer. The oligomer of the silicon compound (Y) is also obtained in the same manner.

Hereinafter, the form of the silicon compound (X) and the silicon compound (Y) will be described in detail.

(Silicon compound (X) represented by the formula (X))

(X) or a multimer thereof (hereinafter simply referred to as "silicon compound (X)") represented by the following formula (X) is used as one of starting materials of the silicone resin in the silicone resin layer 14 .

In the formulas, R ^a and R ^b each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent, and R ^x each independently represents a hydrogen atom, a hydroxyl group or a hydrolyzable group. The plural R ^x can have the same contribution or different contributions.

R ^a and R ^b are the same and each R ^a and R ^b in the formula (D).

R ^x each independently represents a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Examples of the hydrolyzable group include an alkoxy group, a chlorine atom, and an amino group. The number of carbon atoms contained in the alkoxy group is not particularly limited, but is preferably 1 to 3 in view of the heat resistance of the silicone resin layer 14 or the peelability of the glass substrate 16. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group. When R ^x is a hydrogen atom, for example, the Si-H group is converted into a Si-OH group under a predetermined acid catalyst (for example, a 60% nitric acid aqueous solution) The hydrolysis / condensation reaction proceeds.

The compound represented by the formula (X) may be a multimer, and the upper limit of the n value of the n-dimer is not particularly limited. However, from the viewpoint of ease of synthesis, Among them, n is preferably 10 to 500 since heat resistance of the silicone resin layer 14 or releasability of the glass substrate 16 is more excellent.

(Silicon compound (Y) (tetraalkoxysilane compound) represented by the formula (Y))

It is preferable that a silicon compound (Y) represented by the following formula (Y) or a multimer thereof is used as one of starting materials of the silicone resin in the silicone resin layer (14).

In the formula (Y), R ^y each independently represents a hydrogen atom, a hydroxyl group or a hydrolyzable group. Multiple R ^y can have the same contribution or different contributions.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and an amino group. The number of carbon atoms contained in the alkyl group in the alkoxy group is not particularly limited, but is preferably 1 to 3 from the viewpoint of the heat resistance of the silicone resin layer 14 or the peelability of the glass substrate 16. More specifically, examples thereof include a methyl group, an ethyl group, and a propyl group.

The compound represented by the formula (Y) may be a multimer. The upper limit of the n value of the n-dimer is not particularly limited, but is preferably 1500 or less from the viewpoint of ease of synthesis. Among them, n is preferably from 10 to 500 in view of better coating property in forming the silicone resin layer 14, heat resistance of the silicone resin layer 14, or peelability of the glass substrate 16. [

The mixing molar ratio of the silicon compound (X) or a multimer thereof to the silicon compound (Y) or a multimer thereof is not particularly limited, and the silicon resin layer 14 is more excellent in heat resistance and can easily peel off the glass substrate 16 From one point, it is preferable that the molar ratio (D unit / Q unit) of the D unit and the Q unit contained in the silicone resin in the silicone resin layer 14 is adjusted to achieve the above-mentioned range.

As the curable compound for obtaining the condensate polymer, the silicon compound (X) represented by the formula (X) or a mixture thereof and the silicon compound (Y) represented by the formula (Y) or a mixture thereof is used.

As the curable compound, a partial condensate of a silicon compound (X) represented by the formula (X) or a multimer thereof and a silicon compound (Y) represented by the formula (Y) have.

The method of obtaining the partial condensate is not particularly limited and may be a method of hydrolyzing the silicon compound (X) represented by the formula (X) or a mass thereof and the silicon compound (Y) represented by the formula (Y) - Condensation reaction (so-called sol-gel reaction) can proceed to proceed.

In addition, the hydrolysis-condensation reaction may be carried out in the absence of a catalyst or under a catalyst (for example, an acid or a base). For example, the silicon compound (X) and the silicon compound (Y) are mixed and stirred under air to hydrolyze and condense the water in the air as a catalyst to obtain a desired partial condensate.

The reaction of the silicon compound (X) represented by the formula (X) or the oligomer thereof with the silicon compound (Y) represented by the formula (Y) or a multimer thereof may be carried out under a solvent or under no solvent. The type of the solvent to be used is not particularly limited and a known solvent (for example, an alcohol solvent or a hydrocarbon solvent) can be used.

The production conditions of the silicone resin layer 14 using the curable compound will be described later in detail.

When the silicon resin layer 14 is formed, for example, the silicon compound (X) represented by the formula (X) or a multimer thereof and the silicon compound (Y) represented by the formula (Y) The silicone resin layer 14 may be formed by applying a sieve on the base material (for example, a support substrate) to advance the hydrolysis-condensation reaction on the base material. After the partial condensate of the mixture is prepared, (For example, a supporting substrate) of the silicon resin layer 14 to form the silicone resin layer 14.

[Glass laminate and manufacturing method thereof]

The glass laminate 10 of the present invention is a laminate in which the supporting substrate 12, the glass substrate 16 and the silicon resin layer 14 are present as described above.

The method for producing the glass laminate 10 of the present invention is not particularly limited. However, in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), the silicon resin layer 14 is formed on the surface of the support substrate 12 Is preferable. The curable compound is coated on the surface of the supporting substrate 12 and cured to form a silicone resin layer 14 on the surface of the supporting substrate 12. Subsequently, (16) are laminated to form the glass laminate (10).

It is considered that when the curable compound is cured on the surface of the supporting substrate 12, the curing compound is bonded by the interaction with the surface of the supporting substrate 12 during the curing reaction, and the peeling strength of the surface of the silicon resin and the supporting substrate 12 is increased. Therefore, even when the glass substrate 16 and the supporting substrate 12 include the same material, the peeling strength between the silicon resin layer 14 and the both can be made different.

The step of forming the layer of the curable compound on the surface of the supporting substrate 12 and forming the silicon resin layer 14 on the surface of the supporting substrate 12 is hereinafter referred to as a resin layer forming step, And the glass substrate 16 is laminated to form the glass laminate 10 is referred to as a lamination process, and the procedure of each process will be described in detail.

(Resin layer forming step)

In the resin layer forming step, the layer of the curable compound is formed on the surface of the supporting substrate 12, and the silicon resin layer 14 is formed on the surface of the supporting substrate 12. [

In order to form a layer of the curable compound on the supporting substrate 12, a coating composition obtained by dissolving a curable compound in a solvent is used, the composition is coated on the supporting substrate 12 to form a layer of the solution, It is preferable to remove the solvent to form a layer of the curable compound. The thickness of the layer can be controlled by adjusting the concentration of the curable compound in the composition.

The solvent is not particularly limited as long as it is a solvent capable of easily dissolving the crosslinked product in a working environment and capable of easily removing volatilization. Specific examples thereof include toluene, xylene, THF, chloroform, and the like.

The method of applying the curable compound on the surface of the support substrate 12 is not particularly limited, and a 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 and a gravure coating method.

Subsequently, the curable compound on the supporting substrate 12 is cured to form the silicone resin layer 14. [ More specifically, as shown in Fig. 2A, the silicon resin layer 14 is formed on the surface of at least one surface of the supporting substrate 12 in this step.

The method of curing is not particularly limited, but is usually performed by a heat curing treatment.

The temperature condition for thermally curing is not particularly limited within a range in which the heat resistance of the silicone resin layer 14 is improved and the peeling strength (y) after lamination with the glass substrate 16 can be controlled as described above, And more preferably 350 to 450 ° C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes. If the temperature is too low, the heat resistance and the flatness of the silicon resin layer 14 decrease. On the other hand, if the temperature is too high, the peeling strength y becomes too low, May be weakened.

In the heat curing treatment, it is preferable to perform pre-curing (pre-curing) and then curing (final curing) and curing. By performing the pre-curing, the silicone resin layer 14 having excellent heat resistance can be obtained. It is preferable to perform the precure after the removal of the solvent. In this case, the step of forming the layer of the curable compound by removing the solvent from the layer and the step of performing the precure are not particularly distinguished. The removal of the solvent is preferably performed by heating to 100 DEG C or higher, and the precure can be continuously performed by heating to 150 DEG C or higher. The temperature and the heating time for removing the solvent and precuring are preferably 100 to 420 DEG C and 5 to 60 minutes, more preferably 150 to 300 DEG C for 10 to 30 minutes. When the temperature is lower than 420 DEG C, a silicone resin layer which is easy to peel off is obtained.

(Lamination step)

In the laminating step, the glass substrate 16 is laminated on the silicon resin surface of the silicon resin layer 14 obtained in the resin layer forming step, and the layer of the supporting substrate 12, the silicon resin layer 14, And a layer of a glass laminate 10 in this order. More specifically, as shown in Fig. 2 (B), the surface 14a of the silicon resin layer 14 opposite to the supporting base 12 side and the first main surface 16a and the second main surface 16b The silicon resin layer 14 and the glass substrate 16 are laminated with the first main surface 16a of the glass substrate 16 having the first main surface 16a as a lamination surface to obtain the glass laminate 10. [

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

For example, a method of superimposing the glass substrate 16 on the surface of the silicon resin layer 14 under an atmospheric pressure environment. If necessary, the glass substrate 16 may be placed on the surface of the silicon resin layer 14, and then the glass substrate 16 may be pressed onto the silicon resin layer 14 using a roll or press. The bubbles mixed in between the silicone resin layer 14 and the glass substrate 16 are relatively easily removed by pressing by roll or press.

The vacuum lamination method or the vacuum press method is more preferable because it suppresses mixing of bubbles and secures good adhesion. The bubbles do not grow due to heating even when minute bubbles remain, and it is difficult to cause strain defects of the glass substrate 16.

When the glass substrate 16 is laminated, it is preferable that the surface of the glass substrate 16 contacting the silicon resin layer 14 is sufficiently cleaned and laminated in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 16 is.

Further, after the glass substrate 16 is laminated, a pre-annealing treatment (heat treatment) may be carried out if necessary. The adhesion to the silicon resin layer 14 of the laminated glass substrate 16 is improved and the appropriate peeling strength y can be obtained by performing the pre-annealing process, The positional deviation of the member is less likely to occur, and the productivity of the electronic device is improved.

Optimum conditions are appropriately selected according to the type of the silicon resin layer 14 to be used, but the peel strength (y) between the glass substrate 16 and the silicon resin layer 14 is more suitable It is preferable to carry out the heat treatment at 300 占 폚 or higher (preferably 300 to 400 占 폚) for 5 minutes or longer (preferably 5 to 30 minutes).

The formation of the silicone resin layer 14 having a difference in peel strength against the first principal surface of the glass substrate 16 and peel strength against the first principal surface of the supporting substrate 12 is not limited to the above method.

For example, when the support base material 12 having a higher adhesion to the surface of the silicon resin layer 14 than the glass substrate 16 is used, the curable compound is cured on a certain peelable surface to produce a film of a silicone resin , And the film can be laminated at the same time with the glass substrate 16 and the supporting substrate 12 interposed therebetween.

When the adhesion of the curable compound by curing is sufficiently low with respect to the glass substrate 16 and the adhesiveness thereof is sufficiently high with respect to the supporting substrate 12, the adhesion between the glass substrate 16 and the supporting substrate 12 The silicone resin layer 14 can be formed by curing the curable compound.

Even in the case where the supporting substrate 12 includes the same glass material as that of the glass substrate 16, the adhesion of the surface of the supporting substrate 12 is enhanced to increase the peeling strength with respect to the silicon resin layer 14 It is possible. For example, physical methods to increase the surface activity such as chemical (primer treatment) or frame (flame) treatment to improve chemical fixation such as silane coupling agent, increase the surface roughness by sandblast treatment, And a mechanical treatment method for imparting a mechanical strength.

(Glass laminate)

The glass laminate 10 according to the first embodiment of the present invention can be used for various purposes. For example, the glass laminate 10 can be used as a display panel, a PV, a thin film secondary battery, a semiconductor wafer And the like. Further, in the intended use, the glass laminate 10 is often exposed (for example, 1 hour or more) under high temperature conditions (for example, 450 DEG C or more).

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

≪ Second Embodiment >

3 is a schematic cross-sectional view of a second embodiment of the glass laminate according to the present invention.

As shown in Fig. 3, the glass laminate 100 is a laminate in which the layer of the supporting substrate 12, the layer of the glass substrate 16, and the silicon resin layer 14 are present therebetween.

In the glass laminate 100 shown in Fig. 3, unlike the glass laminate 10 shown in Fig. 1 described above, the silicon resin layer 14 is fixed on the glass substrate 16, The substrate 20 is peelably laminated (tightly adhered) on the supporting substrate 12 such that the silicon resin layer 14 in the glass substrate 20 with the resin layer directly contacts the supporting substrate 12. [ In the present invention, the peeling strength (i.e., the stress required for peeling) differs between the fixation and the peelable adhesion, and the fixation means that the peel strength is high with respect to adhesion. That is, in the glass laminate 100, the peel strength at the interface between the silicon resin layer 14 and the glass substrate 16 is higher than the peel strength at the interface between the silicon resin layer 14 and the support base 12.

More specifically, the interface between the glass substrate 16 and the silicon resin layer 14 has a peeling strength z and the peeling strength z is greater than the peeling strength z at the interface between the glass substrate 16 and the silicon resin layer 14 When the stress in the peeling direction is applied, the interface between the glass substrate 16 and the silicon resin layer 14 is peeled off. The interface between the silicone resin layer 14 and the supporting substrate 12 has a peeling strength w and a stress in the peeling direction exceeding the peeling strength w is applied to the interface between the silicon resin layer 14 and the supporting substrate 12 The interface between the silicon resin layer 14 and the supporting substrate 12 is peeled off.

In the glass laminate 100, the peel strength z is higher than the peel strength w. The glass laminate 100 of the present invention is formed by stacking the silicon resin layer 14 and the support base material 12 (the glass base material 12) ) And separated into the glass substrate 20 and the supporting substrate 12 with the resin layer.

The peel strength z is preferably sufficiently high as compared with the peel strength w. Raising the peel strength z means that the adhesion force of the silicone resin layer 14 to the glass substrate 16 is increased and a relatively high adhesion force to the support substrate 12 can be maintained after the heat treatment .

Examples of a method for increasing the adhesion of the silicone resin layer 14 to the glass substrate 16 include a method of increasing the adhesion of the silicone resin layer 14 to the support substrate 12, A method of forming the silicon resin layer 14 on the substrate 16, and the like. The silicone resin layer 14 bonded to the glass substrate 16 with a high bonding force can be formed by the adhesive force at the time of curing.

On the other hand, the bonding force of the silicone resin layer 14 after curing with respect to the supporting substrate 12 is generally lower than the bonding force generated at the time of forming. The glass laminate 100 satisfying the desired peeling relationship can be obtained by forming the silicon resin layer 14 on the glass substrate 16 and then laminating the supporting substrate 12 on the surface of the silicon resin layer 14. [ Can be produced.

Each of the layers (the supporting substrate 12, the glass substrate 16, and the silicone resin layer 14) constituting the glass laminate 100 agrees with each layer constituting the above-described glass laminate 10, The description is omitted.

The surface roughness Ra of the surface of the silicon resin layer 14 on the side of the supporting substrate 12 is not particularly limited, but is preferably 0.1 to 20 nm, more preferably 0.1 to 10 nm, in view of better lamination and releasability of the glass substrate Is more preferable.

The measurement of the surface roughness Ra is performed in accordance with JIS B 0601-2001.

The water contact angle of the surface of the silicone resin layer 14 on the side of the supporting substrate 12 is not particularly limited, but is preferably 70 degrees or more and 105 degrees or less from the viewpoint of better lamination and releasability of the glass substrate.

As a method of measuring the water contact angle, a water contact angle is measured by placing 1 mu L of water droplet on the surface of one glass plate using a contact angle meter (DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2 manufactured by Krus).

The method for producing the glass laminate 100 is not particularly limited, but the glass substrate 16 may be used instead of the supporting substrate 12 in the above-described method for producing the glass laminate 10, , The desired glass laminate 100 can be manufactured. More specifically, the glass laminate 100 can be manufactured by forming the silicone resin layer 14 on the glass substrate 16 and then laminating the supporting substrate 12 on the silicon resin layer 14. [

(Modification of Second Embodiment)

As a modification of the second embodiment of the glass laminate, there is a form in which the layer of the supporting substrate is a laminated supporting substrate comprising a layer of the supporting glass plate and a second silicon resin layer disposed on the layer of the supporting glass plate.

4, unlike the glass laminate 100 shown in Fig. 3 described above, the laminated supporting substrate 120 is divided into the supporting glass plate 30 and the supporting glass plate And a second silicon resin layer (32) disposed on the second silicon resin layer (30). Here, in the modified example of the second embodiment, the silicon resin layer on the glass substrate side is referred to as a first silicon resin layer, and the silicon resin layer on the support glass plate side is referred to as a second silicon resin layer. The silicone resin in the second silicone resin layer 32 can be cured by curing the curable organopolysiloxane containing the siloxane unit (A) represented by the formula (1) and the siloxane unit (B) represented by the formula (2) Water. The first silicon resin layer 14 is disposed in direct contact with the second silicon resin layer 32 in the glass laminate 200 and the glass substrate 20 with the resin layer is disposed in contact with the second silicon resin layer 32, (Adhered) to each other in a peelable manner.

By forming the second silicon resin layer 32 in the glass laminate body 200, the heat resistance of the glass laminate itself is increased, and the glass substrate is easily peeled off even after the high-temperature heat treatment, and the laminate property of the glass substrate is also excellent In particular, good lamination properties are obtained even when the surface roughness of both (or both) on the lamination surface of the first silicone resin layer and the second silicone resin layer is rough).

As described above, the second silicon resin layer 32 is fixed on the support glass plate 30 on one surface, and is peelably adhered to the first silicone resin layer 14 on the other surface. The peel strength v of the interface between the second silicon resin layer 32 and the supporting glass plate 30 is larger than the peeling strength w of the interface between the second silicon resin layer 32 and the first silicon resin layer 14. [ . As described above, the peel strength z of the interface between the first silicon resin layer 14 and the glass substrate 16 is the same as the peel strength z of the interface between the first silicon resin layer 14 and the laminated support substrate 120 (The interface between the first silicone resin layer 14 and the second silicone resin layer 32).

Therefore, when a stress in the direction in which the support glass plate 30 and the glass substrate 16 are separated from each other is applied to the glass laminate 200, the glass laminate 200 is separated from the first silicone resin layer 14, And is separated at the interface of the glass substrate 32 and the glass substrate 20 with the resin layer.

The second silicone resin layer 32 is bonded to the surface of the supporting glass plate 30 with a strong bonding force such as an adhesive force or an adhesive force. For example, as described later, the curable organopolysiloxane is cured on the surface of the support glass plate 30, so that a silicone resin as a cured product is adhered to the surface of the support glass plate 30 to obtain a high bonding force. The surface of the support glass plate 30 and the second silicon resin layer 32 are subjected to a treatment (for example, a treatment using a coupling agent) that generates a strong bonding force between the surface of the support glass plate 30 and the second silicon resin layer 32, The bonding force between the paper layers 32 can be increased.

On the other hand, the bonding force of the second silicone resin layer 32 including the curable organopolysiloxane to the silicone resin layer 14 is generally lower than the bonding force generated at the time of curing. Thus, the second silicone resin layer 32 is formed by curing the curable organopolysiloxane on the support glass plate 30, and then the second silicone resin layer 32 and the first silicone resin layer 14 are opposed to each other The desired glass laminate body 200 can be manufactured by laminating the glass substrate 20 with the resin layer on the surface of the second silicon resin layer 32. [

In some cases, the surface of the second silicone resin layer 32 before lamination or the surface of the first silicone resin layer 14 before lamination may be subjected to a treatment for weakening the bonding force therebetween and laminated. The bonding strength between the interface of the second silicone resin layer 32 and the first silicone resin layer 14 can be weakened and the peeling strength w can be lowered have.

The glass laminate body 200 shown in Fig. 4 has the same structure as the glass laminate body 100 shown in Fig. 3, except that it has the laminated supporting substrate 120, The description thereof will be omitted and the laminated support base material 120 will be mainly described.

The laminated support substrate 120 includes a support glass plate 30 and a second silicon resin layer 32.

The support glass plate 30 corresponds to the case where the support base 12 is a glass plate, and its fit is as described above.

The silicone resin in the second silicone resin layer 32 preferably contains a cured organopolysiloxane curing agent. In particular, the siloxane unit (A) represented by the formula (1) and the siloxane unit represented by the formula (2) Is preferably a cured product of the curable organopolysiloxane containing the unit (B).

Hereinafter, the form of the curable organopolysiloxane and its cured product will be described in detail.

(Curable organopolysiloxane and its cured product)

As the curable organopolysiloxane for obtaining the silicone resin in the second silicone resin layer 32, the siloxane unit (A) represented by the following formula (1) and the siloxane unit (B) represented by the formula (2) Curable organopolysiloxanes are preferred.

The basic constituent unit of organopolysiloxane is usually a bifunctional siloxane unit classified into a number of monovalent organic groups represented by methyl groups and phenyl groups bonded to silicon atoms and having two organic groups called D units shown below, , A trifunctional siloxane unit bonded with one organic group called a unit, a monofunctional siloxane unit bonded with three organic groups called M unit, and a tetrafunctional siloxane unit having no organic group called Q unit. The Q unit is a unit which does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as a siloxane unit. In the following formulas, R represents a monovalent organic group represented by a methyl group or a phenyl group.

In the siloxane unit, the siloxane bond is regarded as one half of the silicon atoms per silicon atom in the siloxane bond in that two silicon atoms are bonded through one oxygen atom, and O < _1/2 &_gt; Is expressed. More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to another silicon atom, so that the formula is -O _1/2 - (R) ₂ Si-O _1/2 -. O _1/2 is in that there are two D units will normally be expressed as _{(R) 2 SiO 2/2} . However, in the present invention, M units, D units, T units, and Q units are expressed using O _1/2 expressions for individual oxygen atoms in accordance with the A unit expression described below.

When the terminal unit of the polymer chain is a unit other than the M unit, the atoms other than the silicon atom bonded to O < _1/2 > of the terminal unit are 1/2 oxygen atoms, Oxygen atom in the group or the alkoxy group. In the same manner as the expression of the siloxane units described below, for example, the hydroxyl group bonded to the silicon atom of the terminal unit is -O _1/2 -H.

In the siloxane unit (A) to be described later, each of two silicon atoms is bonded to an oxygen atom, and each oxygen atom is bonded to a silicon atom other than the unit, so that it is expressed as O _{1/2 in the} formula (1). The siloxane unit (A) can be regarded as a D unit in terms of bifunctionality. The siloxane unit (B) described later can also be regarded as a D unit for the same reason. Hereinafter, the siloxane unit (A) and the siloxane unit (B) in the present invention are regarded as one kind of D unit, and the curable organopolysiloxane is explained.

Each of R ¹ to R ⁴ in the formula (1) independently represents an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent. Specific examples of the alkyl group having 4 or less carbon atoms include a methyl group, an ethyl group, a vinyl group, an allyl group, and an ethynyl group.

Examples of the phenyl group which may have a substituent include a methyl group, an ethyl group, a vinyl group, an allyl group and an ethynyl group.

The above-mentioned R ¹ to R ⁴ are preferably a methyl group or a phenyl group in that decomposition of the silicone resin under high-temperature treatment conditions is further suppressed.

In the formula (1), Ar represents a phenylene group which may have a substituent. The phenylene group is preferred because it is excellent in adhesion to the first silicone resin layer 14 and peelability.

Examples of the substituent include, but are not limited to, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, an arylalkyl group, an aryloxy group, a heterocyclic group, an amino group, a nitro group and a cyano group .

The curable organopolysiloxane is a polymer containing only a siloxane unit (A) and a siloxane unit (B) as a siloxane unit or a copolymer containing a siloxane unit (A) and a siloxane unit (B) and other siloxane units. The curable organopolysiloxane is preferably a linear polymer, and the other siloxane unit is preferably a D unit other than the siloxane unit (A) or the siloxane unit (B). When the curable organopolysiloxane is a linear polymer, the curable organopolysiloxane is a polymer comprising only a siloxane unit (A) and a siloxane unit (B), a polymer comprising a siloxane unit (A) and a siloxane unit (B) , Polymers containing siloxane units (A), siloxane units (B) and M units, polymers containing siloxane units (A) and siloxane units (B) and other D units and M units. However, the siloxane unit (A), the siloxane unit (B), the other D unit, and the M unit may each be present in two or more species.

The curable organopolysiloxane may also be a nonlinear polymer having a small number of branches. In this case, D units in the linear polymer or M units in some cases are further provided, except that the T unit or the Q unit resulting in branching is a prime number.

In the siloxane unit (B) represented by the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 4 or less carbon atoms or an alkenyl group having 3 or less carbon atoms. Provided that at least a part of the siloxane unit (B) is a siloxane unit in which at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms.

R ⁵ and R ⁶ are preferably a methyl group or a vinyl group in that degradation of the silicone resin under high temperature treatment conditions is further suppressed.

As a preferred form of the siloxane unit (B), the siloxane unit (B) is a siloxane unit in which R ⁵ and R ⁶ (B-1), which is an alkyl group having 4 or less carbon atoms, and a siloxane unit (B-1) which is an alkyl group having 4 or less carbon atoms in both of R ⁵ and R ⁶ , in the case where the alkenyl group is other than the corresponding alkenyl group. 2), and the siloxane unit (B) in the curable organopolysiloxane contains only the siloxane unit (B-1) or contains the siloxane unit (B-1) and the siloxane unit (B-2) .

At least one of R ⁵ and R ⁶ in the siloxane unit (B-1) is an alkenyl group having 3 or less carbon atoms, preferably a vinyl group. When R ⁵ and R ⁶ are other than an alkenyl group, the alkyl group is not more than 4 carbon atoms, and preferably a methyl group.

The preferred form of the siloxane unit (B-1) is a form in which one of R ⁵ and R ⁶ is a methyl group and the other is a vinyl group in that decomposition of the silicone resin under high temperature treatment conditions is further suppressed have.

In the siloxane unit (B-2), both of R ⁵ and R ⁶ are alkyl groups having not more than 4 carbon atoms, preferably a methyl group.

When the siloxane unit (B) contains the siloxane unit (B-1) and the siloxane unit (B-2), the ratio of the siloxane unit (B- 1)] / [siloxane unit (B-1) + siloxane unit (B-2)]] is not particularly limited, but the curing in the curable organopolysiloxane is further progressed, Is preferably from 30 to 80 mol%, more preferably from 40 to 60 mol%, from the viewpoint that the adhesion and releasability of the second silicone resin layer (32) to the first silicone resin layer (14) Do.

In addition, the curable organopolysiloxane may contain siloxane units (for example, M units, T units and Q units) other than the above-mentioned siloxane unit (A) and siloxane unit (B). However, if there are many units having branches (T units or Q units), the flexibility of the cured product (silicone resin) is lowered, and if a large number of M units are present, a polymer having a low number average molecular weight becomes a polymer, There is a concern. Therefore, as described later, the content of units other than D units (siloxane unit (A) and siloxane unit (B)) is preferably 0 to 20 mol%, more preferably 0 to 5 mol % Is more preferable.

When the siloxane unit (A) and the siloxane unit (B) are contained as the curable organopolysiloxane, the flexibility is high and the adhesion of the second silicone resin layer 32 to the first silicone resin layer 14 is good. In addition, the curability is improved and decomposition of the cured product (silicone resin) under high temperature treatment conditions is further suppressed.

The ratio of the siloxane unit (A) to the total of the siloxane unit (A) and the siloxane unit (B) in the curable organopolysiloxane is such that the decomposition of the silicone resin under high temperature treatment conditions is further suppressed, Is preferably 10 to 90 mol%, more preferably 30 to 90 mol%, still more preferably 40 to 60 mol% in view of better adhesion and peelability to the first silicone resin layer (14) Do.

In addition, the ratio of the sum of the siloxane unit (A) and the siloxane unit (B) to the total siloxane units in the curable organopolysiloxane is such that the decomposition of the silicone resin under the high temperature treatment condition is further suppressed and the second silicone resin layer 32 Is preferably from 80 to 100 mol%, more preferably from 95 to 100 mol%, from the viewpoint of better adhesion to the first silicone resin layer (14) and peelability.

The bonding type of the siloxane unit (A) and the siloxane unit (B) in the curable organopolysiloxane is not particularly limited, and may be, for example, a random copolymer, a block copolymer, or an alternating copolymer. Among them, an alternating copolymer is preferable in that decomposition of the silicone resin under high-temperature treatment conditions is further suppressed.

In the present invention, the alternating copolymer of the siloxane unit (A) and the siloxane unit (B) means that the combination of the siloxane unit (A) and the siloxane unit (B) (B) and the siloxane unit (B). The combination of these three species can be distinguished, for example, by ¹ H NMR measurement and ²⁹ Si NMR measurement, and by the measurement, the ratio of the relative number of these bonds can be calculated. The alternating copolymer of the siloxane unit (A) and the siloxane unit (B) in the present invention may contain a small number of random bonding portions or block bonding portions. The ratio of the siloxane unit (A) to the siloxane unit (B) in the alternating copolymer is preferably from 80 to 100 mol%, more preferably from 90 to 100 mol% based on the total of the three kinds of bonds, And more preferably 95 to 100 mol%. In the case where the curable organopolysiloxane of the present invention is an alternating copolymer, the siloxane unit (A) and the siloxane unit (B) in the alternate copolymer are not distinguished from each other in terms of the total amount of the siloxane unit The ratio of the unit (A) is preferably 50 ± 5 mol%.

The alternating copolymer in the present invention may be one kind of silicone resin, or two or more kinds of silicone resins may be mixed so that the ratio of the bonding of the siloxane unit (A) to the siloxane unit (B) becomes the above preferable ratio .

The number average molecular weight of the curable organopolysiloxane is not particularly limited, but it is excellent in handleability, and also has excellent film forming properties and further suppresses decomposition of the silicone resin under high temperature treatment conditions. Thus, the gel permeation chromatography (GPC) The number average molecular weight in terms of polystyrene is preferably 5,000 to 30,000, more preferably 5,000 to 15,000.

The number average molecular weight of the curable organopolysiloxane can be controlled by controlling the reaction conditions. For example, the molecular weight can be controlled by changing the end group amount, type, and monomer mixture ratio. When the amount of the terminal group is increased, a low molecular weight material is obtained, while when the amount is decreased, a high molecular weight material is obtained. When the monomer ratio is shifted, a low molecular weight material is obtained, and when the ratio is made equal, a high molecular weight material is obtained.

The method for producing the curable organopolysiloxane containing the siloxane unit (A) represented by the above-mentioned formula (1) and the siloxane unit (B) represented by the formula (2) is not particularly limited. For example, by polymerizing a silane compound represented by the formula (3) and a silane compound represented by the formula (4) by a condensation reaction or a hydrolysis-condensation reaction. The curable organopolysiloxane having another siloxane unit can also be prepared by using a silanol compound or a silane compound having at least one hydrolyzable group. The polymerization reaction is usually carried out in an inert solvent, and the reaction can be carried out only by heating in the absence of a catalyst. A reaction catalyst may be used if necessary.

The production method of the curable organopolysiloxane is basically known, and is described in, for example, Japanese Patent Application Laid-Open Nos. 9-59387 and 2008-280402. The curable organopolysiloxane and its production method in the present invention may be those described in these known documents.

Formula (3) and (4) of, R ¹ to R ⁶ is R ¹ to R ⁶ and copper in the formula (1) and (2).

In the formula (3), X and Y each independently represent a hydroxyl group or a hydrolysable group (for example, an amino group, a halogen group, an alkoxy group or the like of a primary to tertiary amino group such as an amino group, a monoalkylamino group or a dialkylamino group).

The alternating copolymer can be obtained by polymerizing two kinds of monomers having different reactivity. For example, the ratio X of the polymerization reactive group of the silane compound represented by the formula (3) to be the siloxane unit (A) and the Y of the polymerization reactive group of the silane compound represented by the formula (4) serving as the siloxane unit (B) Is selected to be higher than the reactivity between X and the reactivity between Y, and the alternating copolymer is produced by reacting substantially equimolar amounts of the two silane compounds. When the reactivity of X and Y is higher than that of reactivity between X and Y, reactivity of X and Y is higher than that of reactivity between X and Y, whereby an alternating copolymer with less random bonding portion or less block bonding portion is obtained.

When an alternate copolymer is produced, it is preferable that one of X and Y is a hydroxyl group and the other is a primary to tertiary amino group such as an amino group, a monoalkylamino group, and a dialkylamino group. In particular, it is preferable that one is a hydroxyl group and the other is a dialkylamino group, more preferably X is a hydroxyl group and Y is a dialkylamino group. The alkyl group in the monoalkylamino group or dialkylamino group is preferably an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.

Alternating copolymers of organopolysiloxanes and their preparation are basically known and are described, for example, in Macromolecules 1998, 31, 8501 or Journal of Applied Polymer Science, Vol. 106, 1007, 2007 describes alternating copolymers of organopolysiloxanes and their preparation. The alternate copolymer in the present invention and the production method thereof may be those described in these known documents.

Specific examples of the preparation method include an organic solvent solution of a silane compound (X is a hydroxyl group) represented by the formula (3) and a silane compound (Y is a dimethylamino group) represented by the formula (4) A method in which the two silane compounds are mixed at a ratio equivalent to an equimolar amount and reacted while heating and stirring; and a method in which the other organic solvent solution is dividedly or continuously added to one of the organic solvent solutions under heating and stirring, Coalescence can be produced.

The curable organopolysiloxane cures through a predetermined curing reaction and becomes a cured product which is a silicone resin. The type of curing (crosslinking) is not particularly limited, and a well-known type can be adopted depending on the kind of the curable group contained in the curable organopolysiloxane. For example, a hydrosilylation reaction, condensation reaction or heat treatment of a silanol group, high energy ray treatment, or radical reaction with a radical polymerization initiator.

More specifically, when the curable organopolysiloxane has a radical reactive group such as an alkenyl group or an alkynyl group, the radical reactive group through the radical reaction is crosslinked by a reaction between them to form a cured product (silicone resin).

When the curable organopolysiloxane has a silanol group, the silanol groups are crosslinked by a condensation reaction to form a cured product.

In addition, when the curable organopolysiloxane has an alkenyl group or a hydrogen atom bonded to a silicon atom, it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum catalyst) to form a cured product.

Among these curing types, a radical reaction type is preferable in that generation of by-products due to the reaction is suppressed, and a more densified and highly heat-resistant silicone resin can be obtained.

At the time of the curing reaction, two or more types of curable organopolysiloxanes containing a siloxane unit (A) represented by the formula (1) and a siloxane unit (B) represented by the formula (2) Other curing organopolysiloxanes other than the curable organopolysiloxane containing the siloxane unit (A) represented by the formula (1) and the siloxane unit (B) represented by the formula (2) may be used in combination.

Further, the curing of the curable organopolysiloxane to form a cured silicone resin is hereinafter simply referred to as curing of the curable organopolysiloxane.

(Manufacturing Method of Second Silicon Resin Layer 32)

The method of producing the second silicone resin layer 32 is not particularly limited. However, when the curable organopolysiloxane is cured on the surface of the support glass plate 30 as described above, the interaction with the surface of the support glass plate 30 during the curing reaction And the peel strength between the surface of the second silicon resin layer 32 and the surface of the support glass plate 30 is considered to be high.

Hereinafter, with respect to the procedure of the step of forming the layer of the curable organopolysiloxane on the surface of the support glass plate 30 and forming the second silicone resin layer 32 by curing the curable organopolysiloxane on the surface of the support glass plate 30 Will be described in detail.

In this step, a layer of a curable organopolysiloxane is formed on the surface of the support glass plate 30, and a second silicone resin layer 32 is formed by curing the curable organopolysiloxane on the surface of the support glass plate 30.

In order to form a layer of the curable organopolysiloxane on the supporting glass plate 30, a coating composition in which a curable organopolysiloxane is dissolved in a solvent is used, and this composition is coated on a supporting glass plate 30 to form a layer of a solution And then the solvent is removed to form a curable organopolysiloxane layer. The thickness of the layer of the curable organopolysiloxane can be controlled by adjusting the concentration of the curable organopolysiloxane in the composition.

The solvent is not particularly limited as long as it is a solvent capable of easily dissolving the curable organopolysiloxane in the working environment and easily removing volatilization. Specific examples thereof include toluene, xylene, THF, chloroform, and the like.

The method of applying the composition containing the curable organopolysiloxane on the surface of the support glass plate 30 is not particularly limited and a 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 and a gravure coating method.

Subsequently, the curable organopolysiloxane on the support glass plate 30 is cured to form the second silicone resin layer 32. [

The method of curing is appropriately selected in accordance with the curing type (crosslinking type) of the curable organopolysiloxane as described above. Particularly, when the curable organopolysiloxane has a radically polymerizable group, the second silicone resin layer 32 is produced by thermal curing because a silicone resin excellent in adhesion and heat resistance to the first silicone resin layer 14 can be obtained . Hereinafter, the form of thermosetting will be described in detail.

The temperature condition for thermally curing the curable organopolysiloxane is such that the heat resistance of the second silicone resin layer 32 is improved and the peeling strength after lamination with the second silicone resin layer 32 is specifically restricted within the range But is preferably 300 to 475 DEG C, more preferably 350 to 450 DEG C. [ The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes.

It is also preferable that the curable organopolysiloxane is cured by performing pre-curing (pre-curing) and then curing (final curing). The second silicone resin layer 32 having excellent heat resistance can be obtained by performing the pre-curing. The pre-cure is preferably carried out subsequent to the removal of the solvent. In this case, the step of forming the layer of the curable organopolysiloxane by removing the solvent from the layer and the step of performing the precure are not particularly distinguished. The removal of the solvent is preferably performed by heating to 100 DEG C or higher, and the precure can be continuously performed by heating to 150 DEG C or higher. The temperature and the heating time for removing the solvent and precuring are preferably 100 to 420 DEG C and 5 to 60 minutes, more preferably 150 to 300 DEG C for 10 to 30 minutes. When the temperature is lower than 420 DEG C, the second silicone resin layer 32 is easily peeled off.

[Glass substrate with member and method of manufacturing the same]

In the present invention, the above-described glass laminate (glass laminate (10), glass laminate (100), or glass laminate (200)) can be used to manufacture an electronic device.

Hereinafter, the mode using the above-described glass laminate 10 will be described in detail.

By using the glass laminate 10, a glass substrate (a glass substrate with a member for an electronic device) containing a glass substrate and a member for an electronic device is manufactured.

The method of manufacturing the glass substrate with the member is not particularly limited. However, from the point of view of the excellent productivity of the electronic device, the electronic device member is formed on the glass substrate in the glass laminate, It is preferable that the glass substrate side of the silicon resin layer is peeled off from the obtained laminated body for electronic devices to separate the glass substrate with the member and the supporting substrate with resin layer.

Hereinafter, the step of forming the electronic device member on the glass substrate in the glass laminate to produce the laminated body for the electronic device is referred to as a member forming step, a step of forming a glass substrate side interface of the silicon resin layer The step of separating the glass substrate with the member into the supporting substrate with the resin layer is referred to as a separation step.

Hereinafter, materials and procedures used in each step will be described in detail.

(Member forming process)

The member forming step is a step of forming an electronic device member on the glass substrate 16 in the glass laminate 10 obtained in the laminating step. More specifically, as shown in Fig. 2C, the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16, (24).

First, the electronic device member 22 used in the present step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Member for electronic device (functional element))

The member 22 for the electronic device is a member formed on the glass substrate 16 in the glass laminate 10 and constituting at least a part of the electronic device. More specifically, the electronic device member 22 may be a member used for a display device panel, a solar cell, a thin-film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, Member for a battery, member for a thin film secondary battery, circuit for an electronic part).

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

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

As a circuit for an electronic component, a metal of a conductive part, a silicon oxide of an insulating part and silicon nitride can be cited in a CCD or a CMOS. In addition, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board, And the like.

(Process procedure)

The method of manufacturing the laminated body 24 for electronic devices described above is not particularly limited and may be carried out by a conventionally known method depending on the type of the constituent members of the electronic device member, And the member 22 for an electronic device is formed on the surface of the second main surface 16b.

The electronic device member 22 is not limited to all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as "Quot; partial member "). The glass substrate with the partial members peeled off from the silicon resin layer 14 may be made a glass substrate (corresponding to an electronic device described later) with all the members in the subsequent steps.

Further, another electronic device member may be formed on the peeling surface (first main surface 16a) of the glass substrate with the entire member peeled off from the silicon resin layer 14. [ Alternatively, the electronic device may be manufactured by assembling the laminated body having the entire members, and thereafter peeling the supporting substrate 12 from the laminated body with the entire members. Further, it is also possible to manufacture a glass substrate with two glass substrates by assembling two glass substrates with two glass substrates, by peeling the two glass substrates from the entire stacked member .

For example, in the case of manufacturing an OLED, for example, the surface of the glass laminate 10 opposite to the side of the silicon resin layer 14 of the glass substrate 16 (the second main surface 16b of the glass substrate 16) , A hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and the like are deposited on a surface on which a transparent electrode is formed to form an organic EL structure, a back electrode is formed, And various layers such as sealing are formed and processed. Specific examples of such layer formation and treatment include film forming treatment, vapor deposition treatment, and adhesion treatment of a sealing plate.

In the case of manufacturing a TFT-LCD, for example, a TFT-LCD may be manufactured by a general film forming method such as a CVD method and a sputtering method using a resist solution on the second main surface 16b of the glass substrate 16 of the glass laminate 10 A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film to be formed on the glass substrate 16; A CF forming step of forming a color filter CF by use of a pattern and a bonding step of laminating the CF deposited laminate obtained in the TFT deposited laminate and the CF forming step obtained in the TFT forming step.

In the TFT forming step and the CF forming step, TFTs or CFs are formed on the second main surface 16b of the glass substrate 16 by well-known photolithography or etching techniques. At this time, a resist solution is used as the coating liquid for pattern formation.

Further, the second main surface 16b of the glass substrate 16 may be cleaned before forming the TFT or CF, if necessary. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

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

(Separation step)

2 (D), the interface between the silicon resin layer 14 and the glass substrate 16 is peeled off from the laminated body 24 for electronic devices, which is obtained in the member forming step The electronic device member 22 and the glass substrate 16 are separated by the glass substrate 16 (the glass substrate with the member) on which the electronic device member 22 is laminated and the silicon resin layer 14 and the supporting substrate 12, To obtain a glass substrate (26) with a member.

If the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members may be formed on the glass substrate 16 after the detachment.

The method of peeling the glass substrate 26 with the member and the supporting substrate 18 with the resin layer is not particularly limited. Specifically, for example, a sharp blade-like shape may be inserted into the interface between the glass substrate 16 and the silicone resin layer 14, and after a moment of peeling is given, a mixed fluid of water and compressed air may be sprayed have. Preferably, the supporting substrate 12 of the laminated body 24 with the electronic device member is provided on the upper surface side and the electronic device member 22 side is disposed on the lower surface side, (In the case where the supporting base material is laminated on both sides), the blade is first introduced into the interface between the glass substrate 16 and the silicone resin layer 14 in this state. Thereafter, the support substrate 12 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pads are sequentially raised from the vicinity of the position where the blade is inserted. By doing so, an air layer is formed at the interface between the silicon resin layer 14 and the glass substrate 16, and this air layer spreads over the whole surface of the interface, so that the supporting base material 18 with the resin layer can be easily peeled off.

In addition, the resin laminated body 18 with the resin layer can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

When peeling the glass substrate 26 with the member and the supporting base material 18 with the resin layer, it is preferable that the peeling is performed while spraying the release auxiliary agent to the interface between the glass substrate 16 and the silicone resin layer 14. The release aid is intended to be a solvent, such as water, as described above. Examples of the release aid to be used include water, an organic solvent (for example, ethanol), a mixture thereof, and the like.

When separating the glass substrate 26 with the member from the laminated body 24 for electronic devices, the pieces of the silicone resin layer 14 are separated from the glass substrate 26 with the member by controlling the spraying and the humidity by the ionizer, It is possible to further suppress the electrostatic adsorption on the substrate.

The above-described method of manufacturing the glass substrate with the member 26 is suitable for manufacturing a small-sized display device used in a mobile terminal such as a cellular phone or a PDA. The display device is mainly an LCD or an OLED, and examples of the LCD include TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type and the like. It can basically be applied to any of passive drive type and active drive type display devices.

As the member glass substrate 26 manufactured by the above method, there can be used a display panel having a glass substrate and a display device member, a solar cell having a glass substrate and a member for a solar cell, a thin film 2 having a glass substrate and a member for a thin film secondary battery A secondary battery, an electronic component having a glass substrate and a member for an electronic device, and the like. The display panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

Although the embodiment using the glass laminate 10 has been described in detail above, an electronic device may be manufactured according to the same procedure as above using the glass laminate 100 or the glass laminate 200. [

When the glass laminate 100 is used, the supporting substrate 12 and the silicone resin layer 14 are peeled off at the interface between the supporting substrate 12 and the silicone resin layer 14 in the separating step, And is separated into an electronic device including a glass substrate 16 and a member 22 for an electronic device.

Alternatively, in the case of using the glass laminate 200, the laminated support base material 120 and the first and second silicon resin layers 14 and 14 are peeled off at the interface between the laminated support base material 120 and the first silicone resin layer 14 during the separation step, An electronic device including a silicon resin layer 14, a glass substrate 16, and a member 22 for an electronic device.

[Example]

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

(Synthesis Example 1: synthesis of sol-gel A)

7.20 g of tetraethoxysilane was added slowly while stirring a mixture of 0.09 g of nitric acid (61%), 81.78 g of denatured ethanol solmix AP-11 (manufactured by Nippon Alcohol Co., Ltd.) and 11.85 g of pure water at room temperature, 0.40 g of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane was further added dropwise over 1 hour. The resulting mixed solution was stirred for 3 hours while maintaining the temperature at 10 to 20 占 폚 to obtain a desired mixed solution (sol-gel A).

The obtained mixed solution contained a hydrolysis-condensation product (partial condensation polymer) of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane and tetraethoxysilane. Also, the molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane to tetraethoxysilane (molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane / Mole of tetraethoxysilane) was 5:95.

(Synthesis Example 2: synthesis of sol-gel B)

2.60 g of tetraethoxysilane was added slowly while stirring at room temperature with a mixture of 0.09 g of nitric acid (61%), 81.78 g of denatured ethanol solmix AP-11 (manufactured by Nippon Alcohol Co., Ltd.) and 11.85 g of pure water, 1.30 g of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane was further added dropwise over 1 hour. The resulting mixed solution was stirred for 3 hours while maintaining the temperature at 10 to 20 占 폚 to obtain a desired mixed solution (sol-gel B).

The obtained mixed solution contained a hydrolysis-condensation product (partial condensation polymer) of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane and tetraethoxysilane. Also, the molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane to tetraethoxysilane (molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane / Mole of tetraethoxysilane) was 33:67.

(Synthesis Example 3: synthesis of sol-gel C)

3.10 g of tetraethoxysilane was added slowly while stirring at room temperature with a mixture of 0.09 g of nitric acid (61%), 81.78 g of denatured ethanol solmix AP-11 (manufactured by Nippon Alcohol Co., Ltd.) and 11.85 g of pure water, 2.40 g of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane was further added dropwise over 1 hour. The resulting mixed solution was stirred for 3 hours while maintaining the temperature at 10 to 20 占 폚 to obtain a desired mixed solution (sol-gel C).

The obtained mixed solution contained a hydrolysis-condensation product (partial condensation polymer) of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane and tetraethoxysilane. Also, the molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane to tetraethoxysilane (molar ratio of 1,3-dimethoxy-1,1,3,3-tetramethylsiloxane / Mole of tetraethoxysilane) was 43:57.

(Synthesis Example 4: Preparation of liquid material containing curable organopolysiloxane (S1)

1,4-bis (hydroxydimethylsilyl) benzene (35 parts by mass, manufactured by Gelest) was added to toluene (90 parts by mass) in a nitrogen atmosphere. Subsequently, the reaction solution was heated to 110 占 폚 and toluene (40 parts), in which bis (dimethylamino) dimethylsilane (11 mass parts, manufactured by Gelest) and bis (dimethylamino) methylvinylsilane Mass part) solution was added dropwise to the reaction solution over about 5 minutes. Thereafter, the reaction solution was stirred at 110 DEG C for 1 hour. After the completion of the stirring, the reaction solution was naturally cooled to room temperature, and the reaction solution was added to methanol (3250 parts by mass) to perform reprecipitation treatment. Subsequently, the precipitate was recovered and vacuum-dried to obtain a curable organopolysiloxane (S1) which was colorless and transparent and in a liquid state.

The number average molecular weight (in terms of polystyrene) of the curable organopolysiloxane (S1) obtained by GPC (gel permeation chromatography) was 1.2 x 10 ⁴ . Further, the temperature of the curable organopolysiloxane (S1) was elevated from room temperature to 700 ° C at a temperature raising rate of 15 ° C / min and a nitrogen atmosphere (100 ml / min) using a thermogravimetric analyzer (manufactured by T.A. The% weight loss temperature was 535 ° C.

Subsequently, the curable organopolysiloxane (S1) (30 parts by mass) was dissolved in xylene (70 parts by mass) to prepare a liquid material containing the curable organopolysiloxane (S1).

(Example 1)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.5 mm and a linear expansion coefficient of 38 × 10 ^-7 / ° C was prepared as a supporting substrate, To clean the surface. Subsequently, the sol-gel A prepared above was applied on the surface (first main surface) on which the support substrate had been cleaned (first main surface) with a size of 278 mm in the vertical direction and 278 mm in the horizontal direction with a spin coater (coating amount 15g / m ² ). Further, the solution was heated and cured at 350 占 폚 in the air for 30 minutes to form a silicone resin layer having a thickness of 0.2 占 퐉 to obtain a support A.

Subsequently, the releasable surface of the silicone resin layer of the support A and the first main surface of a glass substrate (" AN100 ", manufactured by Asahi Kasei Corporation) having the same size as the silicon resin layer and having a thickness of 0.2 mm were opposed to each other at room temperature , And both substrates were stacked so that the centers of gravity of both substrates were superimposed with a lamination apparatus under atmospheric pressure to obtain a glass laminate S1.

The obtained glass laminate S1 corresponds to the glass laminate 10 of Fig. 1 described above. In the glass laminate S1, the peel strength (x) between the interface of the supporting substrate layer and the silicone resin layer is smaller than the peeling strength Was higher than the peel strength (y) at the interface of the glass substrate.

Then, the following measurements using the obtained glass laminate S1 were carried out. The following evaluation results are summarized in Table 1 to be described later.

[Evaluation of peelability]

A 50 mm square sample was cut out from the glass laminate S1. The sample was placed in a hot air oven heated to 450 DEG C, left for 60 minutes, and then taken out. Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the glass laminate S1 at the interface between the glass substrate and the silicone resin layer at one corner, after the second main surface of the glass laminate S1 of the glass laminate S1 was vacuum- A peeling moment was given between the first main surface of the glass substrate and the peelable surface of the silicon resin layer. The second main surface of the supporting substrate of the glass laminate S1 is adsorbed by a plurality of vacuum adsorption pads at a pitch of 90 mm and then sequentially lifted from the adsorption pads nearer to the corner portions to form the first main surface of the glass substrate and the silicon resin layer The peelable surface was peeled off. It was evaluated whether the glass laminate S1 was peeled off without breakage of the glass substrate or breakage of the silicon resin layer. In addition, the maximum pull-up strength at the time of performing this treatment was measured in N / 25 mm units.

Practically, the peel strength is preferably 10 N / 25 mm or less.

[Heat resistance evaluation]

A 50 mm square sample was cut out from the glass laminate S1. The sample was placed in a hot air oven heated at 450 DEG C, left for 60 minutes, and taken out to evaluate whether or not foaming phenomenon was confirmed in the sample.

[Flatness evaluation]

The average value of the arithmetic mean roughness Ra at five arbitrarily selected points on the surface of the silicon resin layer as the laminated surface of the glass laminate S1 and the surface of the glass substrate was obtained. The arithmetic average roughness Ra is an arithmetic average roughness Ra defined in JIS B 0601-2001 and is obtained by measuring a measurement area of 5 占 퐉 占 5 占 퐉 at each point by an atomic force microscope.

[Measurement of film thickness]

A part of the silicon resin layer was cut and the step difference of the silicon resin layer was measured by using a known touch-sensitive surface shape measuring device to confirm the film thickness of the silicone resin layer.

(Example 2)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.2 mm and a coefficient of linear expansion of 38 × 10 ^-7 / ° C was prepared as a glass substrate, To clean the surface. Subsequently, the sol-gel A was coated on the surface (first main surface) subjected to the cleaning treatment of the glass substrate by a spin coater with a size of 278 mm in length and 278 mm in width (coating amount 15 g / m ² ). Further, it was heated and cured at 350 캜 for 30 minutes in the air to form a 0.2 탆 thick silicone resin layer to obtain a glass substrate B.

Subsequently, the releasable surface of the silicone resin layer of the glass substrate B and the first main surface of a supporting substrate (" AN100 ", manufactured by Asahi Glass Co., Ltd.) having the same size as the silicon resin layer and having a thickness of 0.5 mm were opposed to each other at room temperature Both substrates were superimposed on each other so that the centers of gravity of both substrates were superimposed with a lamination device under atmospheric pressure to obtain a glass laminate S2.

The obtained glass laminate S2 corresponds to the glass laminate 100 shown in Fig. 3, and in the glass laminate S2, the peel strength (z) at the interface between the glass substrate layer and the silicone resin layer corresponds to the silicon resin layer Was higher than the peeling strength (w) at the interface of the supporting substrate.

Then, various measurements were made using the obtained glass laminate S2. The evaluation results are summarized in Table 1 to be described later.

Further, in the evaluation of the peelability using the glass laminate S2, a stainless steel blade was inserted between the supporting substrate and the silicone resin layer, and a peeling period was given. In [Flatness Evaluation], the surface roughness of the surface of the silicon resin layer and the surface of the supporting substrate, which are the laminated surfaces of the glass laminate S2, were measured.

(Example 3)

If subjected to the purification treatment of the support for the sol-gel A substrate (first main surface) vertical to the 278mm, was the construction coated with a spin coater to a size of width 278mm (coating construction amount of 150g / m ^2), except in Example 1, a procedure similar to To prepare a glass laminate S3.

The thickness of the formed silicone resin layer was 2.0 mu m.

The obtained glass laminate S3 corresponds to the glass laminate 10 of Fig. 1 described above. In the glass laminate S1, the peel strength (x) between the interface of the supporting substrate layer and the silicone resin layer is smaller than the peeling strength Was higher than the peel strength (y) at the interface of the glass substrate.

Then, various measurements were made using the obtained glass laminate S3. The evaluation results are summarized in Table 1 to be described later.

Further, in the evaluation of the peelability using the glass laminate S3, a stainless steel blade was inserted between the glass substrate and the silicone resin layer, and a peeling period was given. In the [Flatness evaluation], the surface roughness of the surface of the silicon resin layer and the surface of the glass substrate, which are the laminated surfaces of the glass laminate S3, were measured.

(Example 4)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.5 mm and a linear expansion coefficient of 38 × 10 ^-7 / ° C was prepared as a supporting substrate, To clean the surface. Subsequently, the curable organopolysiloxane (S1) prepared above was coated on the surface (first main surface) to which the support substrate had been subjected to the cleaning treatment (first main surface) in a size of 278 mm in the vertical direction and 278 mm in the horizontal direction by a spin coater ² ). Further, the resin layer was heated and cured at 350 占 폚 in the air for 30 minutes to form a resin layer X (corresponding to the second silicone resin layer) having a thickness of 6 占 퐉 to obtain a support C.

Subsequently, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.2 mm and a coefficient of linear expansion of 38 × 10 ^-7 / ° C was prepared as a glass substrate, To clean the surface. Subsequently, the sol-gel A was coated on the surface (first main surface) subjected to the cleaning treatment of the glass substrate by a spin coater with a size of 278 mm in length and 278 mm in width (coating amount 15 g / m ² ). The glass substrate C was heated and cured in air at 350 DEG C for 30 minutes to form a 0.2 mu m-thick silicon resin layer (corresponding to the first silicone resin layer) to obtain a glass substrate C. [

Both substrates were superimposed on each other so that the center of gravity of both substrates was overlapped with a resin layer in the support C opposite to the silicon resin layer in the glass substrate C under a room temperature and an atmospheric pressure with a laminating apparatus to obtain a glass laminate S4.

The obtained glass laminate S4 corresponds to the glass laminate 200 shown in Fig. 4, and in the glass laminate S4, the peel strength (w) at the interface between the resin layer X and the silicone resin layer corresponds to the glass resin layer (Z) at the interface of the substrate and the peel strength (v) at the interface between the resin layer X and the support substrate (support glass plate).

Then, various measurements were made using the obtained glass laminate S4. The evaluation results are summarized in Table 1 to be described later.

Further, in the evaluation of the peelability using the glass laminate S4, a stainless steel blade was inserted between the resin layer X and the silicone resin layer, and a peeling period was given. In [Flatness Evaluation], the surface roughness of the surface of the resin layer and the surface of the silicone resin layer, which are the laminated surfaces of the glass laminate S4, were measured.

(Example 5)

A glass laminate S5 was obtained in the same manner as in Example 4 except that the sol-gel B was used instead of the sol-gel A.

Various measurements were made using the obtained glass laminate S5. The evaluation results are summarized in Table 1 to be described later.

The obtained glass laminate S5 corresponds to the glass laminate 200 shown in Fig. 4, and in the glass laminate S5, the peel strength (w) at the interface between the resin layer X and the silicon resin layer corresponds to the glass resin layer (Z) at the interface of the substrate and the peel strength (v) at the interface between the resin layer X and the support substrate (support glass plate).

(Example 6)

A glass laminate S6 was obtained in the same manner as in Example 4 except that the sol-gel C was used instead of the sol-gel A.

The various measurements using the obtained glass laminate S6 were carried out. The evaluation results are summarized in Table 1 to be described later.

4, and in the case of the glass laminate S6, the peel strength (w) at the interface between the resin layer X and the silicone resin layer is higher than that of the silicon resin layer and the glass (Z) at the interface of the substrate and the peel strength (v) at the interface between the resin layer X and the support substrate (support glass plate).

(Example 7)

If subjected to a cleaning process in the substrate material for a sol-gel A (first main surface) vertical to the 278mm, was the construction coated with a spin coater to a size of width 278mm (coating construction amount of 150g / m ^2), except Example 4 Similarly to the thickness A silicon resin layer (corresponding to the first silicone resin layer) of 2.0 mu m was formed, and a glass substrate C was obtained.

Both substrates were superimposed on each other so that the center of gravity of both substrates was overlapped with a resin layer in the support C opposite to the silicon resin layer in the glass substrate C under a room temperature and atmospheric pressure with a laminating apparatus to obtain a glass laminate S7.

The above-described various measurements were conducted using the obtained glass laminate S7. The evaluation results are summarized in Table 1 to be described later.

The obtained glass laminate S7 corresponds to the glass laminate 200 shown in Fig. 4, and in the glass laminate S7, the peel strength (w) at the interface between the resin layer X and the silicone resin layer corresponds to the glass resin layer and the glass (Z) at the interface of the substrate and the peel strength (v) at the interface between the resin layer X and the support substrate (support glass plate).

(Comparative Example 1)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.5 mm and a linear expansion coefficient of 38 × 10 ^-7 / ° C was prepared as a supporting substrate, To clean the surface.

Subsequently, the first main surface of the supporting substrate subjected to the cleaning treatment (first main surface) and the first main surface of a glass substrate (" AN100 ", manufactured by Asahi Glass Co., Ltd.) Under a room temperature and atmospheric pressure, the glass substrate and the glass substrate were superimposed with the center of gravity of the supporting substrate and the glass substrate stacked together by a lamination apparatus to obtain a glass laminate C1.

Various measurements were made using the obtained glass laminate C1. The evaluation results are summarized in Table 1 to be described later.

(Comparative Example 2)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.5 mm and a linear expansion coefficient of 38 × 10 ^-7 / ° C was prepared as a supporting substrate, To clean the surface. Subsequently, the supporting substrate was exposed in an atmosphere containing a vaporized gas of hexamethyldisilazane (1,1,1,3,3,3-hexamethyldisilazane manufactured by KANTO CHEMICAL Co., Ltd.) Surface treatment was carried out.

Subsequently, the surface of the supporting substrate subjected to the surface treatment and the first main surface of a glass substrate ("AN100" manufactured by Asahi Glass Co., Ltd.) having the same size as the supporting substrate and having a thickness of 0.2 mm were opposed to each other, The glass substrate and the glass substrate were stacked so that the center of gravity of the supporting substrate and the glass substrate were overlapped with each other by a laminating apparatus to obtain a glass laminate C2.

Various measurements were made using the obtained glass laminate C2. The evaluation results are summarized in Table 1 to be described later.

(Comparative Example 3)

First, a non-alkali glass plate ("AN100" manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, a plate thickness of 0.5 mm and a linear expansion coefficient of 38 × 10 ^-7 / ° C was prepared as a supporting substrate, To clean the surface. Subsequently, a solution prepared by diluting dimethylpolysiloxane (SH200, manufactured by Dow Silicone Co., Ltd.) with heptane was applied to the first main surface of the supporting substrate using a spin coater (MIKASA, MS-A100). Subsequently, heat treatment was performed at 500 캜 for 5 minutes in the atmosphere using a hot plate. In this manner, the first main surface of the supporting substrate was subjected to surface treatment for baking silicone oil.

Subsequently, the first main surface of the surface-treated supporting substrate was faced to the first main surface of a glass substrate (" AN100 ", manufactured by Asahi Glass Co., Ltd.) having the same size as the supporting substrate and having a thickness of 0.2 mm, Under the atmospheric pressure, the glass substrate and the glass substrate were overlapped with each other such that the center of gravity of the supporting substrate and the glass substrate were superimposed by a laminating apparatus to obtain a glass laminate C3.

Various measurements were made using the obtained glass laminate C3. The evaluation results are summarized in Table 1 to be described later.

(Comparative Example 4)

Similar to Comparative Example 3, except that dimethylpolysiloxane (SH200, manufactured by Dow Silicone Co., Ltd.) was applied to the first main surface of the supporting substrate using a spin coater (MIKASA, MS-A100) without diluting with heptane To obtain a glass laminate C4.

Various measurements were made using the obtained glass laminate C4. The evaluation results are summarized in Table 1 to be described later.

In Table 1, the constituent layers of the glass laminate used in Examples and Comparative Examples are shown in the column of " Composition of Glass Laminate ". " // " appearing between the respective layers is intended to be a laminate surface, Is intended to occur.

The " value of Ra of the laminated surface " also means the surface roughness Ra of the layer located on the right and left of " // " in the column "Composition of glass laminate". For example, in the first embodiment, the constitution of the glass laminate is " glass substrate // first silicon resin layer / supporting substrate ", and on the first silicon resin layer side of the " The Ra of the surface is 0.8 nm and the Ra of the surface of the "first silicone resin layer" on the right side of "//" on the glass substrate side is 10 nm. Other embodiments and comparative examples are similarly interpreted.

The " film thickness of the silicone resin layer " also means the thickness of the first silicone resin layer. In Examples 3 to 5, the thickness of the first silicone resin layer is shown on the left side and the thickness of the second silicone resin layer is shown on the right side in the "film thickness of the silicone resin layer". Further, in Comparative Examples 2 to 4, the layer thicknesses of HMDS or SH200 are shown.

In the " determination " column, the value of the peel strength is 10 N / 25 mm or less, the case where no foaming is observed is indicated by " ", and the case where either or both of them are not satisfied is " x ".

As shown in Table 1, in the glass laminate comprising a predetermined first silicone resin layer, the peeling strength was low and the foaming of the silicone resin layer was also suppressed. For example, as shown in Example 3 or 7, foaming did not occur even when the thickness of the silicone resin layer (first silicone resin layer) was thick.

On the other hand, in Comparative Examples 1 to 4, which did not satisfy the predetermined requirements, desired effects were not obtained. For example, in Comparative Example 1, the glass substrate could not be peeled off. In Comparative Examples 2 and 3, the peel strength was higher than that of Examples 1 to 7, and the peelability was lowered.

Further, the glass laminate shown in Examples 4 to 7 was able to laminate favorably even when the surface roughness (Ra) of the laminate surface was large.

≪ Example 8 >

In this example, an OLED is manufactured using the glass laminate S1 obtained in the first embodiment.

First, a film of silicon nitride, silicon oxide, and amorphous silicon is formed in this order on the second main surface of the glass substrate in the glass laminate S1 by the plasma CVD method. Subsequently, low-concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, low-concentration phosphorus is injected into the amorphous silicon layer from an etching and ion doping apparatus using a photolithography method to form N-type and P-type TFT areas. Subsequently, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Subsequently, boron and phosphorus at a high concentration are implanted into desired areas of N type and P type, respectively, by photolithography and ion doping apparatus to form a source area and a drain area. Subsequently, an interlayer insulating film is formed on the second main surface side of the glass substrate by the plasma CVD method by the silicon oxide film formation, and a TFT electrode is formed by the sputtering method by aluminum film formation and etching by photolithography. Subsequently, a heat treatment is performed in a hydrogen atmosphere to perform a hydrogenation treatment, and then a passivation layer is formed by film formation of nitrogen silicon by the plasma CVD method. Subsequently, an ultraviolet curing resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Subsequently, indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injection layer on the second main surface side of the glass substrate by vapor deposition, and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) , And 5-dicarbononitrile (BSN-BCN) in an amount of 40% by volume, and Alq ₃ as an electron transporting layer are formed in this order. Next, aluminum is deposited by a sputtering method and is etched by photolithography Next, one glass substrate is further sealed and sealed with an ultraviolet curable adhesive layer interposed therebetween on the second main surface side of the glass substrate. The organic EL structure is formed on the glass substrate by the above procedure. A glass laminate S1 having an organic EL structure on a substrate (hereinafter referred to as panel A) And is a membered laminate for electronic devices.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner of the panel A after the sealing member side of the panel A was vacuum-adsorbed on the surface of the plate, Give the instrument. After the surface of the support substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the blade is carried out while spraying an antistatic fluid on the interface from an ionizer (manufactured by KYENS). Then, the vacuum adsorption pad is pulled up while spraying the water to the peeling wire while spraying the antistatic fluid continuously from the ionizer toward the formed gap. As a result, only the glass substrate having the organic EL structure formed on the surface thereof can be left, and the supporting substrate with the resin layer can be peeled off.

Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. Then, a glass substrate on which the organic EL structure is formed and a counter substrate are assembled to form a module, do. The characteristics of the OLED thus obtained do not occur.

≪ Example 9 >

In this example, an LCD is manufactured using the glass laminate S1 obtained in the first embodiment.

First, two glass laminate S1 are prepared, and a film of silicon nitride, silicon oxide, and amorphous silicon is formed in this order on the second main surface of the glass substrate in one glass laminate S1-1 by the plasma CVD method. Subsequently, low-concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, low-concentration phosphorus is injected into the amorphous silicon layer from an etching and ion doping apparatus using a photolithography method to form N-type and P-type TFT areas. Subsequently, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Subsequently, boron and phosphorus at a high concentration are implanted into desired areas of N type and P type, respectively, by photolithography and ion doping apparatus to form a source area and a drain area. Subsequently, an interlayer insulating film is formed on the second main surface side of the glass substrate by the plasma CVD method by the silicon oxide film formation, and a TFT electrode is formed by the sputtering method by aluminum film formation and etching by photolithography. Subsequently, a heat treatment is performed in a hydrogen atmosphere to perform a hydrogenation treatment, and then a passivation layer is formed by film formation of nitrogen silicon by the plasma CVD method. Subsequently, an ultraviolet curing resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Subsequently, indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Then, one of the glass laminate S1-2 is subjected to heat treatment in an air atmosphere. Then, chromium is deposited on the second main surface of the glass substrate in the glass laminate S1 by the sputtering method, and the light shielding layer is formed by etching by photolithography. Then, a color resist is coated on the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by photolithography and thermal curing. Subsequently, indium tin oxide is formed by a sputtering method, and an opposite electrode is formed. Subsequently, an ultraviolet curable resin liquid is coated on the second main surface side of the glass substrate by a die coating method, and a columnar spacer is formed by photolithography and thermal curing. Then, a polyimide resin solution is applied by a roll coating method, an orientation layer is formed by thermal curing, and rubbing is performed.

Subsequently, the sealing resin liquid was drawn in a frame shape by the dispenser method, liquid crystal was dropped by the dispenser method in the frame, and then the glass laminate S1-1 on which the pixel electrodes were formed was used to form two glass laminate S1 Are bonded to each other, and an LCD panel is obtained by ultraviolet curing and thermosetting.

Subsequently, the second main surface of the supporting substrate of the glass laminate S1-1 was vacuum-adsorbed on the surface plate, and a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-2 , Giving a moment of peeling of the first main surface of the glass substrate and the peelable surface of the resin layer. Here, the insertion of the blade is carried out while spraying an antistatic fluid on the interface from an ionizer (manufactured by KYENS). Subsequently, the vacuum adsorption pad is pulled up while water is injected into the peeling wire while spraying the antistatic fluid from the ionizer toward the formed gap. After the second main surface of the supporting substrate of the glass laminate S1-2 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, it is possible to peel off the supporting substrate with the resin layer, leaving only empty cells of the LCD with the supporting base material of the glass laminate S1-1 on the base glass.

Subsequently, a second main surface of the glass substrate on which the color filter was formed on the first main surface was vacuum-adsorbed on the surface plate, and a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-1 , Giving a moment of peeling of the first main surface of the glass substrate and the peelable surface of the resin layer. After the second main surface of the supporting substrate of the glass laminate S1-1 is adsorbed by the vacuum adsorption pad, water is sprayed between the glass substrate and the resin layer to raise the adsorption pad. As a result, the supporting substrate on which the resin layer is fixed can be peeled off, leaving only the LCD cell on the surface of the substrate. Thus, a plurality of LCD cells constituted by a glass substrate having a thickness of 0.1 mm are obtained.

Subsequently, the cells are divided into a plurality of LCD cells by a cutting process. A process of attaching a polarizing plate to each completed LCD cell is performed, and then a module forming process is performed to obtain an LCD. The LCD thus obtained does not cause any problems due to its characteristics.

≪ Example 10 >

In this example, an OLED is manufactured using the glass laminate S1 obtained in the first embodiment.

First, molybdenum is deposited on the second main surface of the glass substrate in the glass laminate S1 by a sputtering method, and a gate electrode is formed by etching by photolithography. Subsequently, aluminum oxide is further formed on the second main surface side of the glass substrate by sputtering to form a gate insulating film. Subsequently, indium gallium zinc oxide is formed by sputtering and is etched by photolithography to form an oxide semiconductor layer . Subsequently, aluminum oxide is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protection layer, and subsequently, molybdenum is deposited by sputtering and is etched by photolithography to form a source electrode and a drain electrode .

Subsequently, heat treatment is performed in the air. Subsequently, aluminum oxide is further formed on the second main surface side of the glass substrate by a sputtering method to form a passivation layer. Subsequently, indium tin oxide is formed by sputtering and a pixel electrode is formed by etching using a photolithography method do.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injection layer on the second main surface side of the glass substrate by vapor deposition, and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) , And 5-dicarbononitrile (BSN-BCN) in an amount of 40% by volume, and Alq ₃ as an electron transporting layer are formed in this order. Next, aluminum is deposited by a sputtering method and is etched by photolithography Next, one glass substrate is further sealed and sealed with an ultraviolet curable adhesive layer interposed therebetween on the second main surface side of the glass substrate. The organic EL structure is formed on the glass substrate by the above procedure. A glass laminate S1 having an organic EL structure on a substrate (hereinafter referred to as panel B) (A panel for a display device having a supporting substrate).

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the resin layer at the corner of the panel B after the sealing member side of the panel B was vacuum-adsorbed on the surface of the panel. Give the instrument. After the surface of the supporting substrate of the panel B is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the blade is carried out while spraying an antistatic fluid on the interface from an ionizer (manufactured by KYENS). Subsequently, the vacuum adsorption pad is pulled up while injecting the antistatic fluid continuously from the ionizer toward the formed gap, and further adding water to the peeling wire. As a result, only the glass substrate having the organic EL structure formed on the surface thereof can be left, and the supporting substrate with the resin layer can be peeled off.

Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method, and is divided into a plurality of cells. Thereafter, the glass substrate on which the organic EL structure is formed and the counter substrate are assembled, And make them. The characteristics of the OLED thus obtained do not occur.

The present application is based on Japanese Patent Application No. 2013-273147 filed on December 27, 2013, the contents of which are incorporated herein by reference.

10, 100, 200: Glass laminate
12: support substrate
14: a first silicone resin layer
16: glass substrate
18: Resin support layer
20: glass substrate with resin layer
22: member for electronic device
24: Memberless laminate for electronic device
26: Glass substrate without member
30: Support glass plate
32: a second silicone resin layer

Claims (12)

A glass laminate comprising a support substrate layer, a silicone resin layer, and a glass substrate layer in this order,
Wherein the silicone resin of the silicone resin layer is a condensation polymer having a D unit represented by the following formula (D) and a Q unit represented by the following formula (Q)
Wherein the peel strength of the interface between the silicon resin layer and the glass substrate layer is different from the peel strength of the interface between the silicon resin layer and the support substrate layer,

In the formulas, R ^a and R ^b each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent. The glass laminate according to claim 1, wherein the molar ratio (D unit / Q unit) of the D unit to the Q unit in the axial polymeride is 0.02 to 2. The glass laminate according to claim 1 or 2, wherein R ^a and R ^b in formula (D) are all methyl groups. The glass laminate according to any one of claims 1 to 3, wherein the silicon resin layer has a thickness of 5 to 2000 nm. The method according to any one of claims 1 to 4, wherein the axial polymerisate comprises a silicon compound (X) represented by the following formula (X) or a mass thereof and a silicon compound (Y) represented by the following formula Wherein the mixture of the oligomers or the curable compound containing the partial-axis polymerized product of the mixture is a condensation-polymerized axial polymer,

In the formulas, R ^a and R ^b each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent, and R ^x and R ^y each independently represent a hydrogen atom, a hydroxy group or a hydrolysable group. The glass laminate according to claim 5, wherein R ^a and R ^b in formula (X) are all methyl groups and the hydrolyzable group is an alkoxy group having 4 or less carbon atoms. The glass substrate according to any one of claims 1 to 6, wherein a peel strength at an interface of the silicon resin layer with respect to the glass substrate layer is lower than a peel strength at an interface between the silicon resin layer and the support substrate layer Laminates. The glass substrate according to any one of claims 1 to 6, wherein the peel strength of the interface of the first silicon resin layer to the glass substrate layer is higher than the peel strength of the interface of the silicon resin layer to the support substrate layer ≪ / RTI > The method of manufacturing a semiconductor device according to any one of claims 1 to 8, wherein the layer of the supporting substrate is a laminated support substrate having a layer of a supporting glass plate and a second silicon resin layer, the second silicon resin layer being in contact with the silicon resin layer ≪ / RTI > The curable organopolysiloxane according to claim 9, wherein the silicone resin of the second silicone resin layer comprises a curable organopolysiloxane, and the curable organopolysiloxane comprises a siloxane unit (A) represented by formula (1) (B) represented by the following formula

In the formulas, R ¹ to R ⁴ each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group which may have a substituent; R ⁵ and R ⁶ each independently represent an alkyl group having 4 or less carbon atoms or an alkenyl group having 3 or less carbon atoms; Ar represents a phenylene group which may have a substituent; Provided that at least a part of the siloxane unit (B) is a siloxane unit in which at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms. 11. The glass laminate according to claim 9 or 10, wherein the thickness of the second silicon resin layer is larger than the thickness of the silicon resin layer and is 50 m or less. 9. A method of producing a glass laminate according to any one of claims 5 to 8,
A step of applying the curable compound on the surface of one of the glass substrate and the support substrate and performing heat treatment to form a silicone resin layer on the surface of either the glass substrate or the support substrate,
And a step of laminating the other of the glass substrate and the supporting substrate on the silicon resin layer.

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