TW201540497A - Glass laminate - Google Patents

Abstract

Provided is a glass laminate which is suppressed in decomposition of a silicone resin layer even after a high-temperature heat treatment. A glass laminate which sequentially comprises a supporting base layer, a silicone resin layer and a glass substrate layer in this order, and wherein the peel strength at the interface between the supporting base layer and the silicone resin layer is higher than the peel strength at the interface between the glass substrate layer and the silicone resin layer. The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane; and the crosslinkable organopolysiloxane contains a siloxane unit (A) represented by a specific formula (1), but does not substantially contain an alkenyl group and an alkynyl group.

Description

Glass laminate Field of invention

The present invention relates to a glass laminate.

Background of the invention

In recent years, thinner and lighter components (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL panels (OLEDs) have progressed, and the thinning of glass substrates used in these components has also progressed. . However, if the strength of the glass substrate is insufficient due to the thinning, the handleability of the glass substrate is lowered in the manufacturing steps of the module.

Recently, in order to cope with the above-mentioned problems, a method has been proposed in which a glass laminate having a laminated glass substrate and a reinforcing plate is prepared, and a member for an electronic component such as a display device is formed on a thin glass substrate of a glass laminate. The reinforcing plate is separated from the thin glass substrate (for example, refer to Patent Document 1). The reinforcing plate has a supporting plate and a polyoxyalkylene resin layer fixed to the supporting plate, and the polyoxynitride resin layer and the thin glass substrate are peelably adhered together. The interface between the polyoxyxene resin layer of the glass laminate and the thin glass substrate is peelable, and the reinforcing plate that has been separated from the thin glass substrate can be reused by laminating the other thin glass substrate with a glass laminate.

Prior technical literature

Patent literature

Patent Document 1: International Publication No. 2007/018028

Summary of invention

The glass laminate described in Patent Document 1 tends to require higher heat resistance in recent years. With the high functionality and complexity of the electronic component member formed on the glass substrate of the glass laminate, the temperature at which the member for the electronic component is formed becomes higher than the temperature, and the time when the temperature is exposed to the high temperature is also elongated. Quite a lot.

The glass laminate described in Patent Document 1 can be subjected to a treatment at 300 ° C for 1 hour in the atmosphere. However, it has been found by the inventors of the present invention that the polyoxynoxy resin layer in the glass laminate described in Patent Document 1 is decomposed in a short time at 450 ° C to generate a large amount of outgas. The occurrence of such outgasing contaminates the member for electronic components formed on the glass substrate, and as a result, the productivity of the electronic component is lowered.

The present invention has been made in view of the above, and it is an object of the invention to provide a glass laminate which can still suppress decomposition of a polyoxymethylene resin layer after high-temperature heat treatment such as when a member for an electronic component is formed.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that by using a specific polyoxyxylene resin layer, decomposition can be suppressed after high-temperature heat treatment, and the present invention has been completed.

That is, the present invention provides the following [1] to [8].

[1] A glass laminate comprising a support substrate layer, a polyoxyxylene resin layer, and a glass substrate layer, wherein an interfacial peel strength of the support substrate layer and the polyoxyxylene resin layer is higher than the glass substrate The interfacial peeling strength of the layer and the polyoxyxene resin layer; the polyfluorene oxide resin of the polyfluorene oxide resin layer is a crosslinked product of a crosslinkable organopolyoxane, and the crosslinkable organopolyoxane contains the following formula (1) The azide unit (A) shown and substantially free of alkenyl groups and alkynyl groups.

[2] The glass laminate according to [1], wherein R ¹ to R ⁴ in the azide unit (A) are each independently an alkyl group having 4 or less carbon atoms.

[3] The glass laminate according to [1] or [2], wherein the crosslinkable organopolyoxane further contains a siloxane unit (B) represented by the following formula (2).

[4] The glass laminate according to [3], wherein the ruthenium of the crosslinkable organopolyoxane is the total of the oxime unit (A) and the oxime unit (B). The ratio of the oxyalkylene unit (A) is 30 to 90 mol%, and the total ratio of the above-mentioned oxoxane unit (A) to the above-mentioned oxane unit (B) is 80 to 100 mol with respect to the total siloxane unit. ear%.

[5] to [3] or [4] a glass laminate according to the, wherein said silicon siloxane unit (B) based R ⁵ and R ⁶ is phenyl of silicon siloxane units (B-1) or R ⁵ and Any of R ⁶ is an alkyl group having 4 or less carbon atoms and the other is a phenyl alkane unit (B-2).

[6] The glass laminate according to any one of [1] to [5] wherein Ar in the above siloxane unit (A) is a phenyl group, a naphthyl group, a phenyl group or a hydrazine group. Phenyl.

[7] The glass laminate according to any one of [1] to [6], wherein the crosslinking is carried out The total number of alkenyl groups and alkynyl groups which are bonded to the ruthenium atom in one molecule of the organopolysiloxane is 100 or less.

The glass laminate according to any one of the above aspects, wherein the crosslinkable organopolysiloxane has a number average molecular weight of from 5,000 to 100,000 in terms of polystyrene as measured by GPC.

According to the glass laminate of the present invention, the decomposition of the polyoxymethylene resin layer can be suppressed after the high-temperature heat treatment.

10‧‧‧glass laminate

12‧‧‧Support substrate

14‧‧‧Polyoxy resin layer

14a‧‧‧Surface (the first main surface of the polyoxyl resin layer)

16‧‧‧ glass substrate

16a‧‧‧1st main surface of the glass substrate

16b‧‧‧2nd main surface of the glass substrate

18‧‧‧Support substrate with polyoxyl resin layer

20‧‧‧Members for electronic components

22‧‧‧Laminated body with components for electronic components

24‧‧‧ Glass substrate with attached components

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a glass laminate of the present invention.

2(A) to 2(D) are schematic cross-sectional views showing an embodiment of a method of manufacturing a glass substrate of an attached member of the present invention in order of steps.

Form for implementing the invention

The present invention is not limited by the following embodiments, and various modifications and substitutions may be made in the following embodiments without departing from the scope of the invention.

The glass laminate of the present invention is provided with a support substrate layer, a polyoxymethylene resin layer, and a glass substrate layer in this order. That is, a polyoxynitride resin layer is provided between the support base material layer and the glass substrate layer. Therefore, one side of the polyoxynitride resin layer is in contact with the support substrate layer and the other side is in contact with the glass substrate layer.

In the glass laminate of the present invention, the polyoxyxylene resin of the polyoxyxylene resin layer is a crosslinked product of a crosslinkable organopolyoxane described later, whereby the glass base can be used. The panel exhibits a predetermined adhesion and inhibits decomposition of the polyoxyxene resin under high temperature processing conditions. As a result, the occurrence of outgassing or the displacement of the glass substrate can be more suppressed.

The reason why the decomposition of the polyoxymethylene resin can be suppressed is that the main chain of the crosslinkable organopolyoxane contains a divalent aromatic hydrocarbon group (for example, a phenyl group). By containing the aromatic hydrocarbon group, the bonding energy of the crosslinkable organopolysiloxane can be improved, and the mobility of the crosslinkable organopolyoxane can be lowered, and the cracking of the decane bond can be difficult.

As a result, the cyclic compound which forms a oxoxane accompanying the cracking can be suppressed, and the occurrence of outgassing or the displacement of the glass substrate can be further suppressed.

Further, according to the glass laminate of the present invention, the following effects can be exhibited.

For example, a case is considered in which a ruthenium atom (Si) in a crosslinkable organopolyoxane which is hardened to form a polyoxyxylene resin layer is bonded with an alkenyl group or an alkynyl group (represented by a vinyl group (Vi), That is, the vinyl is taken as an example for explanation). At this time, if the crosslinkable organopolysiloxane is heat-hardened, for example, at about 300 ° C or higher, the Si-Vi portion is decomposed or the Si-Vi is partially oxidized to form Si-OH, and the Si-OH is further dehydrated and condensed with each other. Therefore, foaming or cracking sometimes occurs in the obtained polyoxymethylene resin layer. Once foaming or cracking occurs in the polyoxyxene resin layer, the adhesion of the crucible and its laminated glass substrate on the polyoxyalkylene resin layer may be lowered, or the glass may not be laminated on the polyoxyalkylene resin layer from the beginning. Substrate.

Therefore, if the heat-hardening temperature is lowered in order to avoid the occurrence of the foaming or cracking, the resulting Si-OH may not be condensed and remain, and The residual Si-OH improves the peel strength of the glass substrate laminated on the polyoxyalkylene resin layer.

However, in the present invention, the crosslinkable organopolyoxane which becomes a polyoxyxylene resin layer does not substantially have an alkenyl group and an alkynyl group, so that decomposition of the remaining Si-Vi moiety or Si-Vi moiety can be suppressed. As a result of the formation of Si-OH by oxidation, it is possible to suppress the occurrence of foaming and cracking in the polyoxynated resin layer, or to suppress the increase in the peeling strength of the glass substrate when the heat curing temperature is lowered.

Further, in general, as the thickness of the polyoxyxene resin layer increases, there is a tendency that cracks are likely to occur. However, the glass laminate of the present invention does not easily cause cracks in the polyoxymethylene resin layer, and thus can suppress cracks. Occurs at the same time, and the polyoxynoxy resin layer can be thickened.

Fig. 1 is a schematic cross-sectional view showing an example of a glass laminate according to the present invention.

As shown in Fig. 1, the glass laminate 10 is a laminate having a layer supporting the substrate 12, a layer of the glass substrate 16, and a polyoxyalkylene layer 14 present between the layers. One side of the polyoxygenated resin layer 14 is in contact with the layer of the support substrate 12, and the other surface is in contact with the first main surface 16a of the glass substrate 16. In other words, the polyoxyxene resin layer 14 is in contact with the first main surface 16a of the glass substrate 16.

The two-layered portion composed of the layer of the support substrate 12 and the polyoxyxene resin layer 14 is used to reinforce the glass substrate 16 in the member forming step of manufacturing a member for an electronic component such as a liquid crystal panel. On the other hand, the two-layer portion composed of the layer of the support substrate 12 and the polyoxynoxy resin layer 14 which are previously manufactured to produce the glass laminate 10 is referred to as a support substrate 18 of an agglomerated epoxy resin layer.

The glass laminate 10 can be continuously used to form a member to be described later. step. In other words, the glass laminate 10 can be used until a member for an electronic component such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the glass laminate in which the member for electronic components is formed is separated into the glass substrate supporting the substrate 12 and the attached member, and the support substrate 18 of the agglomerated epoxy resin layer does not become a portion constituting the electronic component. The support substrate 18 of the agglomerated epoxy resin layer can be laminated with another new glass substrate 16 for reuse of the new glass laminate 10.

The interface between the support substrate 12 and the polyoxyxene resin layer 14 has a peel strength (x), and when a stress exceeding the peel strength (x) in the peeling direction is applied to the interface between the support substrate 12 and the polyoxyxene resin layer 14, support is provided. The interface between the substrate 12 and the polyoxyxene resin layer 14 is peeled off. The interface between the polyoxyxene resin layer 14 and the glass substrate 16 has a peeling strength (y), and a stress exceeding the peeling strength (y) in the peeling direction is applied to the interface between the polyoxyxylene resin layer 14 and the glass substrate 16 The interface between the resin 14 layer and the glass substrate 16 is peeled off.

In the glass laminate 10 of the present invention (also referred to as a laminate of a member for electronic components to be described later), the peel strength (x) is higher than the peel strength (y). Therefore, when the stress in the direction in which the support substrate 12 and the glass substrate 16 are peeled off is applied to the glass laminate 10 of the present invention, the glass laminate 10 of the present invention is peeled off at the interface between the polyimide resin layer 14 and the glass substrate 16. The support substrate 18 is separated into a glass substrate 16 and an agglomerated epoxy resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means increasing the adhesion of the silicone resin layer 14 to the support substrate 12, and maintaining a relatively high adhesion to the glass substrate 18 after the heat treatment.

In order to increase the adhesion of the polyoxyxene resin layer 14 to the support substrate 12, it is preferred to form the polyoxyxylene resin layer 14 by crosslinking and curing the crosslinkable organopolysiloxane on the support substrate 12 as will be described later. The polyoxynitride resin layer 14 bonded to the support substrate 12 by high bonding force can be formed by the adhesion force at the time of crosslinking hardening.

On the other hand, conventionally, the binding strength of the polyoxyxylene resin of the crosslinked product of the crosslinkable organopolyoxane to the glass substrate 16 is often lower than the bonding force generated when the above crosslinking is hardened. Therefore, it is preferable to crosslink and cure the crosslinkable organopolyoxane to form the polyoxyxene resin layer 14 on the support substrate 12, and then laminate the glass substrate 16 on the surface of the polyoxynoxy resin layer 14 to manufacture the glass laminate 10. .

In the following, the respective layers (the support substrate 12, the glass substrate 16, and the polyoxymethylene resin layer 14) constituting the glass laminate 10 will be described in detail, and then the method for producing the glass laminate and the glass substrate of the member will be described in detail.

[Support substrate]

The support substrate 12 can support and reinforce the glass substrate 16 and prevent deformation, damage, breakage, and the like of the glass substrate 16 when the electronic component member is manufactured in the member forming step (step of manufacturing the electronic component) described later.

As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate can be used. Generally, the member forming step is accompanied by a heat treatment, and therefore the support substrate 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16, and is preferably formed of the same material as the glass substrate 16, that is, the support substrate 12 is made of a glass plate. It is better. In particular, the support substrate 12 is preferably a glass plate composed of the same glass material as the glass substrate 16.

The thickness of the support substrate 12 can be thicker than the glass substrate 16, or thin. The thickness of the support substrate 12 is preferably selected in accordance with the thickness of the glass substrate 16, the thickness of the polyoxyxene resin layer 14, and the thickness of the glass laminate 10. For example, the current member forming step is designed to process a substrate having a thickness of 0.5 mm, so when the sum of the thickness of the glass substrate 16 and the thickness of the polyoxyxene resin layer 14 is 0.1 mm, the thickness of the support substrate 12 is set to 0.4. Mm. The thickness of the support substrate 12 is usually 0.2 to 5.0 mm.

When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more from the viewpoint of good handling and difficulty in cracking. Moreover, it is preferable that the thickness of the glass plate is 1.0 mm or less from the viewpoint of being able to have a rigidity which can be flexed moderately without being broken when forming the member for an electronic component.

The difference between the linear expansion coefficients of the support substrate 12 and the glass substrate 16 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or less, preferably 300 × 10 ^-7 / ° C or less, and 200 × 10 ^-7 / Above °C is better. When the phase difference is too large, the glass laminate 10 is strongly warped or the base material 12 and the glass substrate 16 are peeled off when heated and cooled in the member forming step. When the material of the support substrate 12 is the same as that of the glass substrate 16, the occurrence of such a problem can be suppressed.

[glass substrate]

In the glass substrate 16, the first main surface 16a is in contact with the polyoxynitride resin layer 14, and the electronic component member can be provided on the second main surface 16b on the side opposite to the polyoxynitride resin layer 14 side.

The type of the glass substrate 16 can be a general type, and for example, a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. And as an indicator of heat shrinkage rate, The linear expansion coefficient specified in JIS R 3102 (Amended 1995) is used.

If the linear expansion coefficient of the glass substrate 16 is large, since the member forming step is often accompanied by heat treatment, various troubles are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT has been formed is cooled under heating, there is a fear that the displacement of the TFT becomes excessive due to thermal contraction of the glass substrate 16.

The glass substrate 16 is obtained by molding a molten glass raw material into a plate shape. Such a forming method can be a general method, and for example, a floating glass plate method, a melting method, a flow hole down-draw method, a Fourcault process, a Lubbers method, or the like can be used. Further, in particular, the glass substrate 16 having a small thickness can be formed by a re-extension method in which a glass which is temporarily formed into a plate shape is heated to a moldable temperature, and then stretched and thinned by means of stretching or the like.

The type of the glass of the glass substrate 16 is not particularly limited, and it is preferably an alkali-free borosilicate glass, a borosilicate glass, a soda-lime glass, a sorghum glass, or another oxide-based glass containing cerium oxide as a main component. In the case of the oxide-based glass, it is preferable to use a glass having a cerium oxide content of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 16, a glass suitable for the kind of the member for electronic components or a manufacturing step thereof can be used. For example, from the viewpoint that the elution of the alkali metal component is likely to affect the liquid crystal, the glass substrate for a liquid crystal panel is composed of glass (alkali-free glass) which does not substantially contain an alkali metal component (however, it usually contains an alkaline earth metal component). . In this way, the glass of the glass substrate 16 can be appropriately selected according to the types of components to be applied and the manufacturing steps thereof. Choose.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, and preferably 0.15 mm or less from the viewpoint of thickness reduction and/or weight reduction of the glass substrate 16. When it is 0.3 mm or less, the glass substrate 16 can be provided with favorable flexibility. When it is 0.15 mm or less, the glass substrate 16 can be wound up in a roll shape.

Moreover, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy production of the glass substrate 16 and easy handling of the glass substrate 16.

Further, the glass substrate 16 may be composed of two or more layers. In this case, the materials forming the layers may be the same material or different materials. Further, at this time, "the thickness of the glass substrate 16" means the total thickness of all the layers.

[Polyoxygenated resin layer]

The polyoxyxene resin layer 14 can prevent the glass substrate 16 from being displaced before the operation of separating the glass substrate 16 from the support substrate 12, and can prevent the glass substrate 16 and the like from being broken by the separation operation.

The surface 14a of the polyoxyxene resin layer 14 that is in contact with the glass substrate 16 is peelably adhered to the first main surface 16a of the glass substrate 16. The polyoxyxene resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the interfacial peel strength (y) is lower than the interfacial peel strength between the polyoxynated resin layer 14 and the support substrate 12. (x).

In other words, when the glass substrate 16 and the support substrate 12 are separated, the interface between the first main surface 16a of the glass substrate 16 and the polyoxy-oxygen resin layer 14 is peeled off, and the interface between the support substrate 12 and the polyoxy-oxygen resin layer 14 is difficult. Stripped.

Therefore, the polyoxyxene resin layer 14 has surface characteristics that can be easily peeled off from the first main surface 16a of the glass substrate 16 but can be easily peeled off. which is, The polyoxyxene 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, etc., and at the same time, the glass substrate 16 can be peeled off without damaging the glass substrate 16. The degree of bonding combined with the degree of peeling.

In the present invention, the property of the surface of the polyoxyxene resin layer 14 which can be easily peeled off is referred to as peelability. On the other hand, the first main surface of the support substrate 12 and the polyoxynitride resin layer 14 are bonded by a bonding force which is relatively difficult to peel off.

On the other hand, the interfacial bonding force between the polyoxyxene resin layer 14 and the glass substrate 16 can be changed before and after the member for the electronic component is formed on the surface (the second main surface 16b) of the glass substrate 16 of the glass laminate 10 (that is, the peel strength) (x) or peel strength (y) can be changed). However, even after forming the member for an electronic component, the peel strength (y) is still lower than the peel strength (x).

We believe that the layers of the polyoxyxene resin layer 14 and the glass substrate 16 are bonded by a weak adhesion force or a combination of van der Waals forces. On the other hand, when the polyoxyxene resin layer 14 is formed on the surface layer of the glass substrate 16, if the polyoxyxylene resin of the polyoxyxylene resin layer 14 does not exhibit the adhesion and is sufficiently crosslinked, it is considered to be derived from the van der Waals. The combination of force and force.

However, the polyoxynoxy resin of the polyoxyxene resin layer 14 has a certain degree of weak adhesion and is not limited. In the case where the member for electronic component is to be formed on the laminate after the production of the glass laminate 10, the polyoxynitride layer 14 is condensed by a heating operation or the like. The resin is then applied to the surface of the glass substrate 16, and the bonding force between the layers of the polyimide resin layer 14 and the glass substrate 16 rises.

Optionally, the surface or layer of the polyoxyxide layer 14 before the lamination may be applied. The first main surface 16a of the front glass substrate 16 is subjected to a process of weakening the bonding force therebetween, and then laminated. By performing non-adhesion treatment or the like on the surface to be laminated and then laminating, the interfacial bonding force between the polyoxynoxy resin layer 14 and the layer of the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

The polyoxyxene resin layer 14 is bonded to the surface of the support substrate 12 with a strong bonding force such as an adhesive force or an adhesive force.

For example, as described above, by crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate 12, the crosslinked polyoxyxene resin can be adhered to the surface of the support substrate 12 to obtain high adhesion. Further, by applying a treatment for generating a strong bonding force between the surface of the support substrate 12 and the polyoxyxylene resin layer 14 (for example, treatment using a couplant), the surface between the support substrate 12 and the polyoxyalkyl resin layer 14 can be improved. Binding force.

The combination of the polyoxyxene resin layer 14 and the support substrate 12 with a high bonding force means that the interface peel strength (x) of both is high.

The thickness of the polyoxyxene resin layer 14 is not particularly limited, and is preferably 2 to 100 μm, more preferably 3 to 50 μm, and still more preferably 5 to 20 μm.

When the thickness of the polyoxyxene resin layer 14 is within this range, even if air bubbles or foreign matter are interposed between the polyoxynoxy resin layer 14 and the glass substrate 16, the occurrence of deformation defects of the glass substrate 16 can be suppressed.

Further, when the thickness of the polyoxyxene resin layer 14 is too thick, time and material are required for formation, so that it is not economical and the heat resistance is lowered. On the other hand, if the thickness of the polyoxyxene resin layer 14 is too thin, the adhesion between the polyoxymethylene resin layer 14 and the glass substrate 16 may be lowered.

Further, the polyoxyxene resin layer 14 may be composed of two or more layers. At this time, "joy The thickness of the oxy-resin layer 14" indicates the total thickness of all the layers.

Further, when the polyoxyxene resin layer 14 is composed of two or more layers, the resin forming each layer may be composed of a different crosslinked polyoxymethylene resin.

The polyoxynoxy resin of the polyoxyxene resin layer 14 is a crosslinked product of a crosslinkable organic polyoxyalkylene to be described later.

The details of the crosslinkable organopolyoxane and its crosslinked product will be described below in detail.

(crosslinkable organopolysiloxane and its crosslinks)

The crosslinkable organopolyoxane used in the present invention contains the oxoxane unit (A) represented by the formula (1) and has substantially no alkenyl group and alkynyl group.

In the present invention, the crosslinkable organopolyoxane "substantially free of alkenyl groups and alkynyl groups" specifically means that the crosslinkable organopolysiloxane has a bond to a germanium atom (Si) or the like contained in one molecule. The number of alkenyl groups and alkynyl groups (e.g., vinyl group, ethynyl group, etc.) is preferably 100 or less, preferably 50 or less, more preferably 10 or less, and still more preferably 0.

The number of alkenyl groups and alkynyl groups bonded to a ruthenium atom (Si) or the like can be measured, for example, by NMR or the like.

Further, as will be described later, the crosslinkable organopolysiloxane used in the present invention can be produced by polymerizing a specific decane compound. Therefore, in the present invention, a cross-linking organopolyoxane is produced without using a decane compound having an alkynyl group and/or an alkenyl group, and thus the crosslinkable organopolyoxane can be said to be "substantially free of an alkene. And alkynyl groups.

In general, the basic constituent unit of an organic polyoxane is one in which a monovalent organic group represented by a methyl group or a phenyl group has several bonds to a deuterium atom. To classify, and consist of the following units, etc.: a bifunctional oxirane unit called a D unit bonded with two organic groups, a T-unit bond with an organic group trifunctionality The oxoxane unit, referred to as the M unit, is bonded with three organic monofunctional oxirane units, and is referred to as a Q unit-free organic-bonded tetrafunctional oxoxane unit.

Further, the Q unit is a unit which does not have an organic group bonded to a ruthenium atom (an organic group having a carbon atom bonded to a ruthenium atom), but is still regarded as a siloxane unit in the present invention. In the following formula, R represents a monovalent organic group represented by a methyl group or a phenyl group.

In the oxoxane unit, the oxane bond is a bond in which two ruthenium atoms are bonded via one oxygen atom, so the oxygen atom of each ruthenium atom in the siloxane bond is regarded as 1/2, and It is expressed by O _1/2 in the formula.

More specifically, for example, in one D unit, one of the ruthenium atomic systems is bonded to two oxygen atoms, and each of the oxygen atoms is bonded to the ruthenium atom of the other unit, whereby the formula is -O _{1 / 2} -(R) ₂ Si-O _1/2 -. Since there are two O _1/2 , the D unit is generally represented by (R) ₂ SiO _2/2 . However, in the present invention, the M unit, the D unit, the T unit, and the Q unit are expressed by using the expression of O _1/2 for each oxygen atom in order to match the performance of the oxoxane unit (A) described later.

When the terminal unit of the polymer chain is a unit other than the M unit, an atom other than the 矽 atom of O _1/2 bonded to the terminal unit is equivalent to 1/2 of the oxygen atoms, and together constitute one oxygen atom. To represent an oxygen atom in a hydroxyl group or an alkoxy group or the like. When expressed in the same manner as the performance of the following siloxane unit, for example, the hydroxyl group of the ruthenium atom bonded to the terminal unit is -O _1/2 -H.

[Chemical 1]

In the oxoxane unit (A) described later in the present invention, two ruthenium atoms are respectively bonded to an oxygen atom, and each oxygen atom is bonded to a ruthenium atom outside the unit, and thus in the formula (1) is O _{1 /2} performance. From the viewpoint that the oxoxane unit (A) is bifunctional, it can be regarded as a D unit.

Hereinafter, in the present invention, the cross-linking organopolysiloxane is described by considering the oxoxane unit (A) as one of the D units.

R ¹ to R ^{4 in the} formula (1) each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group.

Examples of the alkyl group having a carbon number of 4 or less include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group and the like, wherein a methyl group or an ethyl group is further used. Preferably, the methyl group is preferred.

The above R ¹ to R ^{4 are} preferably a methyl group or a phenyl group from the viewpoint of suppressing decomposition of the polyfluorene oxide resin under high temperature treatment conditions.

In the formula (1), Ar represents a divalent aromatic hydrocarbon group which may have a substituent. Further, the two bonding positions of Ar are the bonding positions of the carbon atoms constituting the aromatic ring.

The number of carbon atoms contained in the divalent aromatic hydrocarbon group is not particularly limited, and from the viewpoint of suppressing decomposition of the polyoxymethylene resin under high-temperature treatment conditions, it is preferably 6 to 18, and preferably 6 to 12.

Specific examples of the divalent aromatic hydrocarbon group include a stretched phenyl group, an extended naphthyl group, a stretched biphenyl group, and a stretched triphenyl group. Among them, in view of the fact that the flexibility of the polyoxyxene resin layer 14 is good and the adhesion and peelability of the polyoxyxylene resin layer 14 to the glass substrate 16 are excellent, it is preferable to extend the phenyl group.

On the other hand, when it is desired to impart superior heat resistance to the polyoxyxene resin layer 14, it is preferred to use a polycyclic aromatic hydrocarbon group for Ar.

Further, the kind of the substituent is not particularly limited, and examples thereof include a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, an arylalkyl group, an aryloxy group, a heterocyclic group, an amine group, a nitro group, a cyano group, and the like. .

When Ar has a substituent, the polyoxyxylene resin layer tends to be soft; and if Ar does not have a substituent, the heat resistance of the polyoxyalkylene resin layer is easily improved.

The crosslinkable organopolysiloxane of the present invention is a polymer containing only a siloxane unit (A) as a siloxane unit or a copolymer containing a siloxane unit (A) and other siloxane units.

The cross-linkable organopolysiloxane of the present invention is preferably a linear polymer, and the other siloxane units are preferably D units other than the siloxane unit (A).

When the crosslinkable organopolysiloxane is a linear polymer, the crosslinkable organopolyoxane has a polymer containing only a siloxane unit (A) and a siloxane containing unit. (A) and other D unit polymers, polymers containing oxoxane units (A) and M units, and polymers containing siloxane units (A) and other D units and M units. However, two or more types of the siloxane unit (A), other D units, and M units may be present.

Further, the crosslinkable organopolyoxane in the present invention may also be a non-linear polymer having a small number of branches. At this time, in addition to a small number of T units or Q units which cause branching, the D unit in the above linear polymer or, in some cases, the M unit.

The crosslinkable organopolyoxane in the present invention is crosslinkable, for example, an organopolyoxygen composed of only a fluorinated unit (A) in which all of R ¹ to R ⁴ are a methyl group and Ar is a phenyl group. The alkane is crosslinkable and can be crosslinked by heat or ultraviolet rays.

In the cross-linking organopolysiloxane of the present invention, a polymer containing only a siloxane unit (A) as a D unit, and a polymer containing a siloxane unit (A) and other D units are Preferably, the polymer containing the oxoxane unit (A) and other D units is preferred.

The crosslinker (polyanthracene resin) of the organopolyoxane containing other D units is softer than the crosslinker (polyoxyl resin) of the organopolyoxyalkylene containing no other D unit, and the polyfluorene The adhesiveness of the oxygen resin layer to the glass substrate is good.

Further, when the other D unit is a D unit containing an alkenyl group, the crosslinkability can be improved, and the decomposition of the crosslinked product (polyoxymethylene resin) under high temperature treatment conditions can be suppressed.

The D unit other than the siloxane unit (A) is preferably a oxoxane unit (B) represented by the formula (2).

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group.

The alkyl group having a carbon number of 4 or less may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group or the like, wherein a methyl group or an ethyl group is further used. Preferably, the methyl group is preferred.

From the viewpoint of suppressing the decomposition of the polyoxymethylene resin under the conditions of high temperature treatment, R ⁵ and R ⁶ are preferably a methyl group or a phenyl group.

With regard to a preferred aspect of the oxoxane unit (B), a state in which the oxoxane unit (B) is a siloxane unit (B-1) or a siloxane unit (B-2) can be cited. The oxoxane unit (B-1) is that R ⁵ and R ⁶ are a phenyl group, and the oxoxane unit (B-2) is one of R ⁵ and R ⁶ which is an alkyl group having 4 or less carbon atoms and the other It is a phenyl group.

The crosslinkable organopolyoxane may further contain other oxoxane units (for example, M unit, T unit, and Q unit) other than the above-described siloxane unit (A) and the siloxane unit (B).

However, once there are multiple units with branches (T unit or Q unit), the softness of the crosslinked product (polyoxyl resin) is reduced, and once there are multiple M units, it may become an average number. A polymer having a low molecular weight lowers physical properties such as heat resistance.

Therefore, the amount should be less, D unit (矽 单元 单元 unit (A) and 矽 The content of the unit other than the oxyalkyl unit (B)) is preferably 0 to 20 mol%, more preferably 0 to 5 mol%.

When the crosslinkable organopolyoxane contains the above-described oxime unit (A) and the above siloxane unit (B), the total amount of the oxime unit (A) and the oxirane unit (B) The ratio of the alkane unit (A) is preferably from 10 to 90 mol%, more preferably from 30 to 90 mol%, and even more preferably from 40 to 60 mol%.

Further, the total ratio of the oxoxane unit (A) to the oxime unit (B) is preferably from 80 to 100 mol%, based on the total oxane unit in the crosslinkable organopolyoxane, 95~ 100% by mole is preferred.

Further, the bonding form of the oxoxane unit (A) and the oxirane unit (B) in the crosslinkable organopolysiloxane is not particularly limited, and may be, for example, a random copolymer, a block copolymer, or an alternating Any of the copolymers. Among them, an alternating copolymer is preferred from the viewpoint of suppressing decomposition of the polyoxymethylene resin under high-temperature treatment conditions.

In the present invention, the alternating copolymer of the oxoxane unit (A) and the oxoxane unit (B) means that the siloxane unit (A) and the siloxane unit (B) are bonded more than decane. A copolymer of a unit (A) bonded to a siloxane unit (A) and a total of a bond of a siloxane unit (B) and a siloxane unit (B).

These three kinds of linkages can be distinguished by, for example, ¹ H NMR measurement and ²⁹ Si NMR measurement, and the ratio of the relative numbers of the bonds can be calculated by the measurement.

The alternating copolymer of the oxoxane unit (A) and the oxirane unit (B) in the present invention may also contain a small number of random bonding groups or block bonding moieties.

The bonding ratio of the oxoxane unit (A) to the oxirane unit (B) in the alternating copolymer is preferably 80 to 100 mol%, based on the total of the above three types of bonding. 90~100% of the moles is better, and 95% to 100% of the moles is better.

In addition, although it is not used to distinguish whether it is an alternating copolymer, when the cross-linking polysiloxane of the present invention is an alternating copolymer, the oxirane unit (A) and the oxime in the alternating copolymer are The ratio of the alkane unit (A) is preferably 50 ± 5 mol%, based on the total of the alkane units (B).

The alternating copolymer in the present invention may be one type of polyoxynoxy resin, or two or more kinds of polyfluorene oxide resins may be mixed and adjusted so that the bonding ratio of the oxirane unit (A) to the oxirane unit (B) is the above Made with the appropriate ratio.

The number average molecular weight of the cross-linkable organopolysiloxane is not particularly limited, and GPC (gel) is used in view of good handleability, film formation property, and inhibition of decomposition of polyoxyl resin under high-temperature treatment conditions. The number average molecular weight in terms of polystyrene obtained by the osmotic chromatography method is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

The adjustment of the number average molecular weight of the crosslinkable organopolyoxane can be carried out by controlling the reaction conditions. For example, the molecular weight can be controlled by changing the amount or type of terminal groups or the mixing ratio of monomers. If the amount of the terminal group is increased, a low molecular weight substance can be obtained, and the amount of the terminal group can be reduced to obtain a high molecular weight. Further, by varying the monomer ratio, a low molecular weight product can be obtained, and a high molecular weight product can be obtained by making the ratio uniform.

The method for producing the crosslinkable organopolyoxane is not particularly limited as long as it contains the azide unit (A) represented by the above formula (1). For example, a decane compound represented by the formula (3) can be produced by a condensation reaction or a hydrolysis/condensation reaction.

If it is a cross-linking organopolyoxane having a siloxane unit (B), It can be produced using a decane compound represented by the formula (4).

A crosslinkable organopolyoxyalkylene having a further siloxane unit can be produced using a decane compound having one or more sterol groups or hydrolyzable groups.

The polymerization is usually carried out in an inert solvent, and it can be reacted only by heating without a catalyst. The reaction catalyst can also be used according to the needs.

The cross-linkable organopolysiloxane having a siloxane unit (A) and a method for producing the same are known, and are described in, for example, JP-A-H09-59387 and JP-A-2008-280402. The crosslinkable organopolysiloxane of the present invention and a method for producing the same can be used in such well-known documents.

In the formulae (3) and (4), R ¹ to R ^{6 have the} same meanings as R ¹ to R ⁶ in the formula (1) and the formula (2).

In the formula (3), X and Y each independently represent a hydroxyl group or a hydrolyzable group (for example, an amine group, a monoalkylamine group or a dialkylamine group such as a 1 to 3 amino group; a halogen group; an alkoxy group or the like).

The alternating copolymer can be obtained by polymerizing two monomers having different reactivity. For example, it is selected that the mutual reactivity of X and Y is higher than any of the reactivity of X and the reactivity of each other, wherein X is a decane. The polymerization reactive group of the decane compound represented by the above formula (3) in the unit (A), and Y is a polymerization reactive group of the decane compound represented by the above formula (4) in the siloxane unit (B), The two decane compounds are reacted in substantially molar amounts to produce an alternating copolymer. By making the reactivity of X and Y higher than the reactivity of each other and the reactivity of Y with each other, an alternating copolymer having a random bonding portion or a small number of block bonding portions can be obtained.

In the case of producing an alternating copolymer, it is preferred that one of X and Y is a hydroxyl group and the other is a 1 to 3 amine group such as an amine group, a monoalkylamino group or a dialkylamino group. In particular, one of them is a hydroxyl group and the other is a dialkylamine group, and X is preferably a hydroxyl group and Y is a dialkylamine group. Further, the alkyl group in the monoalkylamino group or the dialkylamino group is preferably an alkyl group having 4 or less carbon atoms, and more preferably a methyl group.

Alternate copolymers of organic polyoxyalkylenes and methods for their manufacture are generally known, for example, as described in Macromolecules 1998, 31, 8501 or Journal of Applied Polymer Science, Vol. 106, 1007, 2007. The alternating copolymers of the present invention and the method for producing the same can be used as described in the above-mentioned known documents.

For the specific production method, for example, an alternating copolymer can be produced by the following method: an organic solvent solution of the decane compound (X is a hydroxyl group) represented by the above formula (3) and the above formula (4) a method in which an organic solvent solution of a decane compound (Y is a dimethylamine group) is mixed at a ratio of a molar amount of a dioxane compound to a molar amount, and the reaction is carried out under heating and stirring; and one of the organic solvents is stirred under heating and stirring. The method in which the solution is added to another organic solvent solution in batch or continuously to carry out the reaction.

Crosslinkable organopolyoxane is formed by a predetermined crosslinking reaction The cross-linking is hardened to form a crosslinked product of the polyoxymethylene resin in the present invention.

The cross-linking form in the present invention may be, for example, cross-linking by heat treatment or ultraviolet rays or the like, and crosslinking by heat treatment is preferred.

In the case of heat treatment, any of R ¹ to R ⁴ in the formula (1) contained in the crosslinkable organopolyoxane used in the present invention is an alkyl group having 4 or less carbon atoms (in the case of A The base (Me) is representative, and the following is a case where a methyl group is taken as an example. Therefore, for example, a part of the Si-Me bond is cut at a temperature of 300 ° C or higher, and the cut portion or the like generates a new siloxane chain (Si). -O-Si), that is, cross-linking.

On the other hand, in the following, the reaction of the polyfluorene oxide resin which crosslinks the crosslinkable organopolyoxane to form a crosslinked product is only referred to as hardening of the crosslinkable organopolysiloxane.

[Glass laminate and its manufacturing method]

The glass laminate 10 of the present invention is a laminate having a support substrate 12, a glass substrate 16, and a polyoxyalkylene resin layer 14 interposed therebetween, as described above.

The method for producing the glass laminate 10 of the present invention is not particularly limited, but in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), a predetermined crosslinkable organic layer is formed on the surface of the support substrate 12. A method in which the polyoxyalkylene oxide is hardened to form the polyoxyxylene resin layer 14 is preferred. That is, the method is as follows: a layer of a crosslinkable organopolyoxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is hardened on the surface of the support substrate 12 to form a polyoxyxene resin layer 14, Next, the glass substrate 16 is laminated on the surface of the polyoxynoxy resin layer 14 of the polyoxyxylene resin layer 14 to produce a glass laminate 10 .

It is considered that if the crosslinkable organopolysiloxane is hardened on the surface of the support substrate 12, the interaction with the surface of the support substrate 12 during the hardening reaction is formed to enhance the surface of the polyoxyl resin and the support substrate 12. Peel strength. Therefore, even if the glass substrate 16 and the support base material 12 are made of the same material, the difference in the peeling strength between the polyoxynitride resin layer 14 and the both can be set.

Hereinafter, a step of forming a layer of a crosslinkable organopolysiloxane on the surface of the support substrate 12 and hardening the crosslinkable organopolysiloxane on the surface of the support substrate 12 to form the polyoxyxene resin layer 14 is referred to as In the "resin layer forming step", the step of laminating the glass substrate 16 on the surface of the polyoxyxylene resin layer 14 to form the glass laminate 10 is referred to as a "layering step", and the procedure of each step will be described in detail.

(Resin layer forming step)

In the resin layer forming step, a layer of a crosslinkable organopolyoxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is hardened on the surface of the support substrate 12 to form a polyoxyxene resin layer. 14.

In order to form a layer of the crosslinkable organopolyoxane on the support substrate 12, it is preferred to use a coating composition in which a crosslinkable organopolysiloxane is dissolved in a solvent, and the composition is coated on a support. A layer of a solution is formed on the substrate 12, followed by removal of the solvent to form a layer of a crosslinkable organopolyoxane. The thickness of the layer of the crosslinkable organopolysiloxane can be controlled by adjusting the concentration of the crosslinkable organopolyoxane or the like in the composition.

The solvent is not particularly limited as long as it is a solvent which can easily dissolve the crosslinkable organopolyoxane in an operating environment and can be easily volatilized and removed. Specific examples thereof include toluene, xylene, THF, and trichlorobenzene. Methane, etc.

The method of applying the composition containing the crosslinkable organopolysiloxane to the surface of the support substrate 12 is not particularly limited, and a known method can be used. For example, spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, gravure coating, and the like.

Next, the crosslinkable organopolysiloxane on the support substrate 12 is cured to form the polyoxyxene resin layer 14. More specifically, as shown in FIG. 2(A), a polysilicon oxide resin layer 14 is formed on the surface of at least one side of the support substrate 12 in this step.

The hardening method is preferably as described above by crosslinking by heat treatment. That is, it is preferable to manufacture the polyoxynoxy resin layer 14 by thermal hardening. The details of the thermal hardening are described below.

The temperature condition for thermally curing the crosslinkable organopolyoxane is preferably 300 to 475 ° C, and preferably 350 to 450 ° C. Moreover, the heating time is usually preferably 10 to 300, and preferably 20 to 120.

On the other hand, the crosslinkable organopolysiloxane is preferably cured by hardening (formal hardening) after pre-curing. By performing pre-hardening, the polyoxynitride resin layer 14 excellent in heat resistance can be obtained.

The pre-hardening is preferably carried out immediately after the removal of the solvent, and the step of removing the solvent from the layer to form a layer of the crosslinkable organopolyoxyalkylene and the step of pre-hardening are not particularly distinguished.

The removal of the solvent is preferably carried out by heating to 100 ° C or higher, and by preheating by heating to 150 ° C or higher.

Solvent removal and pre-hardening temperature and heating time at 100 It is preferable to carry out 5 to 60 at ~420 ° C, and it is preferable to carry out 10 to 30 minutes at 150 to 300 ° C. If it is 420 ° C or less, it is easy to produce a polysilicon oxide resin layer which is easy to peel off.

(layering step)

In the lamination step, the glass substrate 16 is laminated on the surface of the polyoxynoxy resin layer 14 of the polyoxynated resin layer 14 obtained in the resin layer forming step, thereby obtaining a layer having the support substrate 12 in sequence, and polyfluorene oxide. The step of the glass laminate 10 of the resin layer 14 and the layer of the glass substrate 16.

More specifically, as shown in FIG. 2(B), the surface 14a of the polyoxyxylene resin layer 14 on the side opposite to the support substrate 12 side and the glass substrate having the first main surface 16a and the second main surface 16b are provided. The first main surface 16a of the 16th layer is used as an accumulation layer, and the polyoxynoxy resin layer 14 and the glass substrate 16 are laminated to obtain a glass laminate 10.

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

For example, a method in which a glass substrate 16 is stacked on the surface of the polyoxyalkylene resin layer 14 under a normal pressure environment. Further, after the glass substrate 16 is stacked on the surface of the polyoxyalkylene resin layer 14 as needed, the glass substrate 16 is pressure-bonded to the polyoxyalkylene resin layer 14 using a roll member or a press. It is preferable to remove bubbles which are mixed between the layers of the polyoxynoxy resin layer 14 and the glass substrate 16 by pressure bonding using a roll member or a press.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum pressing method, it is preferable to suppress the incorporation of air bubbles and ensure good adhesion. By crimping under vacuum, even if tiny bubbles remain, the bubbles are not grown by heating, so there is also a problem that the deformation of the glass substrate 16 is not easily obtained. point.

When the glass substrate 16 is laminated, it is preferable to sufficiently wash the surface of the glass substrate 16 to be in contact with the polyoxynoxy resin layer 14 to laminate in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 16, which is desirable.

After the glass substrate 16 is laminated, a pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the polyoxynitride resin layer 14 can be improved, and an appropriate peel strength (y) can be formed, and the electronic component is less likely to occur in the member forming step described later. The productivity of electronic components can be improved by the displacement of components and the like.

The pre-annealing treatment conditions can be appropriately selected depending on the type of the polyoxynoxy resin layer 14 to be used, and from the viewpoint that the peel strength (y) between the glass substrate 16 and the polyoxyxene resin layer 14 can be more appropriate. It should be heated at 300 ° C or higher (ideally 300 to 400 ° C) for more than 5 minutes (ideally 5 to 30 minutes).

The polyoxyxyl resin layer 14 to be formed to have a difference in peel strength with respect to the first main surface of the glass substrate 16 and peel strength with respect to the first main surface of the support substrate 12 is not limited to the above method.

For example, in the case of using the support substrate 12 having a higher adhesion to the surface of the polyoxyxene resin than the material of the glass substrate 16, the crosslinkable organopolyoxane can be cured on either of the release surfaces to produce A film of a polyoxyxene resin is laminated between the glass substrate 16 and the support substrate 12 while being laminated.

Moreover, the adhesion pair produced by the hardening of the crosslinkable organopolysiloxane When the glass substrate 16 is sufficiently low and the adhesion is sufficiently high enough for the support substrate 12, the crosslinkable organopolysiloxane can be hardened between the glass substrate 16 and the support substrate 12 to form a polyoxyxene resin layer. 14.

Further, even if the support substrate 12 is made of the same glass material as the glass substrate 16, the treatment for improving the adhesion of the surface of the support substrate 12 can be performed to improve the peel strength to the polyoxynated resin layer 14. The following methods and the like can be exemplified by a chemical method (primer treatment) such as a decane coupling agent that chemically raises the fixing force, a physical method such as a flame treatment to increase the surface active group, and a blasting method such as sand blasting. A mechanical treatment method such as treatment for increasing the surface roughness to increase the resistance.

(glass laminate)

The glass laminate 10 of the present invention can be used in various applications, for example, in the manufacture of panels for display devices, PV, thin film secondary batteries, and electronic components such as semiconductor wafers on which circuits are formed on the surface. Further, for this use, the glass laminate 10 is mostly exposed to high temperature conditions (for example, 400 ° C or higher) (for example, 1 hour or longer).

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

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

In the present invention, a glass substrate (a glass substrate with a member for an electronic component) containing a member for a glass substrate and a member for an electronic component is produced by using the laminate.

The method for producing the glass substrate of the member is not particularly limited. However, from the viewpoint of excellent productivity of the electronic component, it is preferable to form a member for an electronic component on the glass substrate in the glass laminate. A laminate having a member for an electronic component, and a glass substrate on the side of the glass substrate of the polyoxyxylene resin layer as a peeling surface from the laminated body of the member for electronic component assembly, and separated into a glass substrate with an attached member and agglomerated oxygen A support substrate for the resin layer.

In the following, a step of forming a laminate for a member for an electronic component by forming a member for an electronic component on a glass substrate in the above-mentioned glass laminate is referred to as a "member forming step", and will be incorporated from a laminate of members for an electronic component. The step of separating the glass substrate of the attached member and the supporting substrate of the agglomerated epoxy resin layer with the peeling surface of the glass substrate side interface of the polyoxyxylene resin layer is referred to as a "separation step".

The materials and procedures used in each step are described in detail below.

(component forming step)

The member forming step is a step of forming a member for an electronic component on the glass substrate 16 in the glass laminate 10 obtained by the above-described laminating step. More specifically, as shown in FIG. 2(C), the electronic component member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16, and the laminated body 22 for the electronic component is obtained.

First, the electronic component member 20 used in this step will be described in detail, and then the step program will be described in detail.

(component for electronic components (functional components))

The electronic component member 20 is a glass base formed in the glass laminate 10 A member on the board 16 that forms at least a portion of the electronic component.

More specifically, the electronic component member 20 includes a member such as a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, a member for a display device). , a member for a solar cell, a member for a film secondary battery, and a circuit for an electronic component).

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

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

Further, examples of the CCD or CMOS include a metal of a conductive portion, ruthenium oxide or tantalum nitride of an insulating portion, and various types of circuits such as a pressure sensor and an acceleration sensor. Various components such as a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board.

(step procedure)

The method for producing the laminated body 22 of the electronic component-attached member is not particularly limited, and the second main surface of the glass substrate 16 of the glass laminate 10 can be formed by a conventionally known method depending on the type of the constituent member of the electronic component member. 16b A member 20 for an electronic component is formed on the surface.

In addition, the electronic component member 20 may not be a member (hereinafter referred to as "total member") which is finally formed on the second main surface 16b of the glass substrate 16, but is a part of the total member (hereinafter referred to as "partial member"). The glass substrate with a part of the member peeled off from the polyoxynoxy resin layer 14 may be a glass substrate (corresponding to an electronic component described later) of the affixing member in a subsequent step.

The member for other electronic components may be formed on the peeling surface (first main surface 16a) of the glass substrate of the total member peeled off from the polyoxynitride resin layer 14.

Further, after assembling the laminated body of the total member, the electronic component can be manufactured by peeling off the supporting base material 18 of the agglomerated silicone resin layer from the laminated body of the additional member. Further, after assembling the laminate of two sheets of the total member, the support substrate 18 of the two agglomerated epoxy resin layers is peeled off from the laminate of the additional member to produce an attachment member having two glass substrates. The glass substrate.

For example, in the case of manufacturing an OLED, the surface of the glass substrate 16 on the side opposite to the side of the polyoxyxene resin layer 14 (corresponding to the second main surface 16b of the glass substrate 16) is formed in the glass laminate 10. The organic EL structure is formed or processed by forming various transparent layers: forming a transparent electrode; further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed; The back electrode; and sealing using a sealing plate. Specific examples of the formation or treatment of the layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, in the production of a TFT-LCD, there are various steps of a TFT forming step of using a resist liquid on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by CVD and sputtering. General law A thin film transistor (TFT) is formed on a metal film and an oxidized metal film formed by a film method, and a CF forming step is performed on the second main surface 16b of the glass substrate 16 of the other glass laminate 10 to form a resist liquid. Forming a pattern to form a color filter (CF); and, the bonding step is to laminate the layered body of the TFT obtained in the TFT forming step and the layered body of the CF obtained in the CF forming step. .

In the TFT formation step or the CF formation step, TFT or CF is formed on the second main surface 16b of the glass substrate 16 by a known photolithography technique, etching technique, or the like. At this time, a resist liquid is used as a coating liquid for pattern formation.

Further, before forming the TFT or CF, the second main surface 16b of the glass substrate 16 can be washed as needed. As the washing method, a well-known dry washing or wet washing can be used.

In the bonding step, the thin film transistor forming surface of the laminated body with the TFT is opposed to the color filter forming surface of the laminated body with CF, and is pasted with a sealant (for example, an ultraviolet curing type sealant for cell formation). Hehe. Then, a liquid crystal material is injected into a cell formed of a laminate body with TFTs and a laminate body with CF. The method of injecting the liquid crystal material is, for example, a vacuum injection method and a dropping injection method.

(separation step)

The separation step is a step shown in Fig. 2(D): the interface between the polyoxyxylene resin layer 14 and the glass substrate 16 is used as a peeling surface in the laminate 22 of the member for electronic component obtained by the above-described member forming step. The glass substrate 16 (the glass substrate with the member) and the support substrate 18 with the agglomerated epoxy resin layer are laminated to the electronic component member 20, and the member 20 for the electronic component is obtained. And a glass substrate 24 attached to the glass substrate 16.

In the case where the electronic component member 20 on the glass substrate 16 is a part necessary for forming the total constituent member at the time of peeling, the remaining constituent members may be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 16 and the support base material 18 of the agglomerated epoxy resin layer is not specifically limited. Specifically, for example, a sharp blade can be inserted into the interface between the glass substrate 16 and the polyoxymethylene resin layer 14, and after the opening end of the peeling is applied, the mixed fluid of water and compressed air is sprayed to perform peeling.

It is preferable that the support substrate 12 of the laminated body 22 with the electronic component member is placed on the upper side and the electronic component member 20 side is on the lower side, and the electronic component member 20 side is vacuum-adsorbed to the fixed plate. Upper (in the case where the support substrate is laminated on both sides), in this state, the cutter is first inserted into the interface between the glass substrate 16 and the polyoxyalkylene resin layer 14. Then, 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 insertion tool. In this way, an air layer can be formed at the interface between the polyoxy-oxygen resin layer 14 and the glass substrate 16 or the agglomerative fracture surface of the polyoxy-oxygen resin layer 14, and the air layer can be spread over the interface or the entire surface of the cohesive failure surface. The support substrate 12 can be easily peeled off.

Further, the support substrate 12 can be laminated with another new glass substrate to produce the glass laminate 10 of the present invention.

Further, when the glass substrate 24 of the member is separated from the glass laminate 10, the moisture of the static eliminator layer 14 or the glass substrate 24 of the member member can be suppressed from being electrostatically adsorbed by the static eliminator or by controlling the humidity.

The manufacturing method of the above-mentioned member glass substrate 24 is suitable for manufacturing A small display device used in mobile terminals such as smart phones or tablet PCs. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, an MIM type, an IPS type, a VA type, and the like. Basically, any of the passive drive type and the active drive type can be applied.

The glass substrate 24 of the member which is produced by the above-mentioned method is a panel for a display device which has a glass substrate and a member for display devices, a solar cell which has a glass substrate and the member for solar cells, and the glass substrate and the film secondary battery A film secondary battery of a member, and an electronic component having a glass substrate and a member for an electronic component. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

Example

The invention will be specifically described by way of examples and the like, but the invention is not limited by the examples.

In the following, a glass plate made of an alkali-free borosilicate glass (a 274 mm in length, a 274 mm in width, a thickness of 0.2 mm, a coefficient of linear expansion of 38 × 10 ^-7 /° C, and a product name "AN100" manufactured by Asahi Glass Co., Ltd.) is used for the glass substrate. ).

In addition, a glass plate (longitudinal 274 mm, horizontal 274 mm, thickness 0.4 mm, linear expansion coefficient 38×10 ^-7 /° C., manufactured by Asahi Glass Co., Ltd.) consisting of the same alkali-free borosilicate glass was used as the support substrate. AN100").

<Production Example 1: Production of crosslinkable organopolysiloxane (Sx1)>

1,4-bis(hydroxydimethylindenyl)benzene (41.6 parts by mass, manufactured by Gelest, Inc.) which is a compound constituting the siloxane unit (A) in a nitrogen atmosphere And bis(dimethylamino)diphenyl decane (54 parts by mass, manufactured by Gelest, Inc.) as a compound constituting the siloxane unit (B), and added to dehydrated toluene (160 parts by mass, manufactured by Kanto Chemical Co., Ltd.) . After the reaction solution was stirred at 85 ° C for 1 hour, the reaction solution was further heated to 110 ° C and stirred 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 (1500 parts by mass) for reprecipitation treatment. Then, the precipitate was collected, and vacuum-dried to obtain a cross-linkable organopolysiloxane (Sx1) which was colorless and transparent and liquid.

The number average molecular weight (in terms of polystyrene) measured by a GPC (gel permeation chromatography) apparatus (manufactured by Tosoh Corporation) of the obtained cross-linkable organopolysiloxane (Sx1) was 5.0 × 10 ³ .

Next, the structure of the crosslinkable organopolyoxane (Sx1) was identified by ¹ H NMR measurement, ²⁹ Si NMR measurement, and ¹³ C NMR measurement. The spectrum assignment in the ¹ H NMR measurement and the ²⁹ Si NMR measurement is described in Journal of Applied Polymer Science, 2007, 106, 1007-1013.

¹ H NMR, ²⁹ Si NMR and ¹³ C NMR measuring devices: ECA600 manufactured by JEOL RESONANCE

¹ H NMR measurement method: CDCL ₃ was added to the sample and prepared so that the sample concentration became 10% by mass. The baseline used tetramethyl decane.

²⁹ Si NMR measurement method: CDCL ₃ was added to the sample and prepared so that the sample concentration became 30% by mass. Further, acetone acetonide chromium salt was added as a tempering reagent, and it was adjusted to 0.1% by mass based on the sample. The baseline used tetramethyl decane.

¹³ C NMR measurement: CDCL ₃ was added to the sample and prepared so that the sample concentration became 10% by mass. The baseline used tetramethyl decane.

The composition of the copolymer was determined from ¹ H NMR measurement. Each of the distributions was determined by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013 from the spectrum obtained by ¹ H NMR measurement.

Bond-related information can be obtained from ²⁹ Si NMR and ¹³ C NMR.

The spectrum obtained from ²⁹ Si NMR measurement was determined by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013.

As a result of the measurement, it was confirmed that the oxirane unit (A) and the oxoxane unit (B) were alternately arranged. Further, it was confirmed that the bond between the siloxane unit (A) and the siloxane unit (B) was 90 mol% in the crosslinkable organopolyoxane (Sx1).

Further, the ratio of the total oxoxane unit in the crosslinkable organopolyoxane (Sx1) is 50 mole % of the siloxane unit (A) and 50 mole % of the siloxane unit (B) .

<Production Example 2: Production of crosslinkable organopolysiloxane (Sx2)>

In a nitrogen atmosphere, 1,4-bis(hydroxydimethylhydrazino)benzene (41.6 parts by mass, manufactured by Gelest, Inc.) as a compound constituting the siloxane unit (A) and as a constituent oxoxane The bis(dimethylamino)methylphenyl decane (41.6 parts by mass, manufactured by Gelest, Inc.) of the compound of the unit (B) was added to dehydrated toluene (183 parts by mass, manufactured by Kanto Chemical Co., Ltd.). After the reaction solution was stirred at 85 ° C for 1 hour, the reaction solution was further heated to 110 ° C and stirred for 1 hour. After the stirring is completed, the reaction solution is naturally cooled to room temperature, and then the reaction solution is added to the solution A. The reprecipitation treatment was carried out in an alcohol (1700 parts by mass). Then, the precipitate was collected, and vacuum-dried to obtain a cross-linkable organic polysiloxane (Sx2) which was colorless and transparent and liquid.

The number average molecular weight (in terms of polystyrene) measured by a GPC (gel permeation chromatography) apparatus (manufactured by Tosoh Corporation) of the obtained cross-linkable organopolysiloxane (Sx2) was 1.0 × 10 ⁴ .

Next, the structure of the crosslinkable organopolyoxane (Sx2) was identified in the same manner as in Production Example 1, and as a result, it was confirmed that the oxirane unit (A) and the siloxane unit (B) were alternately arranged and alternately copolymerized. Things. It was also confirmed that the bond between the siloxane unit (A) and the siloxane unit (B) was 90 mol% in the crosslinkable organopolyoxane (Sx2).

Further, the ratio of the total oxoxane unit in the crosslinkable organopolyoxane (Sx2) is 50 mole % of the siloxane unit (A) and 50 mole % of the siloxane unit (B) .

<Example 1>

(Manufacture of support substrate with agglomerated epoxy resin layer)

First, the obtained cross-linkable organopolysiloxane (Sx1) (30 parts by mass) was dissolved in xylene (70 parts by mass) to prepare a liquid containing a crosslinkable organopolyoxane (Sx1). .

Then, the support substrate is washed with pure water, and then washed with UV to clean and purify.

Next, a liquid material containing a crosslinkable organopolyoxane (Sx1) (coating amount: 120 g/m ² ) was applied onto the first main surface of the supporting substrate by a spin coater.

Then heat-hardened in the atmosphere at 350 ° C for 60 minutes on the support base. A first epoxy resin layer having a thickness of 10 μm was formed on the first main surface of the material to obtain a support substrate having an agglomerated epoxy resin layer. On the other hand, in the support substrate of the obtained agglomerated epoxy resin layer, it was confirmed that the polyoxymethylene resin layer was free from cracks.

(Manufacture of glass laminate S1)

Next, the peelable surface of the polyoxynoxy resin layer of the support substrate of the agglomerated epoxy resin layer is opposed to the first main surface of the glass substrate, and the center of gravity of the two substrates is used at room temperature under a pressure of a laminate device. The two substrates are stacked in an overlapping manner to obtain a glass laminate S1.

Further, the obtained glass laminate S1 corresponds to the glass laminate 10 of Fig. 1 described above, and in the glass laminate S1, the interfacial peel strength (x) of the support substrate layer and the polyoxyxene resin layer is higher than that of the polysiloxane. Interfacial peel strength (y) between the resin layer and the glass substrate.

Next, the following evaluation was carried out using the obtained glass laminate S1.

(heat resistance evaluation)

A 50 mm square sample was cut out from the glass laminate S1, and the sample was placed in a hot air oven heated to 450 ° C (under a nitrogen atmosphere), and placed for 60 minutes, and then taken out. It was confirmed that the polyoxynoxy resin layer in the sample to be taken out was not foamed or colored, and thus it was evaluated that the decomposition of the polyoxymethylene resin layer was suppressed. Moreover, there is no case where the glass substrate is displaced.

(peelability assessment)

A 50 mm square sample was cut out from the glass laminate S1, and the sample was placed in a hot air oven heated to 450 ° C (under a nitrogen atmosphere), and placed for 60 minutes, and then taken out. Next, the second main surface of the glass substrate of the glass laminate S1 is vacuum-adsorbed to the fixed plate, and then is formed at one corner of the glass laminate S1. A stainless steel cutter having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the polyoxyxene resin layer, and a peeling opening was provided between the first main surface of the glass substrate and the peelable surface of the polyoxyalkylene resin layer. Then, the second main surface of the support substrate of the glass laminate S1 is adsorbed by a plurality of vacuum adsorption pads having a gap of 90 mm, and then sequentially rises from the adsorption pad close to the corner portion to form a glass substrate. The first main surface and the peelable surface of the polyoxymethylene resin layer are peeled off.

From the above results, it was confirmed that the glass substrate was peeled off (interfacial peeling) after the high-temperature heat treatment.

Further, the main portion of the polyoxyxene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the interfacial peel strength (x) of the support substrate layer and the resin layer was higher than that of the polyoxyxylene resin layer and the glass substrate. Interfacial peel strength (y).

<Example 2>

A supporting substrate of an agglomerated epoxy resin layer was prepared in the same manner as in Example 1 except that a crosslinkable organopolysiloxane (Sx2) was used instead of the crosslinkable organopolyoxyalkylene (Sx1). Thereafter, the glass laminate S2 was produced in the same manner.

On the other hand, in the support substrate of the obtained agglomerated epoxy resin layer, it was confirmed that the polyoxymethylene resin layer was free from cracks.

Further, in the obtained glass laminate S2, the interfacial peel strength (x) of the support base material layer and the polyoxyxene resin layer is higher than the interfacial peel strength (y) of the polyxanylene oxide resin layer and the glass substrate.

(heat resistance evaluation)

Heat resistance evaluation was performed in the same manner as in Example 1 using the obtained glass laminate S2. As a result, it was confirmed that the polyoxynoxy resin layer in the sample to be taken out was not foamed or colored, and thus it was evaluated that the decomposition of the polyoxynoxy resin layer was suppressed. Moreover, there is no case where the glass substrate is displaced.

(peelability assessment)

The peeling property evaluation was performed in the same manner as in Example 1 using the obtained glass laminate S2. As a result, it was confirmed that the glass substrate was peeled off (interfacial peeling) even after the high-temperature heat treatment.

Further, the main portion of the polyoxyxene resin layer was separated from the glass substrate together with the support substrate, and it was confirmed from the results that the interfacial peel strength (x) of the support substrate layer and the resin layer was higher than that of the polyoxyxylene resin layer and the glass substrate. Interfacial peel strength (y).

<Comparative Example 1>

100 parts by mass of polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KNS-320A) and a platinum-based catalyst (manufactured by Shin-Etsu Lee Co., Ltd.) using a solvent-free addition reaction type release paper having a structure of the formula (1) A glass laminate C1 was obtained in the same manner as in Example 1 except that a mixture of 2 parts by mass of the product name CAT-PL-56) was used instead of the liquid material containing the crosslinkable organopolyoxane (Sx1).

In addition, the aspect of the glass laminate C1 corresponds to the aspect described in Patent Document 1.

(heat resistance evaluation)

Heat resistance evaluation was performed in the same manner as in Example 1 using the obtained glass laminate C1. As a result, it was confirmed that the polyoxyn resin in the sample taken out The layer has foaming and coloring. Therefore, it is presumed that the polysiloxane resin layer has been decomposed.

(peelability assessment)

The peeling property evaluation was performed in the same manner as in Example 1 using the obtained glass laminate C1. As a result, the polyoxyxene resin layer is foamed, and a part of the first main surface adhering to the glass substrate is peeled off as in the state of aggregation failure.

<Example 3>

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

First, a film of tantalum nitride, hafnium oxide, or amorphous tantalum is sequentially formed on the second main surface of the glass substrate in the glass laminate S1 by a plasma CVD method. Next, a low concentration of boron was injected into the amorphous germanium layer by an ion doping apparatus, and subjected to a dehydrogenation treatment by heating at 450 ° C for 60 minutes in a nitrogen atmosphere. Next, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing apparatus. Further, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Then, a germanium 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 sputtering, and by using photolithography. Etching forms a gate electrode. Then, a high concentration of boron and phosphorus is implanted into a desired region of each of the N-type and the P-type by photolithography and an ion doping apparatus to form a source region and a drain region. Then, on the second main surface side of the glass substrate, a ruthenium oxide film is formed by a plasma CVD method to form an interlayer insulating film, aluminum is formed by sputtering, and a TFT electrode is formed by etching using photolithography. Then heated at 450 ° C for 60 minutes in a hydrogen atmosphere After the treatment, the hydrogenation treatment is performed, and a tantalum nitride film is formed by a plasma CVD method to form a passivation layer. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Further, indium tin oxide is formed into a film by sputtering, and the pixel electrode is formed by etching by photolithography.

Next, a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer are formed by sequentially forming a film on the second main surface side of the glass substrate by a vapor deposition method, and the hole injection layer is 4, 4'. 4"-gin(3-methylphenylphenylamino)triphenylamine, the hole transport layer is bis[(N-naphthyl)-N-phenyl]benzidine, and the luminescent layer is attached to 8 - Quinolinol aluminum complex (Alq ₃ ) mixed with 40% by volume of 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl In the case of naphthalene-1,5-dicarbonitrile (BSN-BCN), the electron transporting layer is Alq _3. Then, aluminum is formed into a film by sputtering, and a counter electrode is formed by etching using photolithography. On the second main surface side of the glass substrate, another glass substrate is bonded to each other via an ultraviolet curing type back layer, and an organic EL structure is formed on the glass substrate through the above procedure. The glass having the organic EL structure on the glass substrate is formed. The laminated body S1 (hereinafter referred to as the panel S1) is a laminated body of the member for electronic components of the present invention (a panel for a display device with a supporting substrate).

Next, after the sealing body side of the panel S1 is vacuum-adsorbed to the fixing plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate of the corner portion of the panel S1 and the polyoxyxylene resin layer, and the glass substrate and the polyoxynoxy resin are bonded. The interface of the layer imparts the beginning of the stripping. Further, after the surface of the support substrate of the panel S1 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the cutter is performed when the discharge fluid is sprayed on the interface by a static eliminator (manufactured by Keyence Corporation). Row. Next, the de-energized fluid is continuously sprayed by the static eliminator toward the formed gap while pulling up the vacuum absorbing pad. As a result, only the glass substrate on which the organic EL structure is formed can be left on the fixing plate, and the supporting substrate of the agglomerated epoxy resin layer can be peeled off.

Then, the peeled surface of the separated glass substrate was cleaned and purified in the same manner as in Example 1, and the separated glass substrate was cut and divided into a plurality of portions by a laser cutter or a scribe-break method. After that, the glass substrate on which the organic EL structure is formed is assembled with the counter substrate, and a module forming step is performed to fabricate the OLED. The OLED produced by this method does not cause problems in terms of characteristics.

<Example 4>

In this example, the glass laminate S1 obtained in Example 1 was used to manufacture an LCD.

First, two glass laminates S1 are prepared, and nitridation is sequentially formed by plasma CVD on the second main surface of one of the glass laminates S1 (hereinafter also referred to as "glass laminate S1-1"). A film of tantalum, niobium oxide, or amorphous tantalum. Next, boron of a low concentration is injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment is performed at 450 ° C for 60 minutes in a nitrogen atmosphere, and dehydrogenation treatment is performed. Further, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing apparatus. Next, by using a photolithography etching and ion doping apparatus, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Then, after forming a gate insulating film by a plasma CVD method on the second main surface side of the glass substrate, a molybdenum film is formed by sputtering, and a gate electrode is formed by etching using photolithography. . Next by photolithography and The ion doping apparatus injects a high concentration of boron and phosphorus into a desired region of each of an N-type and a P-type to form a source region and a drain region. Then, an interlayer insulating film is formed by a plasma CVD method on the second main surface side of the glass substrate, a film is formed by sputtering, and a TFT electrode is formed by etching using photolithography. Further, after heat treatment at 450 ° C for 60 minutes in a hydrogen gas atmosphere and hydrogenation treatment, a tantalum nitride film was formed by a plasma CVD method to form a passivation layer. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Then, an indium tin oxide film is formed by sputtering, and a pixel electrode is formed by etching using photolithography.

Next, another glass laminate S1 (hereinafter also referred to as "glass laminate S1-2") was subjected to heat treatment at 450 ° C for 60 minutes in an atmospheric gas atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate S1 by sputtering, and a light shielding layer is formed by etching using photolithography. Then, an anti-staining agent is applied by a die coating method on the second main surface side of the glass substrate, and a color filter layer is formed by photolithography and thermal hardening. An indium tin oxide film is formed by sputtering to form a counter electrode. Thereafter, the ultraviolet curable resin liquid is applied onto the second main surface side of the glass substrate by a die coating method, and a columnar spacer is formed by photolithography and thermal hardening. Further, the polyimide solvent solution was applied by a roll coating method, and an alignment layer was formed by thermal hardening to perform rubbing.

Then, the sealing resin liquid is drawn into a frame shape by a dispensing method, and the liquid crystal is dropped by a dispensing method in the frame, and then the glass substrate of the two glass laminated bodies S1 is formed using the glass laminated body S1-1 in which the pixel electrode is formed. The second main surface sides are bonded to each other, and an LCD panel is obtained by ultraviolet curing and heat curing.

Next, the second main surface of the glass laminate S1-1 is vacuum-adsorbed to the fixed plate, and a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the polyoxyn resin layer at the corner portion of the glass laminate S1-2. The peeling start end of the peeling surface of the first main surface of the glass substrate and the polyoxyalkylene resin layer is applied. Here, the insertion of the cutter is performed when a discharge fluid is sprayed on the interface by a static eliminator (manufactured by Keyence Corporation). Next, the de-energized fluid is continuously sprayed by the static eliminator toward the formed void while pulling up the vacuum adsorption pad. Then, the adsorption pad is raised after the second main surface of the support substrate of the glass laminate S1-2 is adsorbed by the vacuum adsorption pad. As a result, only the LCD empty cell to which the support substrate of the glass laminate S1-1 is attached is left on the fixed plate, and the support substrate of the agglomerated epoxy resin layer is peeled off.

Next, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed to the fixed plate, and the interface between the glass substrate and the polyoxyn resin layer at the corner portion of the glass laminate S1-1 is inserted. A stainless steel cutter having a thickness of 0.1 mm is provided at the peeling end of the peeling surface of the first main surface of the glass substrate and the polyoxyalkylene resin layer. Further, after the second main surface of the support substrate of the glass laminate S1-1 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, the support substrate to which the polyoxyxylene resin layer is fixed can be peeled off by leaving only the LCD unit on the fixed plate. In this way, a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm can be obtained.

Next, the LCD unit is divided into a plurality of LCD units by a cutting step. A step of attaching a polarizing plate to each of the completed LCD units is performed, and then a module forming step is performed to obtain an LCD. The LCD produced in this way does not cause problems in terms of characteristics.

<Example 5>

In this example, the glass laminate S1 obtained in Example 1 was used to produce an OLED.

First, a molybdenum film is formed by sputtering on the second main surface of the glass substrate in the glass laminate S1, and a gate electrode is formed by etching using photolithography. Then, a tantalum nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then an indium gallium zinc oxide film is formed by sputtering, and by using photolithography The etching forms an oxide semiconductor layer. Next, a tantalum nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a channel protective layer, and then a molybdenum film is formed by sputtering, and is formed by etching using photolithography. Source electrode and drain electrode. Then, heat treatment was carried out at 450 ° C for 60 minutes in the atmosphere. Then, a tantalum nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a passivation layer, and then an indium tin oxide film is formed by sputtering, and the pixel is formed by etching using photolithography. electrode.

Next, a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer are formed by sequentially forming a film on the second main surface side of the glass substrate by a vapor deposition method, and the hole injection layer is 4, 4', 4 "-Sodium (3-methylphenylphenylamino)triphenylamine, the hole transport layer is bis[(N-naphthyl)-N-phenyl]benzidine, the luminescent layer is based on 8- The quinolinol aluminum complex (Alq ₃ ) is mixed with 40% by volume of 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene In the case of -1,5-dicarbonitrile (BSN-BCN), the electron transport layer is Alq _{3. An} aluminum film is formed by sputtering, and the opposite electrode is formed by etching using photolithography. The second main surface side is sealed by laminating another glass substrate via an ultraviolet curable adhesive layer. The organic EL structure is formed on the glass substrate by the above procedure. The glass laminate S1 having the organic EL structure on the glass substrate ( The panel S1) is a laminated body of the member for electronic components of the present invention (a panel for a display device with a supporting substrate).

Then, after the sealing body side of the panel S1 is vacuum-adsorbed to the fixing plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the polyoxynated resin layer at the corner of the panel S1, and the glass substrate and the polycrystalline oxygen are bonded to the glass substrate. The interface of the resin layer imparts the beginning of the peeling. Further, after the surface of the support substrate of the panel S1 has been adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the cutter is performed when a discharge fluid is sprayed on the interface by a static eliminator (manufactured by Keyence Corporation). Next, the de-energized fluid is continuously sprayed by the static eliminator toward the formed gap while pulling up the vacuum absorbing pad. As a result, only the glass substrate on which the organic EL structure is formed can be left on the fixing plate, and the supporting substrate of the agglomerated epoxy resin layer can be peeled off.

Next, the peeled surface of the glass substrate separated in the same manner as in the first embodiment is cleaned and cleaned, and the separated glass substrate is cut into a plurality of cells by a laser cutter or a scribing split method. The OLED is fabricated by assembling a glass substrate on which an organic EL structure is formed and a counter substrate, and performing a module forming step. The OLED produced in this way does not cause problems in terms of characteristics.

As shown in Examples 1 and 2, since the crosslinked organic polyoxane of the present invention has substantially no alkenyl group and alkynyl group, the occurrence of outgassing can be suppressed even without high heat treatment, and no glass substrate is provided. The displacement is good and the peelability is good.

Industrial availability

The glass laminate of the present invention can be widely used in panels for display devices such as LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS, grating panel, PV, thin film secondary battery, The surface is formed in the field of electronic parts such as semiconductor wafers of circuits.

In addition, the entire contents of the specification, the claims, the drawings and the abstract of the Japanese Patent Application No. 2014-064419, filed on March 26, 2014, are hereby incorporated by reference.

10‧‧‧glass laminate

12‧‧‧Support substrate

14‧‧‧Polyoxy resin layer

14a‧‧‧ surface

16‧‧‧ glass substrate

16a‧‧‧1st main surface of the glass substrate

16b‧‧‧2nd main surface of the glass substrate

18‧‧‧Support substrate with polyoxyl resin layer

Claims (8)

A glass laminate comprising a support substrate layer, a polyoxyxylene resin layer and a glass substrate layer, wherein an interfacial peel strength of the support substrate layer and the polyoxyxylene resin layer is higher than the glass substrate layer and the foregoing The interfacial peeling strength of the polyoxyxene resin layer; the polyfluorene oxide resin of the polyfluorene oxide resin layer is a crosslinked product of a crosslinkable organopolyoxane, and the crosslinkable organopolyoxane contains the formula (1) a oxoxane unit (A) and substantially free of alkenyl and alkynyl groups; (In the formula (1), R ¹ to R ⁴ each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group; however, any of R ¹ to R ⁴ represents an alkyl group having 4 or less carbon atoms; and Ar represents an a divalent aromatic hydrocarbon group having a substituent). The glass laminate according to claim 1, wherein R ¹ to R ⁴ in the azide unit (A) are each independently an alkyl group having 4 or less carbon atoms. The glass laminate according to claim 1 or 2, wherein the crosslinkable organopolyoxane further contains a siloxane unit (B) represented by the formula (2); [Chemical 2] (In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 4 or less carbon atoms or a phenyl group). The glass laminate according to claim 3, wherein, in the crosslinkable organopolyoxane, the aforesaid siloxane unit (the total amount of the oxoxane unit (A) and the aforesaid siloxane unit (B) The ratio of A) is 30 to 90 mol%, and the total ratio of the aforementioned oxoxane unit (A) to the aforementioned oxane unit (B) is 80 to 100 mol% with respect to the total siloxane unit. The glass laminate according to claim 3 or 4, wherein the oxoxane unit (B) is a phenyl oxane unit (B-1) wherein R ⁵ and R ⁶ are phenyl or any of R ⁵ and R ⁶ The alkyl group having a carbon number of 4 or less and the other being a phenyl alkane unit (B-2). The glass laminate according to any one of claims 1 to 5, wherein Ar in the aforementioned siloxane unit (A) is a phenyl group, a naphthyl group, a phenyl group or a triphenyl group. The glass laminate according to any one of claims 1 to 6, wherein the crosslinkable organopolyoxane has a total number of alkenyl groups and alkynyl groups bonded to a halogen atom in one molecule of 100 or less. . The glass laminate according to any one of claims 1 to 7, wherein the crosslinkable organopolyoxane has a number average molecular weight of 5,000 to 100,000 in terms of polystyrene as measured by GPC.