KR20160119080A - Glass laminate - Google Patents

Abstract

A glass laminate capable of easily peeling off a glass substrate even after high-temperature heating treatment and suppressing decomposition of a silicon resin layer is provided. A silicone resin layer, and a glass substrate layer in this order, wherein the silicone resin in the silicone resin layer has an organosiloxy unit represented by T3, and a ratio of T3 to the total organosiloxy unit Wherein the organosiloxy unit (A-1) wherein the total proportion of the organosiloxy units to be displayed is 80 to 100 mol%, R in the T3 is a phenyl group, and the organosiloxy unit (B- (A-1): (B-1)) of 80 to 20: 20 to 80, and satisfies the predetermined peel strength relationship.
_{T3: R-SiO 3/2} ( wherein, R represents a phenyl group or a methyl group)

Description

Glass laminate {GLASS LAMINATE}

The present invention relates to a glass laminate, and more particularly to a glass laminate having a predetermined silicone resin layer.

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

In recent years, in order to cope with the above-mentioned problem, a glass laminate in which a thin plate glass substrate and a reinforcing plate are laminated is prepared, an electronic device member such as a display device is formed on a thin plate glass substrate of a glass laminate, A method of separating a support plate from a substrate has been proposed (see, for example, Patent Document 1). The reinforcing plate has a support plate and a silicone resin layer fixed on the support plate, and the silicone resin layer and the thin plate glass substrate are brought into close contact with each other in a peelable manner. The interface between the silicon resin layer of the glass laminate and the thin plate glass substrate is peeled off and the reinforcing plate separated from the thin plate glass substrate is laminated with a new thin plate glass substrate and can be reused as a glass laminate.

International Publication No. 2007/018028

With respect to the glass laminate described in Patent Document 1, higher heat resistance has been required in recent years. As the electronic device member formed on the glass substrate of the glass laminate becomes more sophisticated and complicated, the temperature for forming the electronic device member becomes higher and the time for exposing to the higher temperature is also longer There are a few cases.

The glass laminate described in Patent Document 1 can withstand treatment at 300 ° C for 1 hour in air. However, according to the study by the present inventors, when the glass laminate described in Patent Document 1 is subjected to the treatment at 450 ° C for 1 hour, when the glass substrate and the support substrate are to be separated from each other, And if it is forcibly peeled off, a part of the glass substrate is destroyed, and as a result, the productivity of the electronic device is deteriorated in some cases.

In addition, the silicon resin layer in the glass laminate described in Patent Document 1 decomposes at 450 캜 in a short time, and a large amount of out gas is generated. Such generation of outgas causes contamination of a member for an electronic device formed on a glass substrate, resulting in a deterioration in the productivity of the electronic device.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a glass laminate capable of easily peeling off a glass substrate even after high-temperature heating treatment and suppressing decomposition of a silicon resin layer.

Means for Solving the Problems The present inventors have intensively studied in order to solve the above problems, and as a result, have completed the present invention.

That is, the present invention relates to a silicone resin composition comprising a support substrate layer, a silicone resin layer and a glass substrate layer in this order, wherein the silicone resin in the silicone resin layer has an organosiloxy unit represented by T3 described later, An organosiloxy unit (A-1) wherein the total proportion of organosiloxy units represented by T3 to siloxy units is 80 to 100 mol%, R in T3 is a phenyl group, and an organosiloxy unit (A-1) / (B-1)) of the organosiloxane unit (B-1) is 80/20 to 20/80, the ratio of the peel strength of the interface to the layer of the glass substrate of the silicon resin layer And the peel strength of the interface with respect to the layer of the support substrate of the resin layer is different.

In the present invention, it is preferable that the silicone resin has an organosiloxy unit represented by Q described later.

In the present invention, it is preferable that the silicone resin is a cured product of a curable organopolysiloxane, and the curable organopolysiloxane has an organosiloxy unit represented by T1 to T3 described later in a ratio (molar amount) : T2: T3 = 0 to 5: 20 to 50: 50 to 80 (provided that the relationship of T1 + T2 + T3 = 100 is satisfied).

In the present invention, the number average molecular weight of the curable organopolysiloxane is preferably 500 to 2,000.

In the present invention, it is preferable that the weight average molecular weight / number average molecular weight of the curable organopolysiloxane is 1.00 to 2.00.

In the present invention, it is preferable that the particle diameter of the curable organopolysiloxane measured by the dynamic light scattering method is 0.5 to 100 nm.

In the present invention, the curable organopolysiloxane is preferably an organopolysiloxane obtained by hydrolyzing phenyltrichlorosilane and methyltrichlorosilane.

In the present invention, the thickness of the silicone resin layer is preferably 0.1 to 30 mu m.

In the present invention, it is preferable that the supporting substrate is a glass plate.

In the present invention, it is preferable that the peel strength at the interface with respect to the glass substrate layer of the silicone resin layer is lower than the peel strength at the interface with the support substrate layer of the silicon resin layer. The present invention in this form is hereinafter also referred to as a first embodiment.

Further, in the present invention, it is preferable that the peel strength of the interface with respect to the layer of the glass substrate of the silicon resin layer is higher than the peel strength of the interface with respect to the layer of the support substrate of the silicon resin layer. The present invention in this form is hereinafter also referred to as a second form.

According to the present invention, it is possible to easily peel off a glass substrate even after high-temperature heating treatment, and to provide a glass laminate in which degradation of the silicon resin layer is suppressed.

1 is a schematic cross-sectional view of a first embodiment of a glass laminate according to the present invention.
2 is a schematic cross-sectional view showing one embodiment of a method of manufacturing a glass substrate having a member according to the present invention in the order of the process.
3 is a schematic cross-sectional view of a second embodiment of the glass laminate according to the present invention.

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

The characteristic feature of the glass laminate of the present invention is that the silicone resin in the silicone resin layer contains a predetermined amount of an organosiloxy unit represented by T3 described later and an organosiloxy unit in which R in the T3 is a phenyl group -1) and the molar ratio ((A-1) / (B-1)) of the organosiloxy unit (B-1) in which R is a methyl group in T3 is within a predetermined range. More specifically, by including a predetermined amount of the organosiloxy unit represented by T3 in the silicone resin, the heat resistance of the silicone resin layer is improved.

The present inventors have also studied the reason why it is difficult to separate the glass substrate and the support substrate from each other in the glass laminate after the high-temperature heat treatment, and found out that the functional groups included in the surface of the silicone resin layer affect the glass substrate. For example, when the Si-Me group is contained in the surface of the silicone resin layer, the Si-OH group is liable to be relatively Si-OH after heating at a high temperature of 250 ° C or higher. Therefore, if the amount of Si-Me groups contained in the silicon resin layer is excessively large, many Si-OH groups appear on the surface of the silicon resin layer after the high-temperature heat treatment and the bonding force with the adjacent substrate (for example, As a result, separation of the silicon resin layer from the substrate adjacent to the silicon resin layer becomes difficult. On the other hand, the Si-Ph group is relatively unlikely to be converted into the Si-OH group. However, if the Si-Ph group is excessively large, cross-linking hardening of the curable organopolysiloxane hardly progresses due to steric hindrance of the substituent, and the degree of crosslinking of the silicone resin layer is lowered. As a result, the mechanical strength of the silicone resin layer is lowered or unreacted Si-OH groups derived from the organopolysiloxane remain on the surface of the silicone resin layer, resulting in deterioration of the releasability of the glass substrate. The present inventors have found out the composition of the silicone resin layer which is liable to peel off the glass substrate even after the high-temperature heat treatment by adjusting the molar ratio ((A-1) / (B-1)) based on the above knowledge.

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

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

≪ First Embodiment >

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

As shown in Fig. 1, the glass laminate 10 is a laminate in which a layer of the supporting substrate 12, a layer of the glass substrate 16, and a silicon resin layer 14 are present therebetween. The silicon resin layer 14 has one side thereof contacting the layer of the supporting substrate 12 and the other side contacting the first main surface 16a of the glass substrate 16.

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

This glass laminate 10 is used until a member forming process described later. That is, this 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. Thereafter, the glass laminate formed with the electronic device member is separated into the supporting substrate 12 and the glass substrate having the member, and the supporting substrate 18 having the resin layer does not constitute a part constituting the electronic device. The supporting base material 18 having a resin layer can be laminated with a new glass substrate 16 and reused as a new glass laminate 10. [

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

In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). The glass laminate 10 is bonded to the silicon resin layer 14 and the glass substrate 16 when stress is applied to the glass laminate 10 in the direction in which the supporting substrate 12 and the glass substrate 16 are peeled off, And is separated into a glass substrate 16 and a supporting substrate 18 having a resin layer.

The peel strength (x) is preferably sufficiently high as compared with the peel strength (y). Raising the peel strength x can increase the adhesion of the first silicon resin layer 14 to the support substrate 12 and maintain a higher adhesion force with respect to the glass substrate 16 after the heat treatment .

In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, it is preferable that the silicone resin layer is formed by crosslinking and curing the curable organopolysiloxane described below on the support substrate 12. [ The silicone resin layer 14 bonded to the supporting substrate 12 with high bonding force can be formed by the adhesive force at the time of crosslinking curing.

On the other hand, it is usual that the bonding force of the silicone resin to the glass substrate 16 after the cross-linking curing is lower than the bonding force which occurs at the time of cross-link curing. The glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the supporting substrate 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14. [

First, each layer (supporting substrate 12, glass substrate 16, and silicone resin layer 14) constituting the glass laminate 10 will be described in detail, and then the glass laminate 10 The manufacturing method will be described in detail.

[Supporting substrate]

The support substrate 12 supports the glass substrate 16 and reinforces the glass substrate 16 so that the glass substrate 16 is deformed during the manufacturing process of the electronic device member in the member forming process , Scratches, breakage, and the like.

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

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

The thickness of the supporting substrate 12 may be thicker or thinner than that of the glass substrate 16. Preferably, the thickness of the supporting substrate 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicon resin layer 14, and the thickness of the glass laminate 10. For example, if the current member forming process is designed to process a substrate with a thickness of 0.5 mm and the sum of the thickness of the glass substrate 16 and the thickness of the silicon resin layer 14 is 0.1 mm, Is set to 0.4 mm. The thickness of the supporting substrate 12 is preferably 0.2 to 5.0 mm in general.

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for ease of handling and difficulty in breaking. Further, it is preferable that the thickness of the glass plate is 1.0 mm or less, since it is desirable that the rigidity to bend properly and not bend when peeling off after formation of the electronic device member.

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

[Glass Substrate]

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

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

If the coefficient of linear expansion of the glass substrate 16 is large, the member forming process often involves heat treatment, and thus various problems are likely to occur. For example, in the case of forming the TFT on the glass substrate 16, if the glass substrate 16 on which the TFT is formed under heating is cooled, there is a fear that the positional deviation of the TFT becomes excessive due to heat shrinkage of the glass substrate 16 have.

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 pull call method, a lubrication method, or the like is used. In particular, the glass substrate 16 having a small thickness can be obtained by heating the glass molded into a plate shape once at a moldable temperature and stretching it by stretching or the like (thinning method) (lead-row method).

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

As the glass of the glass substrate 16, glass suitable for the kind of the electronic device member and the manufacturing process thereof is employed. For example, the glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free from an alkali metal component in that the elution of the alkali metal component tends to be affected by the liquid crystal Earth metal components are included). Thus, the glass of the glass substrate 16 is appropriately selected based on the kind of device to be applied and the manufacturing process thereof.

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

The thickness of the glass substrate 16 is preferably 0.03 mm or more for ease of manufacturing the glass substrate 16, ease of handling of the glass substrate 16, and the like.

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

[Silicone resin layer]

The silicon resin layer 14 prevents the positional deviation of the glass substrate 16 until the operation of separating the glass substrate 16 and the supporting substrate 12 is performed, Thereby preventing damage to the semiconductor device. The surface 14a of the silicon resin layer 14 in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16. [ The peeling strength y of the interface between the silicon resin layer 14 and the supporting substrate 12 is set so that the peeling strength y of the interface between the silicon resin layer 14 and the supporting substrate 12 Is less than the peel strength (x) of the interface between the two layers. The bonding force of the interface between the silicone resin layer 14 and the glass substrate 16 is adjusted by the bonding force between before and after the surface of the glass substrate 16 of the glass laminate 10 (second main surface 16b) . However, even after forming the member for electronic devices, the peel strength (y) is preferably lower than the peel strength (x).

It is believed that the layers of the silicone resin layer 14 and the glass substrate 16 are bonded with a bonding force due to a weak adhesive force or a Bandezval force. In the case where the glass substrate 16 is laminated on the surface of the silicon resin layer 14 after the silicon resin layer 14 is formed, if the silicone resin of the silicone resin layer 14 is sufficiently crosslinked so as not to exhibit the adhesive force, It is believed that they are bonded together. However, the silicone resin of the silicone resin layer 14 often has a weak adhesive strength to some extent. Even when the adhesiveness is extremely low, when the electronic device member is formed on the glass laminate 10 after the production of the glass laminate 10, the silicone resin of the silicone resin layer 14 Is bonded to the surface of the glass substrate 16 and the bonding force between the silicon resin layer 14 and the glass substrate 16 is considered to increase.

It is also possible to laminate the surface of the silicon resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination by performing treatment to weaken the bonding force therebetween. The bonding strength between the interface of the silicon resin layer 14 and the layer of the glass substrate 16 can be weakened and the peeling strength y can be lowered by performing non-adhesive treatment or the like on the surface to be laminated.

The silicone resin layer 14 is bonded to the surface of the support base material 12 with strong bonding force such as an adhesive force or an adhesive force, and a known method can be adopted as a method for enhancing the adhesion between the two. For example, as will be described later, the silicone resin layer 14 is formed on the surface of the supporting substrate 12 (more specifically, a curable organopolysiloxane capable of forming a predetermined silicone resin on the supporting substrate 12) The silicone resin in the silicone resin layer 14 is adhered to the surface of the supporting substrate 12 to obtain a high bonding force. The surface of the supporting substrate 12 and the surface of the silicon resin layer 14 (for example, the surface of the supporting substrate 12) are subjected to a treatment (for example, a treatment using a coupling agent) Can be increased.

The reason why the layer of the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peeling strength (x) at the interfaces between the layers is high.

The thickness of the silicone resin layer 14 is not particularly limited, but the upper limit is preferably 30 占 퐉 (that is, 30 占 퐉 or less), more preferably 20 占 퐉, and even more preferably 8 占 퐉. The lower limit is not particularly limited as long as it is a peelable thickness, but it is often 0.1 占 퐉 or more. When the thickness of the silicon resin layer 14 is within this range, cracks are unlikely to occur in the silicon resin layer 14 and bubbles or foreign matter may be interposed between the silicon resin layer 14 and the glass substrate 16 , The occurrence of deformation defects of the glass substrate 16 can be suppressed.

The thickness is intended to mean the average thickness, and the thickness of the silicone resin layer 14 at arbitrary positions of 5 points or more is measured with a contact type film thickness measuring apparatus and arithmetically averages them.

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

The surface roughness Ra is measured in accordance with JIS B 0601-2001, and the value obtained by arithmetically averaging the Ra measured at any five or more points corresponds to the surface roughness Ra.

The silicone resin layer 14 may include two or more layers. In this case, "the thickness of the silicon resin layer 14" means the total thickness of all the silicone resin layers.

Usually, the curable organopolysiloxane coated on the substrate is dried and removed from the solvent contained in the material under a temperature condition of room temperature to below the thermal deformation temperature of the substrate, and then thermally cured by heating to obtain a silicone resin. In the thermal curing process, silanol groups (-Si-OH) contained in the curable organopolysiloxane undergo dehydration condensation reaction to form siloxane bonds (-Si-O-Si-), crosslinking and curing, . During the heating process, the gel film is densified by the capillary force generated by the evaporation of the solvent and the dehydration condensation reaction proceeding in the film, and the volume reduction rate of the film reaches several tens%. Although the gel film is not a completely elastic body, when it is approximated to an elastic body, deformation is accumulated in the in-plane direction of the film when the film is contracted in the in-plane restrained state along the base. As a result, tensile stress (hereinafter also referred to as "shrinkage stress") occurs in the in-plane direction of the film.

The shrinkage stress of the silicone resin layer in the present invention means the value of the radius of curvature of the silicon wafer before and after the formation of the silicon resin layer measured by a thin film stress measuring apparatus at an ambient temperature of 25 캜, In the in-plane direction of the silicone resin layer calculated by the formula shown by the following formula (1) using the value of the tensile stress. In addition, the measurement procedure will be described in detail in the embodiment.

Wherein, E / (1-ν) is biaxially elastic modulus (crystal face ^{(100): 1.805 × 10 11} Pa) of the silicon wafer and, h is the thickness [m] of the silicon wafer, t is a resin layer thickness of the silicon [m], and R is the difference [m] between the radius of curvature of the silicon wafer before the silicon resin layer is formed and the radius of curvature of the silicon wafer after the silicon resin layer is formed.

The difference R in the radius of curvature of the silicon wafer before and after the silicon resin layer is formed is determined by the thickness h of the silicon wafer, the elastic modulus E of the silicon wafer, the film thickness ratio v of the silicon wafer, the film thickness t and the tensile stress? . When the tensile stress? Is generated in the in-plane direction of the film formed on one side of the silicon wafer, the larger the stress? Generated in the in-plane direction of the film, as can be read from the above equation (1) The warp of the silicon wafer becomes large.

Therefore, when the radius of curvature R of the silicon wafer before and after the silicon resin layer is formed and the film thickness t of the silicon resin layer are examined, the shrinkage stress of the silicon resin layer is obtained. The radius of curvature R is obtained by forming a silicon resin layer on one side of a single crystal silicon wafer and scanning the laser beam on the surface of the silicon wafer on which the silicon resin layer is formed by using a thin film stress measuring apparatus, .

The size of the shrinkage stress of the silicone resin layer 14 is not particularly limited, but after the process of crosslinking and curing the curable organopolysiloxane to form the silicone resin layer 14, it is possible to prevent cracks from occurring during the cooling process, Is preferably 50 MPa or less, and more preferably 45 MPa or less in that the warpage of the manufactured glass laminate 10 can be further suppressed. The lower limit is not particularly limited, but is usually 15 MPa or more in many cases.

The silicone resin layer 14 includes a silicone resin containing a predetermined organosiloxy unit. The silicone resin is usually obtained by crosslinking and curing a curable organopolysiloxane which can be made into a silicone resin by a curing treatment.

The curable organopolysiloxane in the present invention is a partially hydrolyzed condensate (organopolysiloxane) obtained by a partial hydrolysis and condensation reaction of a mixture (monomer mixture) of a hydrolyzable organosilane compound as a monomer. In addition, the partial hydrolyzed condensate may contain an unreacted monomer.

In order to crosslink and cure the curable organopolysiloxane, the crosslinking reaction is usually conducted by heating to cure (i.e., heat cure). By thermosetting the curable organopolysiloxane, a silicone resin is obtained. However, there is a case in which heating is not necessarily required for curing, and it is also possible to cure at room temperature.

Typical silicone resins (organopolysiloxane) include monofunctional organosiloxy units called M units, bifunctional organosiloxy units called D units, trifunctional organosiloxy units called T units, and Q And a tetrafunctional organosiloxy unit called a " unit ". The Q unit is a unit which does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as an organosiloxy unit (silicon-containing bonding unit) in the present invention. The monomer forming the T unit is hereinafter referred to as T monomer. Monomers forming M units, D units and Q units are likewise referred to as M monomers, D monomers and Q monomers.

In the organosiloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, and the oxygen atom per one silicon atom in the siloxane bond is regarded as 1/2, and O _{1 / 2} < / RTI > More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms and each oxygen atom is bonded to another silicon atom, so that the formula is -O < _{1 > / 2} - (R) ₂ Si-O _1/2 -. O _1/2 by the presence of two, D units will normally be expressed as _{(R) 2 SiO 2/2} .

In the following description, the oxygen atom O ^* bonded to another silicon atom is an oxygen atom which bonds two silicon atoms and is intended to be an oxygen atom in a bond represented by Si-O-Si. Thus, O ^* is present between the silicon atoms of the two organosiloxy units.

In general, T unit is, R-SiO _3/2 is intended the organo siloxy units represented by (R represents a hydrogen atom or organic). That is, the T unit is a unit having one silicon atom, one hydrogen atom bonded to the silicon atom, or a monovalent organic group and three oxygen atoms O ^* bonded to another silicon atom.

However, in the present specification, a case in which a functional group capable of bonding to another silicon atom is substituted for a part or all of the oxygen atom O ^* bonded to another silicon atom is also regarded as a T unit. The functional group capable of bonding to the other silicon atom is a hydroxyl group or a group which becomes a hydroxyl group by hydrolysis (hereinafter referred to as a hydrolyzable group). More specifically, in this specification, T units, and the total of the functional group that can be bonded to the other silicon-oxygen atom O ^* and other silicon atoms bonded to atom 3 pieces, an oxygen atom O ^* and the other is bonded to another silicon atom Depending on the difference in the number of functional groups capable of bonding to the silicon atom, the T unit is classified into three types of units called T1 unit, T2 unit and T3 unit. T1 is one unit the number of the oxygen atom O ^* is bonded to two other silicon atoms, T2 units are in number of two atoms of oxygen O ^*, T3 unit of the oxygen atom O ^* number of the dog 3. In the present specification, Z represents a monovalent functional group capable of bonding to other silicon atoms.

Monomer (hydrolysable organosilane compound) is represented by the _{normal, (R'-) a Si (-Z} ) 4 -a. A represents an integer of 0 to 3, R 'represents a hydrogen atom or a monovalent organic group, and Z represents a hydroxyl group or a hydrolyzable group. In this formula, the compound of a = 3 is an M monomer, the compound of a = 2 is a D monomer, the compound of a = 1 is a T monomer, and the compound of a = 0 is a Q monomer. In the monomers, the Z group is usually a hydrolyzable group. When two or three R 's exist (when a is 2 or 3), plural R' s may be different.

The curable organopolysiloxane which is a partially hydrolyzed condensate is obtained by a reaction of converting a part of the Z group of the monomer into an oxygen atom O ^* . When Z group is a hydrolyzable group of the monomer, Z groups singer is converted to a hydroxyl group by the reaction, and subsequently by the dehydration condensation reaction between the two hydroxyl groups bonded to separate silicon atoms, and two silicon atoms are oxygen atom O ^* Lt; / RTI > In the curable organopolysiloxane, a hydroxyl group (or a group Z which is not hydrolyzed) remains, and when the curable organopolysiloxane is cured, these hydroxyl groups and Z groups are reacted and cured as described above. The cured product of the curable organopolysiloxane is usually a three-dimensionally crosslinked polymer (silicone resin). At the time of curing, it is considered that the Z group of the curable organopolysiloxane is converted into O ^* , but a part of the Z group (particularly hydroxyl group) remains, resulting in a cured product having a hydroxyl group. In the case where the curable organopolysiloxane is cured at a high temperature, the cured organopolysiloxane may be a cured product which hardly contains hydroxyl groups.

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 most cases, a monomer in which the Z group is an alkoxy group is used as the monomer. In the curable organopolysiloxane obtained by using a monomer in which the Z group is an alkoxy group, the alkoxy group is a hydrolyzable group having relatively low reactivity as compared with a chlorine atom and the like. In many cases, an unreacted alkoxy group is present together with a hydroxyl group as an Z group. When the Z group of the monomer is a hydrolyzable group (e.g., a chlorine atom) having a relatively high reactivity, most of the Z groups in the curable organopolysiloxane obtained by using the monomer become a hydroxyl group. Therefore, in ordinary curable organopolysiloxanes, the Z group in each unit constituting the curing organopolysiloxane often contains a hydroxyl group or contains a hydroxyl group and an alkoxy group.

(Silicone resin)

The silicone resin constituting the silicone resin layer 14 is an organosiloxane having an organosiloxy unit represented by T3 (hereinafter simply referred to as T3 unit) and represented by T3 with respect to the total organosiloxy unit Is preferably from 82 to 100 mol% from the viewpoint that the total ratio of the units is 80 to 100 mol% and the resulting silicone resin layer 14 has excellent heat resistance and the peeling of the glass substrate 16 proceeds more easily. And more preferably 85 to 100 mol%. That is, the silicone resin contains, as a main component, an organosiloxy unit represented by T3.

T3: R-SiO _3/2

In the formulas, R represents a phenyl group or a methyl group.

Further, the organosiloxy unit represented by T3 corresponds to one of the T units described above. The silicone resin may contain other units besides the organosiloxy units represented by T3, and the other units include M units, D units, T1 units, T2 units and Q units.

Among them, in view of the fact that there is no cohesive failure of the silicone resin layer 14 at the time of peeling, the mechanical strength of the silicone resin layer 14 is excellent, and the peelability of the glass substrate 16 is excellent, (So-called " Q unit "). The content of the Q units is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total organosiloxy units. Although the upper limit is not particularly limited, there is a fear that the brittleness of the silicone resin layer 14 is lowered due to the increase of the degree of crosslinking, the silicone resin layer 14 may cause cohesive failure at the time of peeling, It is preferably 20 mol% or less from the viewpoint that there is a fear that warping of the glass composite is caused by an increase in shrinkage stress.

Q: SiO _4/2

The total organosiloxy unit is intended to mean the sum of the M units, the D units, the T units and the Q units contained in the silicone resin. The ratio of the M unit, D unit, T unit (T1 to T3 unit) and Q unit (molar amount) can be calculated from the value of the peak area ratio by ²⁹ Si-NMR.

In the silicone resin in the silicone resin layer 14, the molar ratio of the organosiloxy unit (A-1) in which R in the T3 is a phenyl group and the organosiloxy unit (B-1) in which R in the T3 is a methyl group (A-1) / (B-1) = 100) is 80/20 to 20/80. Among them, the molar ratio ((A-1) / (B-1)) is preferably 75/25 to 20/80, more preferably 70/30 to 20/80 More preferable.

The organosiloxy unit (A-1) wherein R is a phenyl group is an organosiloxy unit represented by P-T3. Ph represents a phenyl group.

_{P-T3: Ph-SiO 3} /2

The organosiloxy unit (B-1) in which R is a methyl group is intended to be an organosiloxy unit represented by M-T3.

_{M-T3: Me-SiO 3} /2

The silicone resin can be produced by using a known material.

As described above, examples of the curable organopolysiloxane which can be made into a silicone resin by the curing treatment include a partial hydrolysis condensation product obtained by partial hydrolysis and condensation reaction of a mixture of a hydrolyzable organosilane compound as a monomer Organopolysiloxane) is used. More specifically, as the monomer, a hydrolyzable organosilane compound represented by (Me-) Si (-Z) ₃ and a hydrolyzable organosilane compound represented by (Ph-) Si (-Z) ₃ are used do. The Z group represents a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom such as a chlorine atom, an alkoxy group, an acyl group, an amino group, and an alkoxyalkoxy group.

In addition, the hydrolysis and condensation reaction is a reaction in which a T1 unit is generated from a T monomer, a T2 unit is generated from a T1 unit, and a T3 unit is generated from a T2 unit. The reaction rates of the condensation reaction in which T1 units are generated from T monomers in which at least one of the hydrolyzable groups are converted to hydroxyl groups, the condensation reaction in which T2 units are formed from T1 units, and the condensation reactions in which T3 units are formed in T2 units are carried out in this order It seems to be slow. Even considering the hydrolysis reaction of the hydrolyzable group, it is considered that as the reaction progresses, the peak of the abundance of each unit moves from the T monomer to the T3 unit. When the reaction conditions are relatively mild, it is considered that the shift of the peak of the abundance proceeds relatively smoothly.

As the curable organopolysiloxane that can be used as the silicone resin, a partially hydrolyzed condensation product (organopolysiloxane) obtained from a mixture of hydrolysable organosilane compounds is used as the control and handling of the reaction as described above do. The partially hydrolyzed condensate is obtained by partial hydrolysis and condensation of a monomer mixture in which the hydrolyzable organosilane compound is mixed at a ratio of the respective organosiloxy units. The method of partial hydrolysis and condensation is not particularly limited. Generally, it is prepared by reacting a mixture of hydrolysable organosilane compounds in a solvent in the presence of a catalyst. As the catalyst, an acid catalyst or an alkali catalyst can be used. In addition, water is preferably used for the hydrolysis reaction. The partially hydrolyzed condensate used in the present invention is preferably prepared by reacting a mixture of hydrolysable organosilane compounds in a solvent in the presence of an acid or an aqueous alkali solution.

As a singer used hydrolyzable organosilane compound, the above-described (Me-) Si (-Z) hydrolyzable represented by ₃ organosilane compound and, (Ph-) Si (-Z) 3 hydrolyzable organosilane represented by the Among them, phenyltrichlorosilane (represented by the following formula ((1)) is more preferable in view of handling of the curable organopolysiloxane obtained, high heat resistance and more easily peeling off the glass substrate 16 1)) and methyltrichlorosilane (a compound represented by the following formula (2)) are preferably used. Ph in the formula (1) represents a phenyl group.

As described later, a composition containing a curable organopolysiloxane is used to form a layer of a curable organopolysiloxane. In order to further enhance the stability of the curable organopolysiloxane in the composition, the end of the cured silicone It can also be capped. More specifically, the terminal Si-OH in the curable organopolysiloxane can be reacted with an alcohol under acid catalysis (e.g., in the presence of acetic acid) to protect and cap the Si-OH while removing water. For example, when methanol is used, an Si-OMe group is formed. The type of alcohol used is not particularly limited, and low-boiling alcohols such as methanol, ethanol, 1-propanol, 1-butanol and the like can be mentioned. Of these, methanol and ethanol are preferable because they have good reactivity with the Si-OH group and good solubility of the curable organopolysiloxane.

(A suitable form of the curable organopolysiloxane)

One of the preferable forms of the curable organopolysiloxane includes organosiloxane units having at least any one of the following organosiloxy units represented by T1 to T3 and represented by the following T1 to T3 with respect to all the organosiloxy units (A-2) in which R in the following T1 to T3 is a phenyl group and an organosiloxy unit (B-2) in which R in the following T1 to T3 is a methyl group, 2) ((A-2) / (B-2)) of 80/20 to 20/80 (hereinafter also referred to as organopolysiloxane X). If it is the organopolysiloxane, a desired silicone resin is easily obtained.

T1: R-Si (-OX) 2 O 1/2

T2: R-Si (-OX) O 2/2

T3: R-SiO _3/2

In the formula, R represents a phenyl group or a methyl group. X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R in the above formula is not limited to one, and T1, T2, and T3 may be different from each other.

-OX may be the same or different between the T1 unit and the T2 unit. Two -OX in the T1 unit may be different, for example, one may be a hydroxyl group and the other may be an alkoxy group. Further, when two -OX are all alkoxy groups, they may be different alkoxy groups.

A T unit having only three -OX, which does not have an oxygen atom (O ^* ) connecting two silicon atoms, is hereinafter referred to as T0. T0 actually corresponds to an unreacted T monomer, and is not an organosiloxy unit (silicon-containing bonding unit). This T0 is measured in the same manner as T1 to T3 in the analysis of the units of T1 to T3.

The unit of T1 to T3 in the organopolysiloxane X can be analyzed by measuring the bonding state of silicon atoms by nuclear magnetic resonance analysis ( ²⁹ Si-NMR). The ratio of the number of units (molar amount) of T0 to T3 is determined from the peak area ratio of ²⁹ Si-NMR.

The mass-average molecular weight Mw, the number-average molecular weight Mn and the dispersion degree Mw / Mn of the organopolysiloxane X are values measured with gel permeation chromatography using polystyrene as a standard material. The properties of such an organopolysiloxane X are not one characteristic of a molecule but are obtained as an average characteristic of each molecule.

As described above, the total proportion of the organosiloxy units represented by T1 to T3 in the organopolysiloxane X is preferably 80 to 100 mol% based on the total organosiloxy unit, 82 to 100 mol% is preferable, and 85 to 100 mol% is more preferable because heat resistance of the paper layer 14 is excellent and peeling of the glass substrate 16 proceeds more easily.

From the viewpoint of handleability, the organopolysiloxane X preferably contains at least the T3 unit, and more preferably contains the T2 unit and the T3 unit. As a result of various studies, it is known that when the number of Ph groups (phenyl groups) increases, the proportion of T1 units increases. When the T1 unit is increased, since the shrinkage stress is large at the time of curing in the process of manufacturing the silicone resin layer, the smaller the T1 unit is, the more preferable the shrinkage stress can be lowered.

Further, the organopolysiloxane X may contain other units in addition to the organosiloxy units represented by T1 to T3, and other units may include M units, D units and Q units.

As curable organopolysiloxanes of T-form, polyphenylpolysiloxane, polymethylpolysiloxane and the like are generally known. Silanol-terminated polyphenylpolysiloxane is obtained as an oligomer having a molecular weight of several hundred to several thousands upon hydrolysis of PhSiCl ₃ . When these oligomers are used to produce cured products having a thickness of 0.1 mm or more, they are very fragile and can not withstand use. However, the silicone resin is excellent in heat resistance.

On the other hand, when the substituent on the silicon atom is an aliphatic hydrocarbon group such as a methyl group, RSiZ ₃ Type monomer is high, and the molecular weight of the obtained hydrolysis-condensation product is in most cases 10,000 or more. In order to dissolve the condensate, a large amount of solvent is required, and a thin film for coating application is obtained. However, a cured product having a certain thickness is difficult to obtain due to cracks or the like .

Therefore, it is preferable to use the curable organopolysiloxane X that combines heat resistance and reactivity and improves solubility.

In the curable organopolysiloxane X, the mole ratio of the organosiloxy unit (A-2) in which R in the T1 to T3 is a phenyl group and the organosiloxy unit (B-2) in which R in the T1 to T3 is a methyl group (A-2) / (B-2) = 100) is preferably 80/20 to 20/80. In particular, it is possible to prepare a coating solution having excellent solubility of the curable organopolysiloxane and having an appropriate surface tension (i.e., good wettability) with respect to the cleaned glass substrate, and to reduce the shrinkage stress upon curing , The molar ratio ((A-2) / (B-2)) is preferably 75/25 to 20/80, and more preferably 70/30 to 20/80.

The organosiloxy unit (A-2) in which R is a phenyl group means a T1 unit (hereinafter referred to as P-T1) in which R is a phenyl group, a T2 unit in which R is a phenyl group (hereinafter referred to as P-T2) Unit (hereinafter referred to as " P-T3 "). In the formulas P-T1 to P-T3, Ph represents a phenyl group.

T1-P: Si-Ph (-OX) ₂ O _1/2

P-T2: Si-Ph (-OX) O _2/2

_{P-T3: Ph-SiO 3} /2

Therefore, the content of the organosiloxy unit (A-2) is preferably such that the content of the units represented by P-T1, the units represented by P-T2, and the content of units represented by P-T3 Lt; / RTI >

Examples of the organosiloxy unit (B-2) in which R is a methyl group include a T1 unit (hereinafter referred to as M-T1) in which R is a methyl group, a T2 unit in which R is a methyl group (hereinafter referred to as M-T2) Gt; T3 < / RTI > units (M-T3 below). Herein, among the formulas M-T1 to M-T3, Me represents a methyl group.

M-T1: Me-Si ( -OX) 2 O 1/2

M-T2: Me-Si ( -OX) O 2/2

_{M-T3: Me-SiO 3} /2

Therefore, the content of the organosiloxy unit (B-2) is preferably such that the content of the unit represented by M-T1, the content of the unit represented by M-T2, and the content of units represented by M-T3 Lt; / RTI >

The curable organopolysiloxane (particularly, the curable organopolysiloxane X) is obtained by subjecting the organosiloxy units represented by T1 to T3 to a ratio (molar amount) of the number of units of T1: T2: T3 = 0 to 5: 20 to 50: 50 to 80 (also satisfying the relationship of T1 + T2 + T3 = 100). Within this range, the glass substrate 16 can be more easily peeled off. In other words, the ratio of T1: T2: T3 is 0 to 5 mol% in T1 units, 20 to 50 mol% in T2 units, and 50 to 80 mol% in T3 units have.

(A-2) units and (B-2) units in the curable organopolysiloxane X from the viewpoint that the glass substrate 16 can be easily peeled off and warpage of the glass laminate 10 can be reduced T1: T2: T3 = 0 to 5: 20 to 50: 50 (molar ratio) in the range of from 80/20 to 20/80 (A-2) / (B- It is preferably 50 to 80. [

Further, when the silicone resin layer is formed using the curable organopolysiloxane X, the methyl group and the phenyl group in T1 to T3 may be eliminated depending on the curing conditions to form a Q unit.

The number average molecular weight of the curable organopolysiloxane (in particular, the curable organopolysiloxane X) can be obtained by preparing a silicone resin layer 14 having excellent solubility of the curable organopolysiloxane and having few foreign matter defects, The number average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) measurement is preferably from 500 to 2000, more preferably from 600 to 2000, 1800 is more preferable.

Further, the mass average molecular weight / number average molecular weight of the curable organopolysiloxane (particularly, the curable organopolysiloxane X) is not particularly limited so long as the silicone resin layer 14 having excellent solubility of the curable organopolysiloxane and little foreign matter defect can be prepared Is preferably from 1.00 to 2.00, more preferably from 1.00 to 1.70, and further preferably from 1.00 to 1.50 in that the glass substrate 16 can be easily peeled off.

The molecular weight of the curable organopolysiloxane (particularly, the curable organopolysiloxane X) can be controlled by controlling the reaction conditions. For example, when the concentration of the hydrolyzable organosilane compound is increased by adjusting the amount of solvent when the curable oligomer is prepared, a high molecular weight material is obtained. When the concentration is low, a low molecular weight material is obtained.

The shape of the curable organopolysiloxane (particularly, the curable organopolysiloxane X) is not particularly limited and may be a particle type. That is, when the curable organopolysiloxane (particularly the curable organopolysiloxane X) is added to a solvent, it may be present as fine particles.

In this case, the particle diameter of the curable organopolysiloxane (in particular, the curable organopolysiloxane X) measured by the dynamic light scattering method is not particularly limited, but the silicone resin layer having few foreign matters can be produced, or the glass substrate 16 is more preferably 0.5 to 100 nm, and more preferably 0.5 to less than 40 nm in terms of being able to more easily peel off.

As a measurement method of the dynamic light scattering method, a curable organopolysiloxane (particularly, the curable organopolysiloxane X) was adjusted to 20 mass% in a PEGMEA solution (propylene glycol-1-monomethyl ether-2-acetate) A sample is prepared, and the histogram average particle diameter (D50) is obtained by using a dense particle size analyzer (FPAR-1000, manufactured by Otsuka Chemical Co., Ltd.) to obtain a particle diameter.

The method of producing the above-described silicone resin layer 14 is not particularly limited, and a known method can be employed. As a method of producing the silicone resin layer 14, a layer of a curable organopolysiloxane that is the silicone resin is formed on the supporting substrate 12, and the curable organopolysiloxane is crosslinked and cured to form a silicone resin layer (14). In order to form a layer of the curable organopolysiloxane on the support substrate 12, a solution (a composition containing a curable organopolysiloxane) in which a curable organopolysiloxane is dissolved in a solvent is used, To form a layer of the solution, and then the solvent is removed to form a layer of the curable organopolysiloxane. The thickness of the layer of the curable organopolysiloxane can be controlled by adjusting the solution concentration or the like. Among them, the content of the curable organopolysiloxane in the composition containing the curable organopolysiloxane is preferably within a range from 1 to 10 parts by mass, , Preferably 1 to 100 mass%, and more preferably 1 to 50 mass%.

The solvent is not particularly limited as long as it is a solvent which can easily dissolve the curable organopolysiloxane in the working environment and can easily remove volatilization. Specific examples thereof include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate and the like.

It is also preferable to control the pH in the composition in order to further increase the stability of the curable organopolysiloxane in the composition. Generally, it is known that there is a certain range in the pH at which the silanol group can stably exist, and the gelation is easy to proceed at the vicinity of neutral, and is more stably existed on the acidic side (pH 2 to 4) or the basic side (pH 11 to 14) . In order to increase the stability of the curable organopolysiloxane and to act as a curing catalyst when the curable organopolysiloxane is cured, an acid is preferably used for pH control. Examples of the acid addition include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid and sulfamic acid; And organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid and p-toluenesulfonic acid. Acetic acid is preferable. The amount of the acid to be used is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 20 parts by mass, per 100 parts by mass of the curable organopolysiloxane composition.

Further, in order to further enhance the stability of the curable organopolysiloxane in the composition, alcohol having a higher boiling point than the coating solvent may be added. The kind of alcohol used is not particularly limited, and examples thereof include alcohols such as 1-butanol, 1-methoxy-2-propanol, 2-pentanol, -Ethoxyethoxy) ethanol, and the like. Of these, 1-methoxy-2-propanol, diacetone alcohol and 2- (2-ethoxyethoxy) ethanol are preferable from the viewpoint of good solubility of the curable organopolysiloxane.

In addition, for the purpose of improving coatability on the base material, a defoaming agent and a viscosity adjusting agent may be contained. In addition, additives such as an adhesion promoter may be added for the purpose of improving adhesion to a base material and the coating workability and smoothness of the resulting coating film A leveling agent may be added for the purpose. The blending amount of these additives is preferably 0.01 to 2 parts by mass each of the components relative to 100 parts by mass of the curable organopolysiloxane. In addition, a filler or the like may be added within the range not impairing the object of the present invention.

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

[Glass laminate and manufacturing method thereof]

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

The method for producing the glass laminate 10 of the present invention is not particularly limited. However, in order to obtain a laminate having a peel strength x higher than the peel strength y, the glass laminate 14 is formed on the surface of the support substrate 12, Is preferable. Among them, a curable organopolysiloxane is applied to the surface of the supporting substrate 12 to form a silicone resin layer 14 on the surface of the supporting substrate 12, and subsequently, a silicone resin layer 14 A method of laminating the substrate 16 and manufacturing the glass laminate 10 is preferable.

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

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

(Resin layer forming step)

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

In order to form a layer of the curable organopolysiloxane on the support substrate 12, a coating composition (corresponding to the composition containing the curable organopolysiloxane) in which a curable organopolysiloxane is dissolved in a solvent is used, It is preferable to coat the support substrate 12 to form a layer of the solution, and then to perform the curing treatment to form the silicone resin layer 14. [

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

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

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

The temperature condition for thermally curing is not particularly limited within a range in which the heat resistance of the silicone resin layer 14 is improved and the peeling strength y after lamination with the glass substrate 16 can be controlled as described above, Deg.] C, more preferably 200 to 450 [deg.] C. The heating time is usually 10 to 300 minutes, preferably 20 to 120 minutes. The heating conditions may be changed stepwise by changing the temperature conditions.

By controlling the temperature range and the heating time range, it is possible to control the production rate of the Q unit which is likely to be generated by heating by T1 unit, T2 unit and T3 unit, and 250 ° C or more.

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

(Lamination step)

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

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

For example, a method of overlapping the glass substrate 16 on the surface of the silicon resin layer 14 under atmospheric pressure can be mentioned. If necessary, the glass substrate 16 may be pressed against the silicon resin layer 14 by using a roll or a press after the glass substrate 16 is superimposed on the surface of the silicon resin layer 14. The bubbles mixed in between the silicone resin layer 14 and the glass substrate 16 are relatively easily removed by pressing by roll or press.

The vacuum lamination method or the vacuum press method is more preferable because it suppresses the incorporation of air bubbles and secures good adhesion. Even when minute bubbles remain, there is an advantage that bubbles do not grow due to heating, and it is difficult to lead to deformation defects of the glass substrate 16.

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

Further, after the glass substrate 16 is laminated, a pre-annealing treatment (heat treatment) may be performed if necessary. By performing the pre-annealing process, the adhesion of the laminated glass substrate 16 to the silicon resin layer 14 can be improved and the peel strength (y) can be made suitable. In the member forming process described later, The positional deviation of the member is less likely to occur, and the productivity of the electronic device is improved.

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

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

For example, when the support base material 12 having a higher adhesion to the surface of the silicone resin layer 14 than the glass substrate 16 is used, the curable organopolysiloxane is cured on any releasable surface, And this film is interposed between the glass substrate 16 and the supporting substrate 12 to be laminated at the same time.

When the adhesion of the curable organopolysiloxane by curing is sufficiently low with respect to the glass substrate 16 and the adhesion thereof is sufficiently high with respect to the supporting substrate 12, the glass substrate 16 and the supporting substrate 12 The silicone resin layer 14 can be formed by curing the cross-linked product.

Even in the case where the supporting substrate 12 includes the same glass material as the glass substrate 16, a treatment for increasing the adhesiveness of the surface of the supporting substrate 12 is carried out to improve the peeling strength to the silicon resin layer 14 . For example, chemical methods such as chemical methods (primer treatment) such as silane coupling agent, physical methods to increase the surface activation period such as flame (flame) treatment, increase in surface roughness such as sand blast treatment, And a mechanical treatment method for increasing the amount of the water-soluble polymer.

(Glass laminate)

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

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

≪ Second Embodiment >

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

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

In the glass laminate 100 shown in Fig. 3, unlike the glass laminate 10 shown in Fig. 1 described above, the silicon resin layer 14 is fixed on the glass substrate 16, The glass substrate 20 having the resin layer can be peelably laminated on the support substrate 12 so that the silicon resin layer 14 in the glass substrate 20 having the resin layer directly contacts the support substrate 12, do. The fixation and releasable adhesion have a difference in the peel strength (i.e., the stress required for peeling), and the fixation means that the peel strength is higher than the adhesion. That is, in the glass laminate 100, the peel strength at the interface between the silicon resin layer 14 and the glass substrate 16 is higher than the peel strength at the interface between the silicon resin layer 14 and the support base 12.

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

In the glass laminate 100, the peel strength z is higher than the peel strength w. The glass laminate 100 according to the present invention can be obtained by a method in which the stress is applied to the glass laminate 100 in the direction in which the supporting substrate 12 and the glass substrate 16 are peeled off, (12) and separated into a glass substrate (20) having a resin layer and a supporting substrate (12).

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

In order to increase the adhesion of the silicone resin layer 14 to the glass substrate 16, it is preferable to form the silicone resin layer 14 by crosslinking and curing the curable organopolysiloxane on the glass substrate 16. The silicone resin layer 14 bonded to the glass substrate 16 with high bonding force can be formed by the adhesive force at the time of crosslinking curing.

On the other hand, it is usual that the bonding force of the silicone resin to the support base material 12 after the cross-linking curing is lower than the bonding force that occurs at the time of cross-link curing. Therefore, the glass laminate 100 can be manufactured by forming the silicone resin layer 14 on the glass substrate 16 and then laminating the supporting substrate 12 on the surface of the silicone resin layer 14.

The layers (supporting substrate 12, glass substrate 16, and silicone resin layer 14) constituting the glass laminate 100 are in agreement with the respective layers constituting the above-described glass laminate 10, A description thereof will be omitted here.

Although the surface roughness Ra of the surface of the silicon resin layer 14 on the side of the supporting substrate 12 is not particularly limited, it is preferably 0.1 to 20 nm from the viewpoint of better laminating property and peeling property of the glass substrate 16 And more preferably 0.1 to 10 nm.

The surface roughness Ra is measured in accordance with JIS B 0601-2001, and the value obtained by arithmetically averaging the Ra measured at any five or more points corresponds to the surface roughness Ra.

The method for producing the glass laminate 100 is not particularly limited but a method may be used in which the glass substrate 16 is used in place of the supporting substrate 12 in the method for manufacturing the glass laminate 10 described above, By using the supporting substrate 12 instead, the desired glass laminate 100 can be produced. More specifically, the silicon resin layer 14 is formed on the glass substrate 16, and then the supporting substrate 12 is laminated on the silicon resin layer 14 to produce the glass laminate 100 .

[Glass Substrate Having Member and Method of Manufacturing the Same]

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

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

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

The method of manufacturing the glass substrate having the member is not particularly limited, but it is preferable that the electronic device member is formed on the glass substrate in the glass laminate so that the laminate having the electronic device member It is preferable to separate the glass substrate side surface of the silicon resin layer or the inside of the resin layer from the laminate having the obtained electronic device member to a supporting substrate having a resin layer and a glass substrate having the member as a peeling surface. Further, if necessary, it is more preferable to subsequently clean the release surface of the glass substrate having the member.

Hereinafter, a step of forming a member for an electronic device on a glass substrate in the glass laminate to produce a laminate having an electronic device member is referred to as a member forming step, a step of forming a glass substrate The step of separating the glass substrate having the member into the supporting substrate having the resin layer and the step of separating the glass substrate with the side interfacial surface separated is referred to as a separation process and the process of cleaning the separation surface of the glass substrate having the member is referred to as a purification process. Further, as described above, the purification treatment process is an optional process that is carried out as needed.

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

(Member forming process)

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

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

(Member for electronic device (functional element))

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

For example, as a member for a solar cell, in a silicon type, a transparent electrode such as a tin oxide of a positive electrode, a silicon layer represented by a p layer / an i layer / an n layer, and a metal of a negative electrode, Dye-sensitized type, quantum dot type, and the like.

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

Examples of the circuit for electronic parts include a metal of a conductive portion and a silicon oxide and silicon nitride of an insulating portion in a CCD or a CMOS. In addition, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed substrate, a flexible printed substrate, Various members corresponding to a printed board and the like.

(Process procedure)

The method of manufacturing the laminate 24 having the above-described electronic device member is not particularly limited and the glass substrate 16 of the glass laminate 10 may be formed by a conventionally known method depending on the type of the constituent member of the electronic device member On the surface of the second main surface 16b of the second substrate 16, the electronic device member 22 is formed.

The electronic device member 22 is not a member entirely formed on the second main surface 16b of the glass substrate 16 (hereinafter, referred to as an "entire member"), Quot; partial member "). A glass substrate having a partial member peeled off from the silicon resin layer 14 may be formed as a glass substrate (corresponding to an electronic device described later) having an entire member in a subsequent step.

Further, a glass substrate having an entire member, which is peeled off from the silicon resin layer 14, may be provided with another electronic device member on its peeling surface (first main surface 16a). Alternatively, the electronic device may be manufactured by assembling a laminate having an entire member, and thereafter peeling the supporting substrate 12 from the laminate having the entire member. Further, the two supporting substrates 12 were peeled from the laminate having the entire member by using two sheets of the laminate having the entire members, and then the glass substrate having the two glass substrates was peeled off, . ≪ / RTI >

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

For example, in the case of manufacturing a TFT-LCD, a resist solution may be used on the second main surface 16b of the glass substrate 16 of the glass laminate 10, and a general method such as a CVD method and a sputtering method, A TFT forming step of forming a thin film transistor (TFT) by patterning with a metal film and a metal oxide film formed by a film forming method and a step of forming a thin film transistor on the second main surface 16b of the glass substrate 16 of another glass laminate 10 , A CF forming step of forming a color filter (CF) by using a resist solution in pattern formation, a bonding step of laminating a laminate having CF obtained in the laminate having the TFT obtained in the TFT forming step and the CF forming step Respectively.

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

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

In the bonding step, the thin film transistor formation surface of the laminate having the TFT and the color filter formation surface of the laminate having CF are bonded to each other by using a sealing agent (for example, a UV-curable sealant for forming a cell) . Thereafter, the liquid crystal material is injected into the cell formed of the laminate having the TFT and CF. As a method of injecting the liquid crystal material, for example, there are a reduced pressure injection method and a dropping injection method.

(Separation step)

The separation step is carried out in such a manner that the interface between the silicon resin layer 14 and the glass substrate 16 is peeled off from the layered product 24 having the electronic device member obtained in the member forming step, And a glass substrate 16 which is separated from the glass substrate 16 (the glass substrate having the member), the silicon resin layer 14 and the supporting substrate 12, Is obtained.

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

The method of peeling the glass substrate 26 having the member and the supporting substrate 18 having the resin layer is not particularly limited. Concretely, for example, a sharp blade type is pushed into the interface between the glass substrate 16 and the silicone resin layer 14 to give a moment of peeling, and then a mixed fluid of water and compressed air is sprayed to peel off have. Preferably, the support member 12 of the layered product 24 having the electronic device member is disposed on the upper surface side and the electronic device member 22 side is disposed on the lower surface side, and the electronic device member 22 side Is vacuum-adsorbed on a platen (in the case where the supporting substrate is laminated on both surfaces thereof), the blade is first introduced into the interface between the glass substrate 16 and the silicone resin layer 14 in this state. Thereafter, the side of the supporting substrate 12 is adsorbed by the plurality of vacuum adsorption pads, and the vacuum adsorption pad is raised in order from the vicinity of the point where the blade is pierced. An air layer is formed at the interface between the silicon resin layer 14 and the glass substrate 16 and the air layer spreads over the whole surface of the interface so that the support base material 18 having the resin layer can be easily peeled off.

Further, the supporting substrate 18 having a resin layer can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

When the glass substrate 26 having the member is separated from the laminate 24 having the electronic device member, the silicon substrate layer 14 is formed by controlling the injection and the humidity by the ionizer Electrostatically adsorbing the glass substrate 26 can be further suppressed.

[Purification process]

The cleaning process is a process of performing a cleaning process on the release surface (first main surface 16a) of the glass substrate 16 in the glass substrate 26 having the members obtained in the above separation process. By carrying out the process, it is possible to remove impurities such as metal pieces and dust generated in the silicon resin layer or the silicone resin layer adhered to the release surface and the member forming process attached to the release surface, and the cleanliness of the release surface can be maintained . As a result, the tackiness of the retardation film or the polarizing film attached to the release surface of the glass substrate 16 is improved.

The method of the cleaning treatment is not particularly limited as long as it can remove the resin, dust, etc. adhering to the peeling surface. For example, there are a method of thermally decomposing deposits, a method of removing impurities on the release surface by plasma irradiation or light irradiation (for example, UV irradiation treatment), a method of cleaning treatment using a solvent, and the like .

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

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

In the above, the mode of using the glass laminate 10 is described in detail. However, the electronic laminate 100 may be used to manufacture an electronic device according to the same procedure as described above.

When the glass laminate 100 is used, the supporting substrate 12 and the silicone resin layer 14 are formed by peeling off the interface between the supporting substrate 12 and the silicone resin layer 14 in the separating step 14, a glass substrate 16, and an electronic device member 22, as shown in Fig.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited to these examples. In this Production Example, the evaluation of the curable organopolysiloxane was carried out by the following items and methods.

(1) Analysis of bonding state of silicon atoms in the curable organopolysiloxane (ratio of T units)

The ratio of T1 to T3 was determined using a nuclear magnetic resonance analyzer (solution ²⁹ Si-NMR: ECP400, manufactured by JEOL RESONANCE CO., LTD.).

The ratio of T1 to T3 was determined from the peak area ratio of solution ²⁹ Si-NMR, respectively. The measurement conditions were a pulse width of 20 microseconds, a waiting time of pulse repetition of 30 sec, and a cumulative number of times of 256 scans. Toluene was used as a solvent, and the concentration was adjusted to 30 wt%. Cr (acac) ₃ was added as a relaxation reagent in an amount of 0.1 wt%. The standard of chemical shift was 0 ppm of TMS-derived peak.

The integral calculation range of each structure is as follows.

T1 (Me group): -44 to -49 ppm, T1 (Ph group): -60 to -61 ppm

T2 (Me group): -50 to -60 ppm, T2 (Ph group): -67 to -74 ppm

T3 (Me group): -61 to -67 ppm, T3 (Ph group): -74 to -83 ppm

(2) Analysis of mole percentage of phenyl groups / mole% of methyl groups in the curable organopolysiloxane ((A-2) / (B-2))

The mole fractions of phenyl group mole% / methyl methyl mole% ((A-2) / (B-2)) were determined using a nuclear magnetic resonance analyzer (solution ¹ H-NMR: JEOL RESONANCE, ECP400).

The mole fractions of phenyl group mole / methyl group mole% ((A-2) / (B-2)) were determined from the peak areas of ¹ H-NMR. The measurement conditions were a pulse width of 6.7 mu sec, a waiting time of pulse repetition of 5 sec, and a cumulative count of 16 scans. Deuterated chloroform was used as the solvent and the concentration was adjusted to 1 wt%. As a standard of the chemical shift, the peak derived from chloroform was 7.26 ppm. The chemical shift of ¹ H-NMR derived from each structure is as follows.

A-2 (Ph group): 8.2 to 6.4 ppm

B-2 (Me group): 0.6 to -0.7 ppm

(3) Evaluation of number-average molecular weight Mn, mass-average molecular weight Mw and dispersion degree Mw / Mn

Was determined by gel permeation chromatography (GPC, HLC8220 manufactured by Tosoh Corporation, RI detection, column: TSK-GEL SuperHZ, eluent: tetrahydrofuran).

(4) Evaluation of particle diameter by dynamic light scattering method

The curable organopolysiloxane was used as a 20 mass% PGMEA (propylene glycol-1-monomethyl ether-2-acetate) solution and a histogram average particle diameter (D50) was determined to be the particle diameter.

In the following Examples 1 to 10 and Comparative Examples 1 and 2, a glass substrate, alkali-free borosilicate glass comprising a glass (length 274mm, width 274mm, thickness 0.2mm, the linear expansion coefficient 38 × 10 ^-7 / ℃, Asahi Trade name &quot; AN100 &quot; manufactured by Gallas Corporation) was used. As a supporting plate, a glass plate (274 mm in length, 274 mm in width, 0.4 mm in plate thickness, and a coefficient of linear expansion of 38 x 10 &lt; ^-7 &gt; / ° C; trade name "AN100", manufactured by Asahi Glass Co., Ltd.) containing glass-

&Lt; Preparation Example 1: Preparation of curable organopolysiloxane >

Sodium carbonate (12.7 g, 0.12 mol) and water (80 mL) were added to a reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer, and then methyl isobutyl ketone (80 mL) was further added to obtain a reaction solution . Subsequently, methyltrichlorosilane (7.5 g, 0.05 mol) and phenyltrichlorosilane (10.6 g, 0.05 mol) were added dropwise from the dropping funnel over 30 minutes into the reaction solution. At this time, the temperature of the reaction solution was raised to 40 占 폚. Subsequently, after completion of the dropwise addition, the reaction vessel was immersed in an oil bath at 60 DEG C and the mixture was heated and stirred for 24 hours. After the completion of the reaction, the organic phase was washed until the wash water became neutral, and then the organic phase was dried using a desiccant. Subsequently, after removing the drying agent, the solvent was distilled off under reduced pressure, and vacuum drying was performed overnight to obtain a white solid (curable organopolysiloxane (U1)).

&Lt; Production Examples 2 to 8 &

The curable organopolysiloxanes (U2) to (U8) were prepared in the same manner as in Production Example 1 and in the composition ratios shown in Table 1. (U4) was prepared in the same procedure as in Production Example 1, except that the reaction time was changed from 24 hours to 1 hour, and (U6) was adjusted from 24 hours to 3 hours. (U5) was prepared by preparing (U4), adding 50% by mass of a methanol solution, adding 2% by mass of acetic acid to the solid content, and then distilling off the solvent under reduced pressure to obtain will be.

The term &quot; phenyl group mole / methyl group mole% &quot; in the following Table 1 refers to an organosiloxy unit in which R in T1 to T3 is a phenyl group in the obtained curable organopolysiloxane, and R in T1 to T3 is a methyl group Lt; / RTI &gt; units of organosiloxane units.

The term &quot; ratio of T units &quot; indicates the ratio (mol%) of the number of each of T1 to T3 units in the obtained curable organopolysiloxane, and the sum of the ratios of the numbers of T1 to T3 units is 100 Respectively.

The term &quot; particle diameter &quot; refers to the particle diameter of the curable organopolysiloxane measured by the above-described dynamic light scattering method. It is intended that the particle diameter &quot; &lt; 40 &quot;

The content of each unit was calculated from ²⁹ Si-NMR or ¹ H-NMR.

&Lt; Example 1 >

The resulting curable organopolysiloxane (U1) was dissolved in PEGMEA to prepare a liquid material (solid content concentration: 40 mass%) containing the curable organopolysiloxane (U1) (the curable organopolysiloxane had a particle diameter Lt; / RTI &gt; in the liquid water).

The support substrate was cleaned by pure washing and UV cleaning.

Subsequently, on the first main surface of the supporting substrate, a liquid material having a size of 278 mm in length and 278 mm in width and containing curable organopolysiloxane (U1) was applied by a spin coater (coating amount 30 g / m 2).

Subsequently, this was heated and cured in air at 350 DEG C for 30 minutes to form a 2.8 mu m-thick silicon resin layer on the first main surface of the supporting substrate to obtain a supporting body A (supporting substrate having a resin layer).

Subsequently, the releasable surface of the silicone resin layer of the support A and the first main surface of a glass substrate (&quot; AN100 &quot;, manufactured by Asahi Glass Co., Ltd.) having the same size as the silicon resin layer and having a thickness of 0.2 mm were opposed to each other, Under the atmospheric pressure, both substrates were superposed on each other so that the centers of gravity of the two substrates overlapped each other in the laminating apparatus to obtain a glass laminate S1.

The obtained glass laminate S1 corresponds to the above-described glass laminate 10 of Fig. 1, and in the glass laminate S1, the peel strength (x) between the interface of the supporting substrate layer and the silicone resin layer is the silicon number (Y) of the interface between the layer and the glass substrate.

Then, the following measurements were made using the obtained glass laminate S1. The following evaluation results are summarized in Table 2 to be described later.

[Evaluation of peelability]

A rectangular sample having a side of 50 mm was cut out from the glass laminate S1. The sample was placed in a hot air oven heated at 450 DEG C (in a nitrogen atmosphere), allowed to stand for 60 minutes, and then taken out. Subsequently, after a second main surface of the glass substrate of the glass laminate S1 is vacuum-adsorbed on a surface plate, a stainless steel blade having a thickness of 0.1 mm is stuck to the interface between the glass substrate and the silicone resin layer at one corner of the glass laminate S1 And a peeling moment was given between the first main surface of the glass substrate and the peelable surface of the silicon resin layer. The second main surface of the support substrate of the glass laminate S1 is adsorbed by a plurality of vacuum adsorption pads at a pitch of 90 mm and then sequentially lifted from the adsorption pads close to the corner portions to form the first main surface of the glass substrate and the silicon resin layer Was peeled off.

From the above results, it was confirmed that the glass substrate could be peeled off even after the high-temperature heat treatment.

The main part of the silicone resin layer is separated from the glass substrate together with the supporting substrate and the result shows that the peeling strength (x) between the supporting substrate layer and the resin layer at the interface is higher than the peeling strength at the interface between the silicon resin layer and the glass substrate (y).

[Heat resistance evaluation]

A quadrangular sample with a side length of 50 mm was cut out from the glass laminate S1. The sample was placed in a hot air oven heated at 450 DEG C (under a nitrogen atmosphere), allowed to stand for 60 minutes, and then taken out, .

&Lt; Examples 2 to 10 >

Except that the liquid materials containing the curable organopolysiloxanes (U2) to (U6) shown in the following Table 2 were used in place of the liquid material containing the curable organopolysiloxane (U1) and the conditions of the heat curing treatment were changed , And the glass laminate S2 to S10 were produced according to the same procedure as in Example 1. [

Table 2 shows the type of solvent and solid content concentration used in the production of the liquid material. With respect to Examples 7 and 8, the conditions of heat curing at the time of heat curing were set at 350 ° C for 30 minutes, and the heat curing was carried out at 150 ° C for 30 minutes in the air, Further heat curing ". In Example 9, the heat curing treatment condition at the time of heat curing was set to "350 ° C, 30 minutes", "heat cured at 150 ° C for 30 minutes in the air, then heated at 350 ° C for 60 minutes Cured at 500 ° C for 60 minutes in the atmosphere &quot;.

The obtained glass laminate S2 to S10 correspond to the glass laminate 10 of Fig. 1 described above. In the glass laminate S2 to S10, the peel strength (x) between the interface of the supporting substrate layer and the silicone resin layer Was higher than the peel strength (y) at the interface between the silicon resin layer and the glass substrate.

The obtained laminated glass bodies S2 to S10 were subjected to the above evaluation of peelability and heat resistance evaluation. The results are summarized in Table 2.

&Lt; Comparative Example 1 &

A glass laminate C1 was obtained in the same procedure as in Example 1 except that a liquid material containing the curable organopolysiloxane (U8) shown in the following Table 2 was used in place of the liquid material containing the curable organopolysiloxane (U1) . [Evaluation of peelability and evaluation of heat resistance] were carried out using the obtained glass laminate C1. The results are summarized in Table 2.

&Lt; Comparative Example 2 &

100 parts by mass of a silicone for reactive release material (trade name: KNS-320A, manufactured by Shinetsu Silicone Co., Ltd.) and a platinum-based catalyst (manufactured by Shinetsu Silicone Co., Ltd. under the trade name of CAT- A glass laminate C2 was produced in accordance with the same procedure as in Example 1 except that the mixture (U9) of 2 parts by mass was used. [Evaluation of peelability and heat resistance evaluation] were carried out using the obtained glass laminate C2. The results are summarized in Table 2.

Further, the form of the glass laminate C2 corresponds to the form described in Patent Document 1.

In Table 2, &quot; evaluation of application property &quot; refers to a case where a liquid material containing a curable organopolysiloxane was applied to show that a silicone resin layer can be formed and a case where a silicone resin layer can not be formed is &quot; .

In the "evaluation of peelability", when a blade made of stainless steel is pierced at the interface between the glass substrate and the silicone resin layer, most of the glass substrate and the silicon resin layer are peeled off at the time when the peeling is given, Quot; indicates that the glass substrate can not be peeled off only by the peeling-off timing, &quot;? &Quot; when the glass substrate can be peeled off, the glass substrate can not be peeled off, or the glass substrate is broken Quot; x &quot;.

In the "heat resistance evaluation" column, when there is no "coloring" or "foaming", "no" is shown, and when there is "

In Table 2, in the "silicone resin layer", the term "T3 unit" and "mol% of Q unit" calculated from the peak area ratio by ²⁹ Si-NMR are shown.

In the present examples and comparative examples, analysis of the silicone resin layer was carried out by the following items and methods.

(1) Analysis of bonding state of silicon atoms in silicon resin layer

The content (mol%) of T3 units and Q units was determined using a nuclear magnetic resonance analyzer (solid ²⁹ Si-NMR: JEOL RESONANCE, ECP600).

The content (mol%) of the T3 unit and the Q unit was respectively determined from the peak area ratio of solid ²⁹ Si-NMR. The silicone resin layer was formed by applying a liquid material containing the curable organopolysiloxane used in each of the Examples and Comparative Examples on a glass substrate by a spin coater and heating and curing under the heating conditions of each of Examples and Comparative Examples to obtain a glass substrate After forming a silicone resin layer, a solid sample obtained by cutting the silicone resin layer with a razor blade was used. The measurement method was a DDMAS method, and the measurement conditions were 1.9 占 퐏 ec pulse width, 300 sec wait time of pulse repetition, 300 scans cumulative number of times, and MAS rotation speed of 10 KHz. The standard of the chemical shift was a peak of -22 ppm derived from dimethylsilicone. The chemical shifts of solid ²⁹ Si-NMR derived from each structure are as follows.

T3: -48 to -88 ppm

Q: -96 to -116 ppm

(2) Analysis of the (A-1) / (B-1) ratio of the silicone resin layer

Was determined from the peak area ratio derived from the Ph group and the Me group using a nuclear magnetic resonance analyzer (solid ¹ H-NMR: JEOL RESONANCE, ECP600). The silicone resin layer was formed by applying a liquid material containing the curable organopolysiloxane used in each of the Examples and Comparative Examples on a glass substrate by a spin coater and heating and curing under the heating conditions of each of Examples and Comparative Examples to obtain a glass substrate After forming a silicone resin layer, a solid sample obtained by cutting the silicon resin layer with a razor blade was used. Depth2 was used for the measurement, and the measurement conditions were a pulse width of 2.3 mu sec, a waiting time of pulse repetition of 15 sec, an integration frequency of 16 scans, and a MAS rotation speed of 22 KHz. The peak of the adamantane derived from the chemical shift was 1.7 ppm. The chemical shifts of solid ¹ H-NMR derived from each structure are as follows.

A-1 (Ph group): 18 to 4 ppm

B-1 (Me group): 4 to -10 ppm

(3) Thickness of the silicon resin layer

The film thickness of the silicone resin layer was measured using a surface roughness and contour shape measuring device (Surfcom 1400G-12 manufactured by Tokyo Seimitsu Co., Ltd.) of the contact type pressure-sensitive device.

(4) Shrinkage stress of the silicone resin layer

The wafer was placed in a predetermined position in a thin film stress measuring device FLX-2320 (manufactured by KLA Tencor) with an orientation flat of a silicon wafer having an outer diameter of 4 inches and a thickness of 525 25 m as a reference, The radius of curvature was measured.

Subsequently, the silicon wafer was taken out and the liquid material containing the curable organopolysiloxane used in each of the examples and the comparative examples was coated on the silicon wafer using the spin coat method, To form a silicone resin layer. The curvature radius of the silicon wafer on which the silicon resin layer was formed was measured at an ambient temperature of 25 占 폚 in the same manner as before the silicone-based cured coating was formed.

(100): 1.805 x 10 &lt; ¹¹ &gt; Pa), h is the thickness [m] of the silicon wafer, t is the thickness of the silicon resin layer Is the thickness [m], and R is the difference [m] between the radius of curvature of the silicon wafer before the silicon resin layer is formed and the radius of curvature of the silicon wafer after the silicon resin layer is formed) Shrinkage stress was calculated.

The organosiloxy units of the silicone resin layers in the glass composites S1 to S9 were composed of Q units and T3 units. In the above-described Example 10 and Comparative Example 1, the Q unit was not detected (the measurement limit was below).

As shown in Table 2, in the glass laminate of the present invention, the silicone resin layer exhibited excellent heat resistance and also had excellent releasability (separability) of the glass substrate. In particular, in Examples 1 to 9 including Q units, the peelability was better.

On the other hand, as shown in Comparative Examples 1 and 2, when a silicone resin layer having a predetermined composition ratio was not used, a desired effect was not obtained.

&Lt; Example 11 >

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

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

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injecting layer and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene as a light emitting layer was added to an 8-quinolinol aluminum complex (Alq ₃ ) (BSN-BCN), and Alq ₃ as an electron transporting layer were formed in this order. [0100] Subsequently, aluminum was deposited by a sputtering method, and etching was performed by photolithography Next, another glass substrate is bonded and sealed with an ultraviolet curable adhesive layer on the second main surface side of the glass substrate. By the above procedure, the organic EL structure A glass laminate S1 having an organic EL structure on a glass substrate (hereinafter referred to as panel A) And a member for an electronic device of the present invention.

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

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

&Lt; Example 12 >

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

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

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

Subsequently, the sealing resin liquid was drawn in a frame shape by a dispenser method, liquid crystal was dropped by a dispenser method in the frame, and then the glass laminate S1-1 on which the pixel electrodes were formed was used to form two glass laminate The second main surface side of the glass substrate of the sieve S1 is bonded, and an LCD panel is obtained by ultraviolet curing and thermal curing.

Subsequently, a second main surface of the supporting substrate of the glass laminate S1-1 was vacuum-adsorbed on the surface plate, and a stainless steel blade having a thickness of 0.1 mm was stuck to the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-2 And the peelable surface of the resin layer is peeled off from the first main surface of the glass substrate. Here, the stabbing of the blade is carried out while spraying the antifungal fluid from the ionizer (manufactured by KYENS) to the interface. Subsequently, the vacuum adsorption pad is pulled up while spraying the water on the peeling wire while spraying the antistatic fluid continuously from the ionizer toward the formed void. After the second main surface of the supporting substrate of the glass laminate S1-2 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, the supporting substrate having the resin layer can be peeled off, leaving only empty cells of the LCD with the supporting substrate of the glass laminate S1-1 on the surface of the substrate.

Subsequently, a second main surface of the glass substrate on which the color filter was formed on the first main surface was vacuum-adsorbed on the surface plate, and a stainless steel blade having a thickness of 0.1 mm was stuck to the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-1 And the peelable surface of the resin layer is peeled off from the first main surface of the glass substrate. After the second main surface of the supporting substrate of the glass laminate S1-1 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised while spraying water between the glass substrate and the resin layer. As a result, the supporting substrate on which the resin layer is fixed can be peeled off, leaving only the LCD cell on the surface of the substrate. In this manner, a plurality of LCD cells constituted by a glass substrate having a thickness of 0.1 mm are obtained.

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

&Lt; Example 13 >

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

Molybdenum was first formed on the second main surface of the glass substrate in the glass laminate S1 by the sputtering method, and a gate electrode was formed by etching using a photolithography method. Subsequently, aluminum oxide is further formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film. Subsequently, indium gallium zinc oxide is formed by a sputtering method and the oxide semiconductor is etched by photolithography Layer. Subsequently, aluminum oxide is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protective layer. Subsequently, molybdenum is deposited by a sputtering method, and the source electrode and the drain Electrodes were formed.

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

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injecting layer and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene as a light emitting layer was added to an 8-quinolinol aluminum complex (Alq ₃ ) (BSN-BCN), and Alq ₃ as an electron transporting layer were formed in this order. [0100] Subsequently, aluminum was deposited by a sputtering method, and etching was performed by photolithography Next, another glass substrate is bonded and sealed with an ultraviolet curable adhesive layer on the second main surface side of the glass substrate. By the above procedure, the organic EL structure A glass laminate S1 having an organic EL structure on a glass substrate (hereinafter referred to as panel B) (A panel for a display device having a supporting substrate) having a member for an electronic device of the present invention.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was stuck into the interface between the glass substrate and the resin layer at the corner of the panel B after the sealing member side of the panel B was vacuum-adsorbed on the surface of the panel, Of course. After the surface of the supporting substrate of the panel B is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the stabbing of the blade is carried out while spraying the antifungal fluid from the ionizer (manufactured by KYENS) to the interface. Then, the vacuum adsorbing pad is pulled up while spraying the water to the peeling wire while spraying the antistatic fluid continuously from the ionizer toward the formed gap. As a result, the supporting substrate having the resin layer can be separated while leaving only the glass substrate on which the organic EL structure is formed on the surface of the substrate.

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

Also, Japanese Patent Application No. 2014-022697 filed on February 7, 2014, the entire contents of the specification, claims, abstract, and drawings are incorporated herein by reference and are incorporated herein by reference.

10, 100, 200: Glass laminate
12: support substrate
14: Silicone resin layer
16: glass substrate
18: Supporting substrate having a resin layer
20: glass substrate having a resin layer
22: member for electronic device
24: laminate having member for electronic device
26: glass substrate having members

Claims (11)

A layer of a supporting substrate, a layer of a silicone resin and a layer of a glass substrate are provided in this order,
Wherein the silicone resin in the silicone resin layer has an organosiloxy unit represented by T3 shown below and a total proportion of organosiloxy units represented by the following T3 to all the organosiloxy units is 80 to 100 mol% ,
(A-1) / (B-1) of the organosiloxy unit (A-1) in which R in the following T3 is a phenyl group and the organosiloxy unit (B- ) Is 80/20 to 20/80,
Wherein the peel strength of the interface between the silicon resin layer and the glass substrate layer is different from the peel strength of the interface between the silicon resin layer and the support substrate layer.
T3: R-SiO _3/2
(Wherein R represents a phenyl group or a methyl group) The glass laminate according to claim 1, wherein the silicone resin further has an organosiloxy unit represented by the following formula (Q).
Q: SiO _4/2 The silicone resin composition according to claim 1 or 2, wherein the silicone resin is a cured product of a curable organopolysiloxane,
Wherein the curable organopolysiloxane has an organosiloxy unit represented by the following T1 to T3 in terms of the ratio (molar amount) of the units: T1: T2: T3 = 0 to 5: 20 to 50: 50 to 80 Wherein T1 + T2 + T3 = 100 is satisfied).
T1: R-Si (-OX) 2 O 1/2
T2: R-Si (-OX) O 2/2
T3: R-SiO _3/2
(Wherein R represents a phenyl group or a methyl group, and X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) The glass laminate according to claim 3, wherein the curable organopolysiloxane has a number average molecular weight of 500 to 2000. The glass laminate according to claim 3 or 4, wherein the weight average molecular weight / number average molecular weight of the curable organopolysiloxane is 1.00 to 2.00. The glass laminate according to any one of claims 3 to 5, wherein a particle diameter of the curable organopolysiloxane measured by a dynamic light scattering method is 0.5 to 100 nm. 7. The glass laminate according to any one of claims 3 to 6, wherein the curable organopolysiloxane is an organopolysiloxane obtained by cohydrolytic condensation of phenyltrichlorosilane and methyltrichlorosilane. The glass laminate according to any one of claims 1 to 7, wherein the thickness of the silicon resin layer is 0.1 to 30 占 퐉. The glass laminate according to any one of claims 1 to 8, wherein the supporting substrate is a glass plate. The method according to any one of claims 1 to 9, wherein the peel strength of the interface of the silicon resin layer to the glass substrate layer is lower than the peel strength of the interface of the silicon resin layer to the support substrate layer , Glass laminate. The method according to any one of claims 1 to 9, wherein the peel strength of the interface of the silicon resin layer to the glass substrate layer is higher than the peel strength of the interface of the silicon resin layer to the support substrate layer , Glass laminate.

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