JP2017030324A - Glass laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass laminate in which the occurrence of air bubbles between a glass substrate and a silicone resin layer in high-temperature heating processing is suppressed, and a method for producing the glass laminate.SOLUTION: In a first embodiment, a glass laminate 10 is provided which comprises a supporting base material 12, a silicone resin layer 14 and a glass substrate 16 in this order, and in which after the glass laminate 10 has been heated at 550°C for 10 minutes under nitrogen atmosphere, there is no air bubbles between the silicone resin layer 14 and the glass substrate 16 or when there is the air bubbles, the diameter of the air bubbles is less than 1 mm. In a second embodiment, a glass laminate 10 is provided which is identical to the glass laminate 10 in the first embodiment except that the silicone resin in the silicone resin layer 14 contains 91-99 mol% of an organosiloxy unit (T unit) represented by (R)SiOand 1-9 mol% of an organosiloxy unit (Q unit) represented by SiO.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass laminate and a method for producing the same.

  In order to improve the handleability of the thin glass substrate, a glass laminate is prepared by laminating a glass substrate and a support substrate via a resin layer (so-called silicone resin layer), and a display device or the like is provided on the glass substrate. A method of separating a glass substrate and a support substrate after forming an electronic device member has been proposed (see, for example, Patent Document 1).

International Publication No. 2013/058217

In recent years, with the increase in functionality and complexity of electronic device members to be formed, it is desired to perform treatment under higher temperature conditions (for example, 550 ° C.) when forming electronic device members. Gases attached or contained in the glass substrate or the silicone resin layer are released by the high-temperature heat treatment, and bubbles may be generated between the glass substrate and the silicone resin layer. When bubbles of a predetermined size or more are formed when forming the electronic device member at a high temperature, adverse effects such as displacement of the electronic device member are caused.
According to the knowledge of the present inventor, the glass laminate described in Patent Document 1 does not generate bubbles of a predetermined size or more between the glass substrate and the silicone resin layer in the heat treatment at 450 ° C. In (550 degreeC), the bubble more than a predetermined | prescribed magnitude | size may arise between a glass substrate and a silicone resin layer.

  The present invention has been made in view of the above points, and glass in which generation of bubbles (particularly, bubbles of a predetermined size or more) is suppressed between the glass substrate and the silicone resin layer in high-temperature heat treatment. It aims at providing a laminated body and its manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have suppressed the generation of bubbles between the glass substrate and the silicone resin layer even after high-temperature heat treatment by adopting a specific silicone resin layer. As a result, the present invention has been completed.

That is, the first aspect of the present invention is a glass laminate including a support base, a silicone resin layer, and a glass substrate in this order, and the glass laminate is heated at 550 ° C. for 10 minutes in a nitrogen atmosphere. After that, when there is no bubble between the silicone resin layer and the glass substrate, or there is a bubble, the glass laminate has a diameter of less than 1 mm.
In the first embodiment, the silicone resin in the silicone resin layer contains (R) an organosiloxy unit (T unit) represented by SiO _3/2 and an organosiloxy unit (Q unit) represented by SiO _2. ). R represents a hydrogen atom or an organic group.
In the first embodiment, the proportion of T units is 91 to 99 mol% with respect to all organosiloxy units, and the proportion of Q units is 1 to 9 mol% with respect to all organosiloxy units. It is preferable that
In the first embodiment, the silicone resin preferably further has an organosiloxy unit (D unit) represented by (R) ₂ SiO _2/2 .
In the first embodiment, the proportion of D units is 1 to 40 mol% with respect to all organosiloxy units, and the proportion of T units is 30 to 98 mol% with respect to all organosiloxy units. It is preferable that the ratio of the Q unit is 1 to 30 mol% with respect to the total organosiloxy unit.
Moreover, in the 1st aspect, it is preferable that the ratio of D unit is 1-35 mol% with respect to all the organosiloxy units.
Moreover, in the 1st aspect, it is preferable that the ratio of D unit is 1-15 mol% with respect to all the organosiloxy units.
Moreover, in a 1st aspect, it is preferable that a silicone resin is a hardened | cured material of curable silicone, and the weight average molecular weights of curable silicone are 5000-60000.
Moreover, in the 1st aspect, it is preferable that the thickness of a silicone resin layer is 0.001-100 micrometers.
Moreover, in the 1st aspect, it is preferable that the thickness of a glass substrate is 0.03-0.3 mm.
Moreover, it is preferable that surface roughness Ra by the side of the glass substrate of a silicone resin layer is 0.1-20 nm.
The second aspect of the present invention is that (R) an organosiloxy unit (T unit) represented by SiO _3/2 and an organosiloxy unit (Q unit) represented by SiO ₂ on a supporting substrate. A silicone resin in which the proportion of T units is 91 to 99 mol% with respect to all organosiloxy units, and the proportion of Q units is 1 to 9 mol% with respect to all organosiloxy units. It is a manufacturing method of a glass laminated body which has the process of forming the silicone resin layer containing, and the process of laminating | stacking a glass substrate on a silicone resin layer.
The third aspect of the present invention is that an organosiloxy unit (D unit) represented by (R) ₂ SiO _2/2 and an organo group represented by (R) SiO _3/2 are formed on a supporting substrate. It contains a siloxy unit (T unit) and an organosiloxy unit (Q unit) represented by SiO ₂ , and the proportion of D unit is 1 to 40 mol% with respect to all organosiloxy units, A silicone resin layer containing a silicone resin having a proportion of 30 to 98 mol% with respect to all organosiloxy units and a proportion of Q units of 1 to 30 mol% with respect to all organosiloxy units is formed. It is a manufacturing method of a glass laminated body which has a process and the process of laminating | stacking a glass substrate on a silicone resin layer.

  The present invention provides a glass laminate in which the generation of bubbles (particularly, bubbles of a predetermined size or more) is suppressed between a glass substrate and a silicone resin layer in a high-temperature heat treatment, and a method for manufacturing the same. can do.

It is typical sectional drawing of the glass laminated body which concerns on this invention. It is typical sectional drawing which shows one Embodiment of the manufacturing method of the glass substrate with a member which concerns on this invention in process order.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

FIG. 1 is a schematic cross-sectional view of a glass laminate according to the present invention.
As shown in FIG. 1, the glass laminated body 10 is a laminated body in which the support base material 12, the glass substrate 16, and the silicone resin layer 14 exist among them. The silicone resin layer 14 has one surface in contact with the support base 12 and the other surface in contact with the first main surface 16 a of the glass substrate 16.
In the glass laminate 10, the peel strength at the interface between the silicone resin layer 14 and the glass substrate 16 is lower than the peel strength at the interface between the silicone resin layer 14 and the support base 12, and the silicone resin layer 14 and the glass substrate 16 are It peels and isolate | separates into the laminated body of the silicone resin layer 14 and the support base material 12, and the glass substrate 16. FIG. In other words, the silicone resin layer 14 is fixed on the support base 12, and the glass substrate 16 is detachably laminated on the silicone resin layer 14.
The two-layer portion composed of the support base 12 and the silicone resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel. In addition, the two-layer part which consists of the support base material 12 manufactured in advance for manufacture of the glass laminated body 10 and the silicone resin layer 14 is called the support base material 18 with a resin layer.

  This glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Then, the glass laminated body in which the member for electronic devices was formed is isolate | separated into the support base material 12 and the glass substrate with a member, and the support base material 18 with a resin layer does not become a part which comprises an electronic device. The support substrate 18 with the resin layer is laminated with a new glass substrate 16 and can be reused as a new glass laminate 10.

The interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the silicone resin layer 14. And the interface of the support base material 12 and the silicone resin layer 14 peels. The interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y), and when a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, The interface between the silicone resin layer 14 and the glass substrate 16 is peeled off.
In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, when a stress is applied to the glass laminate 10 in the direction in which the support base 12 and the glass substrate 16 are peeled off, the glass laminate 10 is peeled off at the interface between the silicone resin layer 14 and the glass substrate 16 and glass It isolate | separates into the board | substrate 16 and the support base material 18 with a resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, it is preferable to form a silicone resin layer by crosslinking and curing curable silicone described later on the support substrate 12. The silicone resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of crosslinking and curing.
On the other hand, the bonding force of the silicone resin after cross-linking and curing to the glass substrate 16 is generally lower than the bonding force generated during the cross-linking and curing. Therefore, the glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the support base 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14.

In the glass laminate 10 of the present invention, generation of bubbles of a predetermined size or more is suppressed between the silicone resin layer 14 and the glass substrate 16 after a predetermined heat treatment. More specifically, after heating the glass laminate 10 at 550 ° C. for 10 minutes in a nitrogen atmosphere, there are no bubbles between the silicone resin layer 14 and the glass substrate 16 (no bubbles are observed), or If there are bubbles (bubbles are observed), the bubble diameter is less than 1 mm. Especially, in the point which the position shift of the member for electronic devices does not produce more easily, when there is no bubble or there exists a bubble, it is preferable that the diameter of the bubble is 0.5 mm or less.
The method for heat treatment and the method for observing bubbles after the heat treatment are as follows.
First, as the glass laminate 10 to be used, a glass laminate produced by a method described later is used. Specifically, a glass in which a support base 12, a silicone resin layer 14, and a glass substrate 16 are laminated. A 50 mm square (50 mm long × 50 mm wide) glass laminate for measurement is cut out from the laminate 10. The cutting method is not particularly limited, and the glass laminate 10 having a predetermined size is usually cut out by applying an etching knife from the glass substrate 16 side of the glass laminate 10. Next, the glass laminate for measurement is placed in a hot air oven heated to 550 ° C. and left for 10 minutes. Then, the glass laminate for measurement is taken out from the hot air oven, and the presence or absence of bubbles between the silicone resin layer 14 and the glass substrate 16 is visually observed. The observation target is the entire surface of the measurement glass laminate (length 50 mm × width 50 mm). When bubbles are not observed, it is determined that there are no bubbles, and the glass laminate to be measured satisfies the requirements of the present invention. When bubbles are observed, the diameter of the bubbles is measured. When bubbles are observed, if the diameter of the observed bubbles is less than 1 mm, the glass laminate to be measured satisfies the requirements of the present invention.
Note that the visual observation limit is usually about 0.1 mm in diameter.
When the bubbles are not perfectly circular, the equivalent circle diameter is the above diameter. The equivalent circle diameter is the diameter of a circle having the same area as the observed bubble area.

As a preferred embodiment of the glass laminate 10 of the present invention, there is no bubble between the silicone resin layer 14 and the glass substrate 16 before the heat treatment, or when there is a bubble, the diameter of the bubble is less than 1 mm. It is preferable that
The method for measuring bubbles is the same as described above.

  In addition, as a method of obtaining the glass laminated body which has the above characteristics, the method of using a predetermined silicone resin layer is mentioned, for example so that it may explain in full detail later, The method is not limited.

  Below, each layer (the support base material 12, the glass substrate 16, the silicone resin layer 14) which comprises the glass laminated body 10 is explained in full detail first, and the manufacturing method of a glass laminated body is explained in full detail after that.

[Supporting substrate]
The support base 12 supports the glass substrate 16 and prevents deformation, scratches, breakage, etc. of the glass substrate 16 during the manufacture of the electronic device member in a member forming step (step of manufacturing the electronic device member) described later. To prevent.
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Usually, since the member forming process involves heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16 and more preferably formed of the same material as the glass substrate 16. Preferably, the support base 12 is a glass plate. In particular, the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.
As will be described later, the support base 12 may be a laminate composed of two or more layers.

  When glass is employed as the material of the support substrate 12, for example, glass having various compositions such as glass containing alkali metal oxide (soda lime glass) and non-alkali glass can be used. Of these, alkali-free glass is preferred because of its low thermal shrinkage.

  The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicone resin layer 14, and the thickness of the glass laminate 10. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the silicone resin layer 14 is 0.1 mm, The thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 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 for reasons such as easy handling and difficulty in cracking. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in linear expansion coefficient between the support base 12 and the glass substrate 16 is preferably 150 × 10 ⁻⁷ / ° C. or less, more preferably 100 × 10 ⁻⁷ / ° C. or less, and further preferably 50 × 10 10. ^-7 / ℃ or less. If the difference is too large, the glass laminate 10 may be severely warped or the support substrate 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

[Glass substrate]
As for the glass substrate 16, the 1st main surface 16a touches the silicone resin layer 14, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the silicone resin layer 14 side.
The glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

The linear expansion coefficient of the glass substrate 16 is preferably 150 × 10 ⁻⁷ / ° C. or less, more preferably 100 × 10 ⁻⁷ / ° C. or less, and further preferably 50 × 10 ⁻⁷ / ° C. or less.
If the linear expansion coefficient of the glass substrate 16 is within the above range, when the TFT is formed on the glass substrate 16, the glass substrate 16 on which the TFT is formed under heating is cooled by the thermal contraction of the glass substrate 16. It is possible to suppress the occurrence of TFT position shift.

  The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

  The glass type of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

  As the glass of the glass substrate 16, glass suitable for the type of electronic device member and its manufacturing process is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate 16 is appropriately selected based on the type of device to be applied and its manufacturing process.

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

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

[Silicone resin layer]
The silicone resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support base 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation. A surface 14 a of the silicone resin layer 14 that contacts the glass substrate 16 is in close contact with the first main surface 16 a of the glass substrate 16. The silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peeling strength (y) at the interface is the peeling at the interface between the silicone resin layer 14 and the support base 12. Lower than strength (x).

The silicone resin layer 14 and the glass substrate 16 are considered to be bonded with a bonding force resulting from a weak adhesive force or van der Waals force.
Further, the silicone resin layer 14 is bonded to the surface of the support base 12 with a strong bonding force such as an adhesive force or an adhesive force, and a known method can be adopted as a method for improving the adhesion between the two. The silicone resin layer 14 is made of a silicone resin containing a predetermined organosiloxy unit. For example, as described later, the silicone resin layer 14 is formed on the surface of the support base 12 (more specifically, a curable silicone (organopolysiloxane) capable of forming a predetermined silicone resin is formed on the support base 12. The silicone resin in the silicone resin layer 14 can be adhered to the surface of the support base 12 and high bonding strength can be obtained. Moreover, the process (for example, process using a coupling agent) which produces strong bond strength between the support base material 12 surface and the silicone resin layer 14 is given, and between the support base material 12 surface and the silicone resin layer 14 The binding power of can be increased.

The thickness of the silicone resin layer 14 is not particularly limited, but the upper limit is preferably 100 μm (that is, 100 μm or less), more preferably 50 μm, and even more preferably 10 μm. Although a lower limit will not be specifically limited if it is the thickness which can peel, In many cases, it is 0.001 micrometer or more. When the thickness of the silicone resin layer 14 is in such a range, cracks are unlikely to occur in the silicone resin layer 14, and even if bubbles or foreign substances are present between the silicone resin layer 14 and the glass substrate 16, Generation | occurrence | production of the distortion defect of the glass substrate 16 can be suppressed.
The above thickness is intended to mean the average thickness, and the thickness of the silicone resin layer 14 at an arbitrary position of five or more points is measured with a contact-type film thickness measuring device, and these are arithmetically averaged.
The surface roughness Ra of the surface of the silicone resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably from 0.1 to 20 nm, more preferably from 0.1 to 10 nm, from the viewpoint that the laminateability and peelability of the glass substrate 16 are more excellent. Is more preferable.
In addition, as a measuring method of surface roughness Ra, it was performed according to JIS B 0601-2001, and the value which carried out arithmetic average of Ra measured in arbitrary five or more points | pieces corresponds to the said surface roughness Ra. .
The silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the silicone resin layers.

(Silicone resin)
As described above, the silicone resin layer 14 is made of a silicone resin containing a predetermined organosiloxy unit such that the glass laminate exhibits a predetermined property. The silicone resin is usually obtained by crosslinking and curing a curable silicone that can be converted into the silicone resin by a curing treatment. That is, the silicone resin corresponds to a cured product of curable silicone.
The curable silicone in the present invention is a mixture (monomer mixture) of hydrolyzable organosilane compounds that are monomers, or a partial hydrolysis condensate (organo) obtained by subjecting the monomer mixture to a partial hydrolysis condensation reaction. Polysiloxane). Moreover, the mixture of a partial hydrolysis-condensation product and a monomer may be sufficient. As curable silicone in this invention, the partial hydrolysis-condensation product of a monomer mixture is preferable.
In order to crosslink and cure the curable silicone, the crosslinking reaction is usually advanced by heating to cure (that is, thermosetting). And a silicone resin is obtained by thermosetting curable silicone. However, there are cases where heating is not necessarily required for curing, and room temperature curing can also be performed.

The organosiloxy unit includes a monofunctional organosiloxy unit called M unit, a bifunctional organosiloxy unit called D unit, a trifunctional organosiloxy unit called T unit, and a tetrafunctional organosiloxy unit called Q unit. The Q unit is a unit that does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as an organosiloxy unit (silicon-containing bonded unit) in the present invention. The monomers forming the M unit, D unit, T unit, and Q unit are also referred to as M monomer, D monomer, T monomer, and Q monomer, respectively.
In addition, all the organosiloxy units intend the sum total of M unit, D unit, T unit, and Q unit. The ratio of the number of M units, D units, T units, and Q units (molar amount) can be calculated from the value of the peak area ratio by ²⁹ Si-NMR.

In the organosiloxy unit, the siloxane bond is a bond in which two silicon atoms are bonded via one oxygen atom, so that the number of oxygen atoms per silicon atom in the siloxane bond is considered to be 1/2. Expressed as medium O _1/2 . More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit. The formula is —O _1/2 — (R) ₂ Si—O _1/2 — (R represents a hydrogen atom or an organic group). Since there are two O _{1/2 s} , the D unit is usually expressed as (R) ₂ SiO _2/2 (in other words, (R) ₂ SiO).
In the following description, an oxygen atom O ^* bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is intended to be an oxygen atom in a bond represented by Si—O—Si. To do. Accordingly, one O ^* exists between the silicon atoms of two organosiloxy units.

The M unit means an organosiloxy unit represented by (R) ₃ SiO _1/2 . Here, R represents a hydrogen atom or an organic group. The number (here 3) described after (R) means that three hydrogen atoms or organic groups are connected. That is, the M unit has one silicon atom, three hydrogen atoms or an organic group, and one oxygen atom O ^* . More specifically, the M unit has three hydrogen atoms or organic groups bonded to one silicon atom and an oxygen atom O ^* bonded to one silicon atom.
The D unit means an organosiloxy unit represented by (R) ₂ SiO _2/2 (R represents a hydrogen atom or an organic group). That is, the D unit is a unit having one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and two oxygen atoms O ^* bonded to other silicon atoms.
The T unit means an organosiloxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group). That is, the T unit is a unit having one silicon atom, one hydrogen atom or organic group bonded to the silicon atom, and three oxygen atoms O ^* bonded to another silicon atom.
Q unit means an organosiloxy unit represented by SiO ₂ . That is, the Q unit is a unit having one silicon atom and four oxygen atoms O ^* bonded to other silicon atoms.
Examples of the organic group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Aryl groups; aralkyl groups such as benzyl groups and phenethyl groups; halogen-substituted monovalent hydrocarbon groups such as halogenated alkyl groups such as chloromethyl groups, 3-chloropropyl groups, and 3,3,3-trifluoropropyl groups; Can be mentioned. The organic group is preferably an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms (preferably about 1 to 10 carbon atoms).

The structure of the silicone resin constituting the silicone resin layer 14 is not particularly limited as long as the glass laminate exhibits predetermined characteristics, but (R) an organosiloxy unit (T unit) represented by SiO _3/2 , and It is preferable that at least an organosiloxy unit (Q unit) represented by SiO ₂ is included.

As a 1st suitable aspect of a silicone resin, it contains T unit and Q unit, the ratio of T unit is 91-99 mol% with respect to all the organosiloxy units of a silicone resin, and the ratio of Q unit is, The aspect which is 1-9 mol% with respect to all the organosiloxy units of a silicone resin is mentioned.
In this preferred embodiment, the proportion of T units is preferably 92 to 98 mol%, more preferably 93 to 97 mol%, based on all organosiloxy units of the silicone resin.
In this preferred embodiment, the proportion of the Q unit is preferably 2 to 8 mol%, more preferably 3 to 7 mol%, based on all organosiloxy units of the silicone resin.
When the T unit and the Q unit are within the above ranges, the silicone resin takes a high-density crosslinked structure, and the generation or expansion of bubbles between the glass substrate and the silicone resin layer is suppressed in the high-temperature heat treatment. .
In addition, the ratio of the number (molar amount) of T unit and Q unit can be calculated from the value of the peak area ratio by ²⁹ Si-NMR.

As a 2nd suitable aspect of a silicone resin, it contains D unit, T unit, and Q unit, the ratio of D unit is 1-40 mol% with respect to all the organosiloxy units of silicone resin, The aspect whose ratio is 30-98 mol% with respect to all the organosiloxy units of a silicone resin, and the ratio of Q unit is 1-30 mol% with respect to all the organosiloxy units of a silicone resin is mentioned. .
In this preferred embodiment, the ratio of the D unit is preferably 5 to 40 mol%, more preferably 5 to 35 mol%, and still more preferably 5 to 15 mol% with respect to all organosiloxy units of the silicone resin.
In this preferred embodiment, the proportion of T units is preferably 40 to 90 mol%, more preferably 60 to 90 mol%, and even more preferably 75 to 90 mol% with respect to all organosiloxy units of the silicone resin.
In this preferred embodiment, the proportion of the Q unit is preferably from 5 to 20 mol%, more preferably from 5 to 15 mol%, based on all organosiloxy units of the silicone resin.
When the D unit, the T unit, and the Q unit are within the above ranges, the silicone resin takes a high-density crosslinked structure, and bubbles are generated or expanded between the glass substrate and the silicone resin layer in the high-temperature heat treatment. It is suppressed.
The ratio of the number (molar amount) of D units, T units, and Q units can be calculated from the value of the peak area ratio by ²⁹ Si-NMR.

The definition of R in the D unit ((R) ₂ SiO _2/2 ) and the T unit ((R) SiO _3/2 ) is a hydrogen atom or an organic group as described above. In terms of more excellent effects, R is preferably a monovalent hydrocarbon group, more preferably an alkyl group (preferably a methyl group) or an aryl group (preferably a phenyl group).

The D unit ((R) ₂ SiO _2/2 ) and the T unit ((R) SiO _3/2 ) have an alkyl group (preferably a methyl group) or an aryl group (preferably a phenyl group). Either one or both of them may be included.

The silicone resin can be manufactured using a known material.
For example, the curable silicone that can be converted into the silicone resin by the curing treatment includes a mixture of monomer hydrolyzable organosilane compounds (monomer mixture) and / or partial hydrolysis obtained by partial hydrolysis condensation reaction of the monomer mixture. A decomposition condensate (organopolysiloxane) is used.
The type of monomer used is not particularly limited as long as the above-described silicone resin having a predetermined organosiloxy unit is obtained.

The monomer (hydrolyzable organosilane compound) is usually represented by (R′—) _a Si (—Z) _4-a . However, a represents an integer of 0 to 3, R ′ represents a hydrogen atom or an organic group, and Z represents a hydroxyl group or a hydrolyzable group. In this chemical formula, a compound with a = 3 is an M monomer, a compound with a = 2 is a D monomer, a compound with a = 1 is a T monomer, and a compound with a = 0 is a Q monomer. In the monomer, the Z group is usually a hydrolyzable group. Further, when 2 or 3 R ′ are present (when a is 2 or 3), the plurality of R ′ may be different.

The curable silicone that is a partially hydrolyzed condensate is obtained by a reaction in which a part of the Z group of the monomer is converted to an oxygen atom O ^* . When the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted by a dehydration condensation reaction between two hydroxyl groups bonded to separate silicon atoms. Bonded through an oxygen atom O ^* . In the curable silicone, hydroxyl groups (or Z groups that have not been hydrolyzed) remain, and when the curable silicone is cured, these hydroxyl groups and Z groups react and cure in the same manner as described above. The cured product of curable silicone is usually a three-dimensionally crosslinked polymer (silicone resin).

When the Z group of the monomer is a hydrolyzable group, examples of the Z group include an alkoxy group, a chlorine atom, an acyloxy group, and an isocyanate group. In many cases, a monomer in which the Z group is an alkoxy group is used as the monomer. Such monomers are also referred to as alkoxysilanes.
The alkoxy group is a hydrolyzable group having a relatively low reactivity compared to a chlorine atom and the like, and a curable silicone obtained by using a monomer (alkoxysilane) in which the Z group is an alkoxy group has a hydroxyl group as the Z group. In addition, unreacted alkoxy groups often exist.

The curable silicone that can be the silicone resin is preferably a partially hydrolyzed condensate (organopolysiloxane) obtained from a mixture of hydrolyzable organosilane compounds from the aspects of reaction control and handling. The partially hydrolyzed condensate is obtained by partially hydrolyzing and condensing a monomer mixture in which a hydrolyzable organosilane compound is mixed so as to have the ratio of each of the above organosiloxy units. The method of partially hydrolytic condensation is not particularly limited. Usually, it is produced by reacting a mixture of a hydrolyzable organosilane compound in a solvent in the presence of a catalyst. As the catalyst, an acid catalyst or an alkali catalyst can be used. In addition, it is usually preferable to use water for the hydrolysis reaction. The partial hydrolysis-condensation product used in the present invention is preferably a product produced by reacting a mixture of hydrolyzable organosilane compounds in a solvent in the presence of an acid or alkaline aqueous solution.
A preferred embodiment of the hydrolyzable organosilane compound used is alkoxysilane. In other words, one preferred embodiment of the curable silicone is a curable silicone obtained by hydrolysis and condensation reaction of alkoxysilane.
Alkoxysilane is a hydrolyzable organosilane compound whose hydrolyzable group is an alkoxy group. When alkoxysilane is used, the degree of polymerization of the partially hydrolyzed condensate tends to increase, and the effects of the present invention are more excellent.

  Although the weight average molecular weight (Mw) of the said curable silicone is not restrict | limited in particular, 5000-60000 are preferable and 5000-30000 are more preferable at the point which the effect of this invention is more excellent. When Mw is 5000 or more, it is excellent from the viewpoint of applicability, and when Mw is 60000 or less, solubility in a solvent and applicability may be sufficient.

The manufacturing method in particular of the silicone resin layer 14 mentioned above is not restrict | limited, A well-known method is employable. As a manufacturing method of the silicone resin layer 14, as described later, a curable silicone that becomes the silicone resin is applied on the support base 12, and the curable silicone is crosslinked and cured to form the silicone resin layer 14. preferable. In order to form a layer of curable silicone on the support substrate 12, a curable composition containing curable silicone is used, and this curable composition is applied onto the support substrate 12, and if necessary. The solvent is preferably removed to form a curable silicone layer.
The curable composition may contain a solvent. In that case, the thickness of the curable silicone layer can be controlled by adjusting the concentration of the solvent. Among them, the content of the curable silicone in the curable composition containing the curable silicone is based on the total mass of the composition because the handleability is excellent and the control of the film thickness of the silicone resin layer 14 is easier. 1 to 100% by mass is preferable, and 1 to 50% by mass is more preferable.
The solvent is not particularly limited as long as the curable silicone can be easily dissolved in the working environment and can be easily volatilized and removed. Specific examples include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate and the like.

Moreover, in order to accelerate | stimulate sclerosis | hardenability of curable silicone, the curing catalyst may be contained in the curable composition as needed.
The curing catalyst is a catalyst that accelerates the hydrolysis reaction and / or condensation reaction of the curable silicone. The curing catalyst is preferably an organometallic curing catalyst, for example, an organic tin compound such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octylate; aluminum trimethoxide Organic aluminum compounds such as aluminum tris (acetylacetonate), aluminum tri-n-butoxide, aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), aluminum acetylacetonate; titanium tetra (monoethylethoxy) ), Organic titanium compounds such as titanium tetra (monoethyl ethoxide), titanium tetra (monobutyl ethoxide); zirconium tetra (monomethyl ethoxide) De), zirconium tetra (monoethyl ethoxide), zirconium tetra (monobutyl ethoxide), organic zirconium compound zirconium n-propylate and the like, and the like; and the like, which can be used alone or in combination of two or more.
Although the usage-amount of a curing catalyst is not restrict | limited in particular, 0.01-20 mass parts is preferable with respect to 100 mass parts of curable silicone at the point which the effect of this invention is more excellent, and 0.05-10 mass parts is more. preferable.

  Moreover, various additives may be contained in the curable composition. For example, a leveling agent may be included. Examples of the leveling agent include fluorine-based leveling agents such as Megafac F558, Megafac F560, and Megafac F561 (all manufactured by DIC). Especially, the leveling agent whose surface tension (mN / m) of a 0.1% PGME solution is 19 (mN / m) to 27 (mN / m) is preferable, and the range of the surface tension is 20 ( mN / m) to 25 (mN / m) is more preferable, and 22 (mN / m) to 24 (mN / m) is more preferable.

  The procedure for forming the silicone resin layer using curable silicone will be described in detail later.

[Glass laminate and manufacturing method thereof]
As described above, the glass laminate 10 of the present invention is a laminate in which the support base 12, the glass substrate 16, and the silicone resin layer 14 exist between them.
Although the manufacturing method of the glass laminated body 10 of this invention is not restrict | limited in particular, In order to obtain a laminated body whose peeling strength (x) is higher than peeling strength (y), the silicone resin layer 14 is formed on the support base material 12 surface. Is preferred. Especially, curable silicone is apply | coated to the surface of the support base material 12, a hardening process is performed, the silicone resin layer 14 is formed on the support base material 12 surface, and glass is then formed on the silicone resin surface of the silicone resin layer 14 A method of manufacturing the glass laminate 10 by laminating the substrate 16 is preferable.
When the curable silicone is cured on the surface of the support substrate 12, it is considered that the curable silicone adheres due to the interaction with the surface of the support substrate 12 during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate 12 increases. Therefore, even if the glass substrate 16 and the support base 12 are made of the same material, a difference can be provided in the peel strength between the silicone resin layer 14 and the both.
Hereinafter, a step of forming a curable silicone layer on the surface of the support base 12 and forming the silicone resin layer 14 on the surface of the support base 12 is a resin layer forming step, and a glass substrate is formed on the silicone resin surface of the silicone resin layer 14. The process of laminating 16 to form the glass laminate 10 is called a lamination process, and the procedure of each process will be described in detail.

(Resin layer forming process)
In the resin layer forming step, a curable silicone layer is formed on the surface of the support substrate 12, and the silicone resin layer 14 is formed on the surface of the support substrate 12.
In order to form a layer of curable silicone on the support substrate 12, a coating composition in which the curable silicone is dissolved in a solvent (corresponding to the curable composition) is used, and this composition is used as the support substrate. It is preferable to apply on 12 and form a solution layer, and then apply a curing treatment to form a silicone resin layer 14.

  The method for applying the curable composition on the surface of the support substrate 12 is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating.

Next, the curable silicone on the support substrate 12 is cured to form the silicone resin layer 14. More specifically, as shown in FIG. 2A, in this step, a silicone resin layer 14 is formed on the surface of at least one side of the support base 12.
The curing method is not particularly limited, but is usually performed by a heat curing treatment.
150-550 degreeC is preferable and, as for the temperature conditions to thermoset, 200-450 degreeC is more preferable. The heating time is usually preferably 10 to 300 minutes and more preferably 20 to 120 minutes. Note that the heating condition may be implemented stepwise by changing the temperature condition.

  In the thermosetting treatment, it is preferable to perform curing (main curing) after curing (precuring) and curing. By performing precure, the silicone resin layer 14 excellent in heat resistance can be obtained. Precuring is preferably performed following the removal of the solvent. In that case, there is no particular distinction between the step of removing the solvent from the layer to form a crosslinked layer and the step of performing precuring. The removal of the solvent is preferably performed by heating to 100 ° C. or higher, and precure can be continued by heating to 150 ° C. or higher. The temperature at which the solvent is removed and precured and the heating time are preferably 100 to 420 ° C. and 5 to 60 minutes, and more preferably 150 to 300 ° C. and 10 to 30 minutes. A silicone resin layer that is easily peeled when the temperature is 420 ° C. or lower is obtained.

(Lamination process)
In the laminating step, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the layer of the supporting base 12, the silicone resin layer 14, and the glass substrate 16 are laminated. This is a step of obtaining the glass laminate 10 provided in this order. More specifically, as shown in FIG. 2 (B), a glass substrate having a surface 14a opposite to the support base 12 side of the silicone resin layer 14, and a first main surface 16a and a second main surface 16b. The silicone resin layer 14 and the glass substrate 16 are laminated by using the first principal surface 16a of 16 as a lamination surface, and the glass laminate 10 is obtained.

The method in particular of laminating | stacking the glass substrate 16 on the silicone resin layer 14 is not restrict | limited, A well-known method is employable.
For example, a method of stacking the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 16 is overlaid on the surface of the silicone resin layer 14, the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 using a roll or a press. Air bubbles mixed between the silicone resin layer 14 and the glass substrate 16 can be removed relatively easily by pressure bonding using a roll or a press, which is preferable.

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to lead to a distortion defect of the glass substrate 16.

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

In addition, after laminating | stacking the glass substrate 16, you may perform a pre-annealing process (heat processing) as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 can be improved, and an appropriate peel strength (y) can be obtained. Misalignment of members is less likely to occur, and the productivity of electronic devices is improved.
The conditions for the pre-annealing treatment are appropriately selected according to the type of the silicone resin layer 14 to be used, but the peel strength (y) between the glass substrate 16 and the silicone resin layer 14 is more appropriate. From this point, it is preferable to perform heat treatment at 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or longer (preferably 5 to 30 minutes).

In addition, formation of the silicone resin layer 14 which provided the difference in the peeling strength with respect to the 1st main surface of the glass substrate 16 and the peeling strength with respect to the 1st main surface of the support base material 12 is not restricted to the said method.
For example, in the case where the support base material 12 having a higher adhesion to the surface of the silicone resin layer 14 than the glass substrate 16 is used, the curable silicone is cured on some peelable surface to produce a silicone resin film. The film can be interposed between the glass substrate 16 and the support base 12 and laminated simultaneously.
Moreover, when the adhesiveness by hardening of curable silicone is low enough with respect to the glass substrate 16, and the adhesiveness is high enough with respect to the support base material 12, a crosslinked material is formed between the glass substrate 16 and the support base material 12. The silicone resin layer 14 can be formed by curing.
Furthermore, even when the support base 12 is made of the same glass material as that of the glass substrate 16, it is possible to increase the peel strength with respect to the silicone resin layer 14 by performing a process for improving the adhesion of the support base 12 surface. For example, a chemical method (primer treatment) that improves the fixing force chemically such as a silane coupling agent, a physical method that increases surface active groups such as a flame (flame) treatment, or a surface such as a sandblast treatment Examples of such a mechanical processing method increase the catch by increasing the roughness of the material.

(Glass laminate)
The glass laminate 10 of the present invention can be used for various applications, for example, manufacturing electronic parts such as a display device panel, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface, which will be described later. The use to do is mentioned. In this application, the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 550 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

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

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 10 obtained in the said lamination process. More specifically, as shown in FIG. 2C, the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain a laminate 24 with the electronic device member. .
First, the electronic device member 22 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member 22 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 22, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on its surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body 24 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 16 of the glass laminated body 10 is used. The electronic device member 22 is formed on the surface 16b surface.
The electronic device member 22 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the silicone resin layer 14 can be used as a glass substrate with an all member (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the silicone resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.

  For example, when an OLED is manufactured as an example, an organic EL is formed on the surface of the glass laminate 10 opposite to the silicone resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form a structure, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed. Various layers are formed and processed, such as sealing with a plate. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

  Further, for example, when manufacturing a TFT-LCD, a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 16b of the glass substrate 16 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other using a sealing agent (for example, an ultraviolet curable sealing agent for cell formation). Thereafter, a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

(Separation process)
In the separation step, the glass substrate 16 (on which the electronic device member 22 is laminated) with the interface between the silicone resin layer 14 and the glass substrate 16 as the release surface from the laminate 24 with the electronic device member obtained in the member forming step. This is a step of obtaining a glass substrate 26 with a member including the electronic device member 22 and the glass substrate 16 by separating the glass substrate with a member), the silicone resin layer 14 and the support base 12.
When the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 26 with a member and the support base material 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off. Preferably, the electronic device member-attached laminate 24 is placed on the surface plate so that the support base material 12 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 side is vacuumed on the surface plate. In this state, the blade is first allowed to enter the interface between the glass substrate 16 and the silicone resin layer 14. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed at the interface between the silicone resin layer 14 and the glass substrate 16, and the air layer spreads over the entire interface, so that the support substrate 18 with the resin layer can be easily peeled off.
Moreover, the support base material 18 with a resin layer can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.

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

[Cleaning process]
The cleaning treatment step is a step of performing a cleaning treatment on the peeling surface (first main surface 16a) of the glass substrate 16 in the glass substrate with member 26 obtained in the separation step. By performing this step, it is possible to remove impurities such as silicone resin and silicone resin layer adhering to the release surface, metal pieces and dust generated in the member forming step adhering to the release surface, and cleaning the release surface. Sex can be maintained. As a result, the tackiness of a retardation film, a polarizing film, or the like attached to the release surface of the glass substrate 16 is improved.

  The method for the cleaning treatment is not particularly limited as long as the resin or dust attached to the release surface can be removed. For example, there are a method of thermally decomposing the deposit, a method of removing impurities on the peeled surface by plasma irradiation or light irradiation (for example, UV irradiation treatment), and a cleaning method using a solvent.

  The manufacturing method of the glass substrate 26 with a member mentioned above is suitable for manufacture of the small display apparatus used for mobile terminals, such as a mobile telephone and PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

  As the glass substrate 26 with a member manufactured by the above method, a panel for a display device having a glass substrate and a member for a display device, a solar cell having a glass substrate and a member for a solar cell, a glass substrate and a member for a thin film secondary battery. Examples thereof include a thin film secondary battery, an electronic component having a glass substrate and an electronic device member. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

In the above, although the aspect using the glass laminated body 10 was explained in full detail, an electronic device can also be manufactured using the glass laminated body 100 according to the procedure similar to the above.
In addition, when the glass laminated body 100 is used, in the said isolation | separation process, the support base material 12, the silicone resin layer 14, and the glass substrate 16 are used by making the interface of the support base material 12 and the silicone resin layer 14 into a peeling surface. And an electronic device including the electronic device member 22.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples. In this production example, the curable silicone was evaluated by the following items and methods.
(1) Evaluation of weight average molecular weight Mw The polystyrene conversion molecular weight was calculated | required by the gel permeation chromatography (GPC, HLC8220 by Tosoh Corporation, RI detection, column: TSK-GEL SuperHZ, eluent: tetrahydrofuran).

In Examples 1 to 37 and Comparative Examples 1 to 6 below, as a glass substrate, a glass plate made of non-alkali borosilicate glass (length 274 mm, width 274 mm, plate thickness 0.2 mm, linear expansion coefficient 38 × 10 ⁻⁷ / The product name “AN100” manufactured by Asahi Glass Co., Ltd. was used. Further, as a supporting base material, a glass plate made of non-alkali borosilicate glass (length 274 mm, width 274 mm, plate thickness 0.4 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) )It was used.

<Production Example 1: Production of curable silicone S1>
In a nitrogen atmosphere, methyltriethoxysilane (108 g) and tetraethoxysilane (6.5 g) were charged into a 1 L glass reactor and cooled to 0 ° C. After cooling, a solution obtained by diluting concentrated nitric acid (2 g) with distilled water (17 g) was added dropwise to the reactor. The reaction solution temperature was kept at 0 ° C. and stirred for 3 hours. Subsequently, a solution of tetrahydrofuran (75 g) and concentrated nitric acid (4 g) diluted with distilled water (33 g) was added to the reactor, and the mixture was stirred at room temperature for 1 hour, and then stirred at a reaction solution temperature of 40 ° C. for 4 hours. After completion of the stirring, the reaction solution was naturally cooled to room temperature, and distilled water (300 g) and ethyl acetate (300 g) were added. The ethyl acetate phase was separated and collected. The ethyl acetate phase was dehydrated over anhydrous magnesium sulfate and filtered. By drying in vacuo, a white solid curable silicone S1 was obtained (yield 85%).
The obtained curable silicone S1 had a weight average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) of 6.0 × 10 ⁴ . ^{By 29} Si NMR measurement, the copolymer composition of the curable silicone S1 was obtained as T / Q = 95/5 (molar ratio).

<Production Examples 2 to 43: Production of curable silicones S2 to S43>
Curable silicones S2 to S43 were produced according to the same procedure as in Production Example 1 except that the monomers used and the amounts used were changed as shown in Table 1.
In addition, as curable silicone S42-S43, the curable silicone (S1) and (S6) as described in the Example column of patent document 1 were used.

<Example 1>
The resulting curable silicone (S1) (100 parts by mass), leveling agent MegaFuck F561 (manufactured by DIC, 0.2 parts by mass), and curing catalyst (Wacker (registered trademark) Catalyst F) (manufactured by Asahi Kasei Wacker) 3 parts by mass) was dissolved in cyclohexanone to prepare a liquid (solid content concentration: 40% by mass) containing curable silicone (S1).
The support substrate was cleaned with pure water, and further cleaned by UV cleaning.
Next, a liquid material having a size of 274 mm in length and 274 mm in width and containing curable silicone (S1) was applied on the first main surface of the support base material with a spin coater.
Next, this is heat-cured at 250 ° C. for 30 minutes in the air to form a 4 μm-thick silicone resin layer on the first main surface of the support substrate, and support A (support substrate with resin layer) Got.
Next, the peelable surface of the silicone resin layer of the support A is opposed to the first main surface of a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) having the same size as the silicone resin layer and a thickness of 0.2 mm. Then, the two substrates were superposed at room temperature and atmospheric pressure using a laminating apparatus so that the centers of gravity of both substrates overlapped to obtain a glass laminate S1.

The obtained glass laminate S1 corresponds to the glass laminate 10 shown in FIG. 1 described above. In the glass laminate S1, the peel strength (x) at the interface between the support substrate and the silicone resin layer is a silicone resin. It was higher than the peel strength (y) between the interface between the layer and the glass substrate.
There were no bubbles between the silicone resin layer and the glass substrate.
Next, the following measurements were performed using the obtained glass laminate S1. The following evaluation results are summarized in Table 1 described later.

[Peelability evaluation]
A sample of 50 mm square (length: 50 mm × width: 50 mm) was cut out from the glass laminate S1, this sample was placed in a hot air oven heated to 550 ° C. (in a nitrogen atmosphere), left for 10 minutes, and then taken out. . Subsequently, after vacuum-adsorbing the 2nd main surface of the glass substrate of glass laminated body S1 to a surface plate, thickness 0. between the glass substrate of one corner part of glass laminated body S1, and a silicone resin layer. A 1 mm stainless steel cutting tool was inserted, and a trigger for peeling was given between the first main surface of the glass substrate and the silicone resin layer. And after adsorbing the 2nd main surface of the support base material of glass laminated body S1 with a several vacuum suction pad by 90 mm pitch, it raises in order from the suction pad near the said corner part, and is made into the 1st main surface of a glass substrate. The surface and the silicone resin layer were peeled off.
From the above results, it was confirmed that the glass substrate can be peeled even after the high-temperature heat treatment.
In addition, the main part of the silicone resin layer is separated from the glass substrate together with the support base material, and as a result, the peel strength (x) between the support base material and the silicone resin layer is between the silicone resin layer and the glass substrate. It was confirmed that it was higher than the peel strength (y).

[Foaming evaluation]
When forming the member for electronic devices on the glass substrate of a glass laminated body, the process under high temperature conditions is performed. If bubbles having a diameter of 1 mm or more are present between the silicone resin layer and the glass substrate after this treatment, the position of the electronic device member may be displaced and the process yield may be reduced. Therefore, after the heat treatment, it is important that no bubbles exist between the silicone resin layer and the glass substrate, or the size of the bubbles is less than a predetermined value. Therefore, the following foaming evaluation was performed.
A glass laminate (measurement sample) of 50 mm square (length: 50 mm × width: 50 mm) was cut out from the glass laminate S1 in a state in which the supporting base material, the silicone resin layer, and the glass substrate were laminated, and the cut glass laminate was cut out. Was placed in a hot air oven heated to 550 ° C. in a nitrogen atmosphere, taken out after standing for 10 minutes, and visually observed for the presence of bubbles between the silicone resin layer and the glass substrate in the cut glass laminate. And evaluated according to the following criteria.
“◎”: No bubbles after heating, or bubbles having a diameter of 0.5 mm or less are present “◯”: Bubbles having a diameter of more than 0.5 mm and less than 1 mm are present after heating “×”: Diameter of 1 mm or more after heating Bubbles exist “XX”: The product substrate completely peels off after heating

<Examples 2-37, Comparative Examples 1-6>
According to the same procedure as in Example 1, except that liquid materials containing curable silicones (S2) to (S43) shown in Table 1 below were used instead of the liquid material containing curable silicone (S1). Laminates S2 to S43 were produced.
In addition, the glass laminated body manufactured using curable silicone (SA) (A is an integer of 2-43) here is called glass laminated body SA. For example, a glass laminate manufactured using curable silicone (S3) corresponds to the glass laminate S3.
In addition, obtained glass laminated body S2-S43 corresponds to the glass laminated body 10 of FIG. 1 mentioned above, and in glass laminated body S2-S43, the peeling strength (x) of the interface of a support base material and a silicone resin layer. However, the peel strength (y) at the interface between the silicone resin layer and the glass substrate was higher.
Moreover, said [peelability evaluation] and [foaming evaluation] were implemented using obtained glass laminated body S2-S43. The results are summarized in Table 1.

In Examples 1 to 37, the surface roughness Ra on the glass substrate side of the silicone resin layer was in the range of 0.1 to 20 nm.
Moreover, in Examples 1-37, the thickness of the silicone resin layer was 4 μm.

In Table 1 below, “Me group” is the content (mol%) of the organosiloxy unit containing the Me (methyl) group with respect to all organosiloxy units. The “Ph group” is the content (mol%) of the organosiloxy unit containing a Ph (phenyl) group with respect to all organosiloxy units.
In Table 1 below, the “D unit” column, the “T unit” column, and the “Q unit” column are all D units, T units, and Q units contained in the silicone resin in the silicone resin layer, respectively. The content (mol%) relative to the organosiloxy unit.
The content of each unit was calculated by ²⁹ Si-NMR.
In Table 1, in the “Peelability Evaluation” column, “◯” indicates that the glass substrate can be peeled, and “x” indicates that the glass substrate cannot be peeled or the glass substrate is damaged.

In addition, in this manufacture example and the comparative example, the analysis of the silicone resin layer was performed by the item and method shown below.
(1) Analysis of bonding state of silicon atoms in silicone resin layer Using a nuclear magnetic resonance analyzer (solid ²⁹ Si-NMR: manufactured by JEOL RESONANCE, ECP600), the content (mol%) of each organosiloxy unit is determined. It was.

(2) Analysis of an organosiloxy unit having a methyl group and an organosiloxy unit having a phenyl group in a silicone resin layer Using a nuclear magnetic resonance analyzer (solid ¹ H-NMR: manufactured by JEOL RESONANCE Co., Ltd., ECP600) It calculated | required from the peak area ratio derived from Me group. The silicone resin layer is formed by applying a liquid material containing a curable silicone used in each example and comparative example on a glass substrate with a spin coater and heating and curing under the heating conditions of each example and comparative example. A solid sample in which a silicone resin layer was formed on a glass substrate and then the silicone resin layer was shaved with a razor blade was used. Depth 2 was used as the measurement method, and the measurement conditions were a pulse width of 2.3 μsec, a pulse repetition waiting time of 15 sec, an integration count of 16 scan, and a MAS rotation speed of 22 KHz. The standard of chemical shift was a peak derived from adamantane at 1.7 ppm. The chemical shift of solid ¹ H-NMR derived from each structure is as follows.
Ph group: 18 to 4 ppm
Me group: 4 to -10 ppm

(3) Film thickness of the silicone resin layer The film thickness of the silicone resin layer was measured using a surface roughness / contour shape measuring instrument (Surfcom 1400G-12 manufactured by Tokyo Seimitsu Co., Ltd.), which is a contact film thickness apparatus.

As shown in Table 1 above, in the glass laminate of the present invention, the generation of bubbles having a predetermined size or more was suppressed, and the peelability (separability) of the glass substrate was excellent.
On the other hand, as shown in Comparative Examples 1 to 6, when the predetermined silicone resin layer was not used, the desired effect was not obtained.

<Example 38>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate S1 by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed for dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method. A gate electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after a heat treatment and a hydrogenation treatment are performed in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as the hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel A) is an electron of the present invention. It is a laminated body with a member for devices.
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass A trigger for peeling is given to the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module. The process is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

<Example 39>
In this example, an LCD is manufactured using the glass laminate S1 obtained in Example 1.
First, two glass laminates S1 are prepared, and silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in one glass laminate S1-1 by plasma CVD. . Next, low concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, after a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after a heat treatment and a hydrogenation treatment are performed in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Next, the other glass laminate S1-2 is heat-treated in an air atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate S1 by a sputtering method, and a light shielding layer is formed by etching using a photolithography method. Next, a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing. Next, a film of indium tin oxide is formed by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
Next, the sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass sheets S1-1 on which the pixel electrodes are formed are used. The second main surface sides of the glass substrates of the glass laminate S1 are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.

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

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

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

<Example 40>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, molybdenum was formed into a film by sputtering method on the 2nd main surface of the glass substrate in glass laminated body S1, and the gate electrode was formed by the etching using the photolithographic method. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film, and subsequently an indium gallium zinc oxide film is formed by a sputtering method. An oxide semiconductor layer was formed by etching. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protective layer. Subsequently, a molybdenum film is formed by a sputtering method, and etching is performed using a photolithography method. A source electrode and a drain electrode were formed.
Next, heat treatment is performed in the atmosphere. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a passivation layer. Subsequently, indium tin oxide is formed by a sputtering method, and etching is performed using a photolithography method. A pixel electrode is formed.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as the hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by sputtering, followed by photolithography. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel B) is an electronic device according to the present invention. It is a laminated body with a member for devices (panel for display devices with a supporting substrate).
Subsequently, after vacuum-adsorbing the sealing body side of the panel B to the surface plate, a stainless steel blade having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner of the panel B, and glass A trigger for peeling is given to the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel B with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module. The process is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

DESCRIPTION OF SYMBOLS 10 Glass laminated body 12 Support base material 14 Silicone resin layer 16 Glass substrate 18 Support base material with a resin layer 22 Electronic device member 24 Laminated body with electronic device member 26 Glass substrate with member

Claims (13)

A glass laminate comprising a supporting substrate, a silicone resin layer, and a glass substrate in this order,
After the glass laminate is heated at 550 ° C. for 10 minutes in a nitrogen atmosphere, there is no bubble between the silicone resin layer and the glass substrate, or when there is a bubble, the diameter of the bubble is 1 mm. The glass laminate is less than. The silicone resin in the silicone resin layer includes (R) an organosiloxy unit (T unit) represented by SiO _3/2 and an organosiloxy unit (Q unit) represented by SiO _2. The glass laminate according to 1. R represents a hydrogen atom or an organic group. The proportion of the T unit is 91 to 99 mol% with respect to the total organosiloxy unit,
The glass laminated body of Claim 2 whose ratio of the said Q unit is 1-9 mol% with respect to all the organosiloxy units. The glass laminate according to claim 2, wherein the silicone resin further has an organosiloxy unit (D unit) represented by (R) ₂ SiO _2/2 . R represents a hydrogen atom or an organic group. The ratio of the D unit is 1 to 40 mol% with respect to all organosiloxy units,
The proportion of the T unit is 30 to 98 mol% with respect to all organosiloxy units,
The ratio of the Q unit is 1 to 30 mol% with respect to all organosiloxy units.
The glass laminated body of Claim 4.   The glass laminated body of Claim 5 whose ratio of the said D unit is 1-35 mol% with respect to all the organosiloxy units.   The glass laminated body of Claim 5 or 6 whose ratio of the said D unit is 1-15 mol% with respect to all the organosiloxy units.   The glass laminate according to any one of claims 1 to 7, wherein the silicone resin in the silicone resin layer is a cured product of curable silicone, and the weight average molecular weight of the curable silicone is 5000 to 60000. .   The glass laminated body of any one of Claims 1-8 whose thickness of the said silicone resin layer is 0.001-100 micrometers.   The glass laminated body of any one of Claims 1-9 whose thickness of the said glass substrate is 0.03-0.3 mm.   The glass laminated body of any one of Claims 1-10 whose surface roughness Ra by the side of the said glass substrate of the said silicone resin layer is 0.1-20 nm. On the supporting substrate, it contains an organosiloxy unit (T unit) represented by (R) SiO _3/2 and an organosiloxy unit (Q unit) represented by SiO ₂ , and the proportion of the T unit is: Forming a silicone resin layer containing a silicone resin that is 91 to 99 mol% with respect to all organosiloxy units, and the ratio of the Q unit is 1 to 9 mol% with respect to all organosiloxy units; ,
And a step of laminating a glass substrate on the silicone resin layer. R represents a hydrogen atom or an organic group. On the supporting substrate, an organosiloxy unit (D unit) represented by (R) ₂ SiO _2/2 , an organosiloxy unit (T unit) represented by (R) SiO _3/2 , and SiO ₂ Organosiloxy units represented (Q units), the proportion of the D units is 1 to 40 mol% based on the total organosiloxy units, and the proportion of the T units is based on the total organosiloxy units. A step of forming a silicone resin layer containing a silicone resin that is 30 to 98 mol% and the ratio of the Q unit is 1 to 30 mol% with respect to all organosiloxy units;
And a step of laminating a glass substrate on the silicone resin layer. R represents a hydrogen atom or an organic group.