JP6361440B2 - Glass laminate, method for producing the same, and method for producing electronic device - Google Patents

Description

  The present invention relates to a glass laminate, a method for manufacturing the same, and a method for manufacturing an electronic device.

  In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

Recently, in order to cope with the above problems, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared, and a member for an electronic device such as a display device is formed on the glass substrate of the glass laminate, and then the glass substrate. A method of separating the reinforcing plate from the substrate has been proposed (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 glass substrate are detachably adhered to each other. The reinforcing plate separated from the glass substrate after the interface between the silicone resin layer of the glass laminate and the glass substrate is peeled off can be laminated with a new glass substrate and reused as a glass laminate.
Moreover, in patent document 2, the technique which grind | polishes the glass substrate in a glass laminated body and makes the glass substrate surface a flat surface is disclosed. In particular, the surface waviness on the exposed surface of the resin layer is set to a predetermined value or less, and the glass substrate disposed on the resin layer is polished. As illustrated in FIG. 4 of Patent Document 2, when a glass substrate is disposed and polished on a resin layer having a large surface waviness, the surface waviness on the surface of the resin layer is followed when the glass substrate is peeled off. The surface of the resin layer side of the glass substrate that has been in contact with the glass substrate returns to flatness, while the undulation of the resin layer surface is transferred to the polished surface of the glass substrate. The size of the surface swell is adjusted. When the surface waviness is transferred to the polished surface, which is the formation surface of the electronic device member of the glass substrate, the positional deviation of the electronic device member occurs and the performance of the electronic device deteriorates (for example, display unevenness). May result in a decrease in the productivity of the electronic device.

International Publication No. 2007/018028 JP2013-149713A

On the other hand, in the method of Patent Document 2, in order to form a resin layer having a flat surface, a method in which the resin layer forming composition is applied on a support substrate and then allowed to stand for a predetermined time is employed. If such a method of standing for a certain period of time is adopted, the production efficiency of the glass laminate is lowered, and it cannot be said that it is necessarily an efficient method.
Accordingly, there has been a demand for a glass laminate that is less likely to deteriorate the performance of the obtained electronic device even when the surface waviness on the surface of the resin layer is large, and that can suppress a decrease in productivity of the electronic device.

The present invention has been made in view of the above problems, and is a glass laminate that can efficiently produce an electronic device in which performance deterioration is suppressed even when the surface waviness of the resin layer surface is large. It is an object to provide a body and a method for manufacturing the same.
Another object of the present invention is to provide a method for producing an electronic device using the glass laminate.

As a result of intensive studies to solve the above problems, the present inventors have found that a desired effect can be obtained by using a glass laminate in which the surface shape of the glass substrate is controlled, The present invention has been completed.
That is, the first aspect of the present invention is a support substrate, a resin layer disposed on the support substrate and having a convex portion on the surface opposite to the support substrate side, and a shape of the surface having the convex portion of the resin layer. A glass substrate disposed on the resin layer so as to follow the glass substrate, and the peel strength at the interface between the support substrate and the resin layer is greater than the peel strength at the interface between the resin layer and the glass substrate, The glass substrate has a convex portion at a position directly above the convex portion of the resin layer on the surface opposite to the resin layer side, and the filtered center line waviness X of the surface having the convex portion of the glass substrate is It is a glass laminate that is smaller than the filtered centerline waviness Y of the surface having a convex portion.
In the first aspect, the thickness of the glass substrate is preferably 0.3 mm or less.
In the first aspect, it is preferable that the filtering centerline waviness Y of the surface having the convex portion of the resin layer is more than 0.040 μm and 1.00 μm or less (more preferably, more than 0.040 μm and 0.20 μm or less).
In the first aspect, the difference between the filtered center line waviness Y and the filtered center line waviness X is preferably 0.005 to 0.80 μm (more preferably 0.005 to 0.080 μm).
In the first aspect, the thickness of the resin layer is preferably 2 to 100 μm.
In the first aspect, the resin layer is preferably a silicone resin layer.
In the first embodiment, the silicone resin layer is a layer obtained by curing a crosslinkable organopolysiloxane, and the crosslinkable organopolysiloxane includes an organoalkenylpolysiloxane having an alkenyl group and a hydrogen atom bonded to a silicon atom. It is preferable to contain the organohydrogenpolysiloxane which has.
In the first aspect, the support substrate is preferably a glass plate.
A second aspect of the present invention is a method for manufacturing a glass laminate according to the first aspect, and is a support substrate and a resin that is disposed on the support substrate and has a convex portion on the surface opposite to the support substrate side. Layer and the resin layer are arranged on the resin layer so as to follow the shape of the surface having the convex portion, and the convex portion is placed on the surface opposite to the resin layer side at a position immediately above the convex portion on the resin layer. A step of polishing the surface of the glass substrate in the laminated article having the glass substrate, and the filtering center line undulation X of the surface having the convex portion of the glass substrate while polishing the surface leaving the convex portion on the glass substrate surface. This is a method for producing a glass laminate, which is carried out so as to be smaller than the filtered center line undulation Y of the surface having the convex portions of the resin layer.
According to a third aspect of the present invention, there is provided a member forming step of forming a member for an electronic device on the surface of the glass substrate in the glass laminate of the first aspect to obtain a laminate with a member for an electronic device; A separation step of removing the support substrate with a resin layer including the support substrate and the resin layer from the laminate with the member to obtain an electronic device having a glass substrate and a member for an electronic device is provided.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the surface waviness of the resin layer surface is large, the glass laminated body which can produce efficiently the electronic device by which performance degradation was suppressed, and its manufacturing method are provided. it can.
Moreover, this invention can also impose that the manufacturing method of an electronic device using this glass laminated body is provided.

It is typical sectional drawing from the grinding | polishing process in a prior art to the isolation | separation process which isolate | separates a glass substrate. It is typical sectional drawing from the grinding | polishing process in this invention to the isolation | separation process which isolate | separates a glass substrate. It is typical sectional drawing of one Embodiment of the glass laminated body of this invention. It is typical sectional drawing which shows one Embodiment of the manufacturing method of the glass laminated body of this invention in order of a process.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

As one of the characteristic points of the glass laminate of the present invention, the relationship between the filtered centerline waviness X of the surface having the convex portion of the glass substrate and the filtered centerline waviness Y of the surface having the convex portion of the resin layer Is controlled. Hereinafter, the features of the glass laminate will be described in detail with reference to the drawings.
First, FIG. 1 is a schematic view when a polishing process performed in the prior art is performed. First, FIG. 1A shows a laminated article on which a polishing process is performed. In the laminated article, a support substrate 12, a resin layer 14, and a glass substrate 16 are laminated. The resin layer 14 has a convex portion 30 on the surface 14a opposite to the support substrate 12 side. Further, the first surface 16a on the resin layer 14 side of the glass substrate 16 follows the shape of the surface 14a of the resin layer 14, and has a convex portion 32 on the second surface 16b opposite to the resin layer 14 side. The convex part 32 is located immediately above the convex part 30. When the second surface 16b of the glass substrate 16 in such a laminated article is subjected to a polishing process in the same manner as in the prior art, a convex portion is formed from the second surface 16b of the glass substrate 16 as shown in FIG. 32 is removed, resulting in a flat surface. Next, when the glass substrate 16 is peeled from the obtained laminated article, the first surface 16a of the glass substrate 16 is flattened by the action of returning to the flatness, and the convex portion 30 is removed on the second surface 16b. As a result, the thickness of the glass substrate is reduced, so that the recess 34 is formed. Such a recess 34 becomes deeper as the second surface 16b of the glass substrate 16 in FIG. 1B is flatter, and there is a risk of causing a positional shift of the electronic device member disposed on the second surface 16b. is there.
Next, an embodiment of the present invention will be described in detail with reference to FIG. FIG. 2 (A) is a laminated article that is subjected to a polishing treatment as in FIG. 1 (A). In the present invention, as shown in FIG. 2B, the convex portion 32 remains, and the filtering center line beat of the second surface 16b of the glass substrate 16 beats the filtering center line of the surface 14a of the resin layer 14. A predetermined glass laminate 100 is obtained by polishing so as to be smaller than that. As shown in FIG. 2C, when the glass substrate 16 is peeled from the obtained glass laminate 100, a recess 34 is formed on the second surface 16b of the glass substrate 16 as in FIG. However, in the embodiment of FIG. 2C, unlike FIG. 1C, the depth of the concave portion 34 at which the second surface 16b of the glass substrate 16 appears is not so deep, and therefore is arranged on the second surface 16b. It is difficult for the electronic device member to be displaced.

FIG. 3 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 3, the glass laminated body 100 is a laminated body in which the support substrate 12, the glass substrate 16, and the resin layer 14 exist between them. The resin layer 14 has one surface in contact with the layer of the support substrate 12 and the other surface in contact with the first surface 16 a of the glass substrate 16. In other words, the resin layer 14 is in contact with the first surface 16 a of the glass substrate 16.
The two-layer portion composed of the layer of the support substrate 12 and the resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel. In addition, the two-layer part which consists of the support substrate 12 manufactured beforehand for manufacture of the glass laminated body 100 and the resin layer 14 is called the support substrate 18 with a resin layer.

  This glass laminated body 100 is used until the member formation process mentioned later. That is, the glass laminate 100 is used until an electronic device member such as a liquid crystal display device is formed on the surface of the second surface 16 b of the glass substrate 16. Then, the glass laminated body in which the member for electronic devices was formed is isolate | separated into the support substrate 18 with a resin layer, and the glass substrate with a member, and the support substrate 18 with a resin layer does not become a part which comprises an electronic device. The support substrate 18 with a resin layer is laminated with a new glass substrate 16 and can be reused as a new glass laminate 100.

The interface between the support substrate 12 and the resin layer 14 has a peel strength (x). When a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the resin layer 14, The interface of the resin layer 14 is peeled off. The interface between the resin layer 14 and the glass substrate 16 has a peel strength (y). When a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the resin layer 14 and the glass substrate 16, The interface of the glass substrate 16 peels off.
In the glass laminate 100 (which also means a laminate with an electronic device member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when a stress in the direction of peeling the support substrate 12 and the glass substrate 16 is applied to the glass laminate 100, the glass laminate 100 of the present invention peels off at the interface between the resin layer 14 and the glass substrate 16. 16 and a support substrate 18 with a resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the resin layer 14 to the support substrate 12 can be increased and a relatively higher adhesion can be maintained after the heat treatment than to the glass substrate 16.
In order to increase the adhesion of the resin layer 14 to the support substrate 12, a layer (coating film) of a curable resin composition containing a predetermined component is cured (crosslinked) on the support substrate 12 as described later. It is preferable to form the resin layer 14. The resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of curing.
On the other hand, the bond strength of the cured product after curing to the glass substrate 16 is generally lower than the bond strength generated during the curing. Accordingly, the layer of the curable resin composition is cured on the support substrate 12 to form the resin layer 14, and then the glass substrate 16 is laminated on the surface of the resin layer 14 to manufacture the glass laminate 100. It is preferable.

  Below, each layer (the support substrate 12, the resin layer 14, the glass substrate 16) which comprises the glass laminated body 100 is explained in full detail first, Then, the manufacturing method of a glass laminated body and a glass substrate with a member is explained in full detail.

<Support substrate>
The support substrate 12 supports and reinforces the glass substrate 16, and the glass substrate 16 is deformed, scratched, or damaged when the electronic device member is manufactured in a member forming step (step of manufacturing an electronic device member) described later. Prevent such as.
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Usually, since the member forming process involves heat treatment, the support substrate 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16, and more preferably formed of the same material as the glass substrate 16. The support substrate 12 is preferably a glass plate. In particular, the support substrate 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

  The support substrate 12 may be thicker than the glass substrate 16 or thinner. Preferably, the thickness of the support substrate 12 is selected based on the thickness of the glass substrate 16, the thickness of the resin layer 14, and the thickness of the glass laminate 100. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 16 and the thickness of the resin layer 14 is 0.1 mm, the support is provided. The thickness of the substrate 12 is 0.4 mm. In general, the thickness of the support substrate 12 is preferably 0.2 to 5.0 mm.

  When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient at 25 to 300 ° C. between the support substrate 12 and the glass substrate 16 is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less, Preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 100 may be warped severely or the support substrate 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support substrate 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

<Resin layer>
The resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support substrate 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation. A surface 14a of the resin layer 14 in contact with the glass substrate 16 is in close contact with a first surface 16a of the glass substrate 16 described later so as to be peelable. The resin layer 14 is bonded to the first surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) at the interface is the peel strength (x) at the interface between the resin layer 14 and the support substrate 12. Lower than.
That is, when the glass substrate 16 and the support substrate 12 are separated, the glass substrate 16 is peeled off at the interface between the first surface 16a of the glass substrate 16 and the resin layer 14, and is hardly peeled off at the interface between the support substrate 12 and the resin layer 14. . For this reason, the resin layer 14 is in close contact with the first surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the resin layer 14 is bonded to the first surface 16a of the glass substrate 16 with a certain degree of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In this invention, the property which can peel this resin layer 14 surface easily is called peelability. On the other hand, the support substrate 12 and the resin layer 14 are bonded with a bonding force that is relatively difficult to peel.
The bonding force at the interface between the resin layer 14 and the glass substrate 16 may change before and after the electronic device member is formed on the second surface 16b of the glass substrate 16 of the glass laminate 100 (that is, the peel strength). (X) and peel strength (y) may be changed). However, even after the electronic device member is formed, the peel strength (y) is lower than the peel strength (x).

The resin layer 14 and the layer of the glass substrate 16 are considered to be bonded by a bonding force resulting from weak adhesive force or van der Waals force. When the glass substrate 16 is laminated on the surface after the resin layer 14 is formed, if the resin of the resin layer 14 is sufficiently cross-linked so as not to exhibit adhesive strength, the resin layer 14 is bonded with a bonding force due to van der Waals force. It is thought that. However, the resin of the resin layer 14 often has a certain degree of weak adhesive strength. Even when the adhesiveness is extremely low, the resin of the resin layer 14 adheres to the glass substrate 16 by a heating operation or the like when the electronic device member is formed on the laminated body after the glass laminated body 100 is manufactured. Then, it is considered that the bonding force between the resin layer 14 and the glass substrate 16 increases.
In some cases, the surface of the resin layer 14 before lamination or the first surface 16a of the glass substrate 16 before lamination can be laminated by performing a process of weakening the bonding force between them. By performing non-adhesive treatment or the like on the surface to be laminated and then laminating, the bonding strength at the interface between the resin layer 14 and the glass substrate 16 can be weakened and the peel strength (y) can be lowered.

The resin layer 14 is preferably bonded to the surface of the support substrate 12 with a strong bonding force such as an adhesive force or an adhesive force. For example, as described above, by curing the layer of the curable resin composition on the surface of the support substrate 12, the resin that is a cured product can be adhered to the surface of the support substrate 12, and high bonding strength can be obtained. Further, a treatment for generating a strong bonding force between the surface of the support substrate 12 and the resin layer 14 (for example, a treatment using a coupling agent) is performed to increase the bonding force between the surface of the support substrate 12 and the resin layer 14. It can also be increased.
The fact that the resin layer 14 and the layer of the support substrate 12 are bonded with a high bonding force means that the peel strength (x) at the interface between them is high.

Although the thickness of the resin layer 14 is not specifically limited, It is preferable that it is 2-100 micrometers, It is more preferable that it is 3-50 micrometers, It is further more preferable that it is 7-20 micrometers. When the thickness of the resin layer 14 is within such a range, even if bubbles or foreign matter may be present between the resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 can be suppressed. Can do. Further, if the thickness of the resin layer 14 is too thick, it takes time and materials to form the resin layer 14, which is not economical and the heat resistance may be lowered. Moreover, when the thickness of the resin layer 14 is too thin, the adhesiveness of the resin layer 14 and the glass substrate 16 may fall.
The resin layer 14 may be composed of two or more layers. In this case, “the thickness of the resin layer 14” means the total thickness of all the layers.

The surface 14 a on the glass substrate 16 side of the resin layer 14 has a convex portion 30. The convex portion 30 is a portion protruding from the flat surface of the resin layer 14 surface. In FIG. 3, only one convex portion 30 is shown, but a plurality of convex portions 30 may be provided.
The filtered center line waviness Y (W _CA ) of the surface 14a of the resin layer 14 (the surface having the convex portion 30) is preferably 1.00 μm or less, more preferably 0.50 μm or less, and It is further preferably 40 μm or less, more preferably 0.30 μm or less, and 0.20 μm or less in that an electronic device with suppressed performance deterioration can be more efficiently produced. Particularly preferred is 0.15 μm or less, and most preferred is 0.10 μm or less. When the filtered center line undulation Y is in the above range (preferably 0.50 μm or less), the laminate property of the glass substrate 16 on the resin layer 14 is more excellent. The lower limit of the filtered center line waviness Y (W _CA ) of the surface 14a of the resin layer 14 is not particularly limited, but is usually more than 0.040 μm in many cases. In the present invention, the desired effect can be obtained even if the filtered center line waviness Y exceeds 0.10 μm. In particular, when an LCD device is manufactured as an electronic device, the filtered center line undulation Y is preferably more than 0.040 μm and not more than 0.20 μm.
Here, “surface waviness” is a value obtained by measuring W _CA (filtered centerline waviness) described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. In the present invention, the cutoff value of the filtered waviness curve is 0.8 mm, and the measurement length is 40 mm.
In addition, although the width | variety of a convex part is not restrict | limited in particular, 10 mm or less is preferable.

Although the kind of resin which comprises the resin layer 14 is not restrict | limited in particular, For example, an acrylic resin, polyolefin resin, a polyurethane resin, and a silicone resin are mentioned. Of these, silicone resins are preferred from the viewpoints of heat resistance and peelability. That is, the resin layer 14 is preferably a silicone resin layer (a layer containing a silicone resin).
Hereinafter, the aspect of a silicone resin layer is explained in full detail.

The silicone resin contained in the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the silicone resin preferably has a three-dimensional network structure.
The type of the crosslinkable organopolysiloxane is not particularly limited, and the structure is not particularly limited as long as it is cross-linked and cured through a predetermined cross-linking reaction to obtain a cross-linked product (cured product) constituting the silicone resin. What is necessary is just to have sex. The form of crosslinking is not particularly limited, and a known form can be appropriately employed depending on the kind of the crosslinkable group contained in the crosslinkable organopolysiloxane. Examples thereof include a hydrosilylation reaction, a condensation reaction, a heat treatment, a high energy ray treatment, or a radical reaction using a radical polymerization initiator.
More specifically, when the crosslinkable organopolysiloxane has a radical reactive group such as an alkenyl group or an alkynyl group, the cured product (crosslinked silicone resin) is crosslinked by a reaction between the radical reactive groups via the radical reaction. )
Moreover, when crosslinkable organopolysiloxane has a silanol group, it crosslinks by the condensation reaction of silanol groups, and it becomes a hardened | cured material.
In addition, the crosslinkable organopolysiloxane has an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (ie, an organoalkenylpolysiloxane), and a hydrogen atom bonded to a silicon atom (a hydrosilyl group). In the case where the organopolysiloxane (that is, organohydrogenpolysiloxane) is contained, it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum-based catalyst) as necessary to form a cured product.

Among them, the crosslinkable organopolysiloxane is an organopolysiloxane having an alkenyl group at both ends and / or side chains (hereinafter also referred to as organopolysiloxane A as appropriate) because the silicone resin layer can be easily formed and is excellent in releasability. And an organopolysiloxane having hydrosilyl groups at both ends and / or side chains (hereinafter also referred to as organopolysiloxane B as appropriate) are preferred.
In addition, although it does not specifically limit as an alkenyl group, For example, a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group etc. are mentioned, Especially from the point which is excellent in heat resistance. A vinyl group is preferred.
Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly an alkyl group having 4 or less carbon atoms).

The position of the alkenyl group in the organopolysiloxane A is not particularly limited. However, when the organopolysiloxane A is linear, the alkenyl group may be present in any one of the M unit and D unit shown below. And D units may be present. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.
The M unit and D unit are examples of basic structural units of organopolysiloxane. The M unit is a monofunctional siloxane unit in which three organic groups are bonded. The D unit is bonded to two organic groups. Bifunctional siloxane unit. In the siloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, so that the oxygen atom per silicon atom in the siloxane bond is regarded as ½, Expressed as O _1/2 .

The number of alkenyl groups in the organopolysiloxane A is not particularly limited, but is preferably 1 to 3 per molecule and more preferably 2.
The position of the hydrosilyl group in the organopolysiloxane B is not particularly limited. However, when the organopolysiloxane A is linear, the hydrosilyl group may be present in either the M unit or the D unit. It may be present in both D units. It is preferable that it exists in at least D unit from the point of a cure rate.
The number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, but it is preferably at least 3 per molecule, and more preferably 3.

  The mixing ratio of organopolysiloxane A and organopolysiloxane B is not particularly limited, but the molar ratio of hydrogen atoms bonded to silicon atoms in organopolysiloxane B and all alkenyl groups in organopolysiloxane A (hydrogen atoms / The alkenyl group is preferably adjusted to 0.7 to 1.05. Especially, it is preferable to adjust a mixing ratio so that it may become 0.8-1.0.

As the hydrosilylation catalyst, a platinum group metal catalyst is preferably used. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity. As the platinum group metal catalyst, known catalysts can be used. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
The amount of the hydrosilylation catalyst used is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total mass of the organopolysiloxane A and the organopolysiloxane B.

The number average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and is more resistant to decomposition of the silicone resin under high temperature processing conditions. The weight average molecular weight in terms of polystyrene as measured by chromatography is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.
The viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPa · s, more preferably 15 to 3000 mPa · s.

  Moreover, as a commercially available brand name or model number of the crosslinkable organopolysiloxane, KNS-320A and KS-847 (both manufactured by Shin-Etsu Silicone Co., Ltd.) are used as the crosslinkable organopolysiloxane having no aromatic group. ), TPR6700 (made by Momentive Performance Materials Japan GK), vinyl silicone “8500” (made by Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (made by Arakawa Chemical Industries), vinyl A combination of silicone “11364” (Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11365” (Arakawa Chemical Industries) and methylhydrogenpolysiloxane “ 12031 "(Arakawa Chemical Industries Such as a combination of a Ltd.) and the like.

  The formation method in particular of the resin layer 14 is not restrict | limited, A well-known method is employ | adopted. In the latter part, it explains in full detail regarding the aspect whose resin layer 14 is a silicone resin layer.

<Glass substrate>
As for the glass substrate 16, the 1st surface 16a is in contact with the resin layer 14, and the member for electronic devices is provided in the 2nd surface 16b on the opposite side to the resin layer 14 side.
The glass substrate 16 is arrange | positioned on the resin layer 14 so that the shape of the surface 14a which has the convex part 30 of the resin layer 14 may be followed. Therefore, the glass substrate 16 has the convex part 32 in the position just above the convex part 30 of the resin layer 14 on the 2nd surface 16b. In FIG. 3, only one protrusion 32 is shown, but the number of protrusions 32 is not particularly limited, and a plurality of protrusions 32 may be provided. In addition, since the position of the convex part 32 of the glass substrate 16 exists on the convex part 30 of the resin layer 14, when there are a plurality of convex parts 30 in the resin layer 14, the glass substrate 16 is directly above each convex part 30. The convex portions 32 are located, and the number of the convex portions 32 of the glass substrate 16 usually corresponds to the number of the convex portions 30 of the resin layer 14.

The size of the filtering centerline undulation X of the second surface 16b where the convex portion 32 of the glass substrate 16 is present is not particularly limited, but from the filtering centerline undulation Y of the surface 14a where the convex portion 30 of the resin layer 14 is described above. Is also small. The difference between the filtered centerline undulation Y and the filtered centerline undulation X (filtered centerline undulation Y-filtered centerline undulation X) is not particularly limited, but more efficiently produces electronic devices with suppressed performance degradation. 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less, particularly preferably 0.080 μm or less, more particularly preferably 0.050 μm or less, and 0.040 μm. The following are most preferred. The lower limit is preferably 0.005 μm or more, and more preferably 0.01 μm or more. In particular, when an LCD device is manufactured as an electronic device, the difference between the filtered centerline waviness Y and the filtered centerline waviness X is preferably 0.005 μm or more and 0.080 μm or less.
The size of the filtering centerline waviness X of the second surface 16b where the convex portion 32 of the glass substrate 16 is present is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.20 μm or less, 0.15 μm. The following is more preferable.
The method for measuring the filtered center line undulation is as described above.
The width of the protrusion 32 is not particularly limited, but is preferably 10 mm or less.

  The glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  When the linear expansion coefficient of the glass substrate 16 is large, the member forming process often involves a heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.

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

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

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

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.10 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. It is. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

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

<Glass laminate and production method thereof>
As described above, the glass laminate 100 of the present invention is a laminate in which the support substrate 12, the glass substrate 16, and the resin layer 14 exist between them.
The manufacturing method of the glass laminated body 100 of this invention will not be restrict | limited especially if the glass laminated body of the aspect which satisfy | fills the structure mentioned above is obtained, A well-known method can be employ | adopted. For example, a method of laminating the glass substrate 16 on the resin layer 14 of the support substrate 18 with the resin layer in which the resin layer 14 is disposed on the support substrate 12 and then polishing the surface of the glass substrate 16 is preferable.

In particular, in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), the resin layer 14 is formed by crosslinking and curing a predetermined curable resin composition on the surface of the support substrate 12. A method of forming the resin layer 14 is preferable.
In particular, an embodiment in which a silicone resin layer is obtained using a crosslinkable organopolysiloxane as the curable resin composition is preferable. That is, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate, the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate to form a silicone resin layer (crosslinked silicone resin), and then the silicone resin layer A method of laminating a glass substrate on the silicone resin surface to produce a laminated article, and further polishing the surface of the glass substrate in the laminated article.
When the crosslinkable organopolysiloxane is cured on the surface of the support substrate, it is considered that the crosslinkable organopolysiloxane adheres due to interaction with the surface of the support substrate during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate increases. Therefore, even if the glass substrate and the support substrate are made of the same material, a difference can be provided between the silicone resin layer and the peel strength between them.
Hereinafter, a step of forming a silicone resin layer by forming a layer containing a crosslinkable organopolysiloxane on the surface of the support substrate and crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate, The process of laminating a glass substrate on a silicone resin surface to form a laminated article is referred to as a laminating process, and the process of polishing the surface of the glass substrate is referred to as a polishing process, and the procedure of each process will be described in detail.

(Resin layer forming process)
In the resin layer forming step, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate, and the silicone resin layer is formed by crosslinking the crosslinkable organopolysiloxane on the support substrate surface.
In order to form a layer containing a crosslinkable organopolysiloxane on a support substrate, a coating composition in which the crosslinkable organopolysiloxane is dissolved in a solvent is used, and this composition is applied onto the support substrate to form a solution. It is preferable to form a layer containing the crosslinkable organopolysiloxane by removing the solvent. The thickness of the layer containing the crosslinkable organopolysiloxane can be controlled by adjusting the concentration of the crosslinkable organopolysiloxane in the composition.
The solvent is not particularly limited as long as it can easily dissolve the crosslinkable organopolysiloxane in a working environment and can be easily volatilized and removed. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like.

A method for applying the composition containing the crosslinkable organopolysiloxane on the surface of the supporting substrate is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating.
Then, if necessary, a drying process for removing the solvent may be performed. The method for the drying treatment is not particularly limited, and examples thereof include a method of removing the solvent under reduced pressure conditions and a method of heating at a temperature at which the curing of the crosslinkable organopolysiloxane does not proceed.

Next, the crosslinkable organopolysiloxane on the support substrate is crosslinked to form a silicone resin layer. More specifically, as shown in FIG. 4A, in this step, a silicone resin layer 114 is formed on at least one surface of the support substrate 12.
As described above, the curing (crosslinking) method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment. In particular, when a crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, a silicone resin having excellent adhesion and heat resistance to a glass substrate is obtained, and a silicone resin layer is produced by thermosetting. It is preferable.
Hereinafter, the aspect of thermosetting is explained in full detail.

The temperature condition for thermosetting the crosslinkable organopolysiloxane is not particularly limited as long as the heat resistance of the silicone resin layer 114 is improved and the peel strength (y) after lamination with the glass substrate can be controlled as described above. 150 to 300 ° C is preferable, and 180 to 250 ° C is more preferable. The heating time is usually preferably 10 to 120 minutes, more preferably 30 to 60 minutes.
Normally, when the crosslinkable organopolysiloxane is cured (particularly, thermosetting), the above-described convex portions 30 are formed on the surface 114a of the silicone resin layer 114. The size of the filtering center line undulation of the surface 114a having the convex portion 32 is synonymous with the size of the filtering center line undulation of the surface 14a of the resin layer 14 described above.

  The crosslinkable organopolysiloxane may be cured by precuring (precuring) and then postcuring (main curing). By performing the pre-cure, it is possible to obtain a silicone resin layer 114 that is superior in heat resistance. Precuring is preferably performed following the removal of the solvent. In that case, there is no particular distinction between the step of removing the solvent from the layer to form a layer containing a crosslinkable organopolysiloxane and the step of performing precuring.

(Lamination process)
In the lamination step, a glass substrate is laminated on the silicone resin surface of the silicone resin layer obtained in the resin layer formation step, and a laminated article including a support substrate layer, a silicone resin layer, and a glass substrate layer in this order. It is the process of obtaining. More specifically, as shown in FIG. 4B, a silicone resin layer 114 is formed with a surface 114a opposite to the support substrate 12 side of the silicone resin layer 114 and a first surface 16a of the glass substrate 16 as a laminated surface. The layer 114 and the glass substrate 16 are laminated to obtain a laminated article 40. In addition, the glass substrate 16 in the laminated article 40 is subjected to a polishing process described later.

The method in particular of laminating | stacking the glass substrate 16 on the silicone resin layer 114 is not restrict | limited, A well-known method is employable.
For example, a method of stacking the glass substrate 16 on the surface of the silicone resin layer 114 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 16 is overlaid on the surface of the silicone resin layer 114, the glass substrate 16 may be pressure-bonded to the silicone resin layer 114 using a roll or a press. Air bubbles mixed between the silicone resin layer 114 and the glass substrate 16 can be removed relatively easily by pressure bonding using a roll or a press, which is preferable.

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

  When laminating the glass substrate 16, it is preferable that the surface of the glass substrate 16 in contact with the silicone resin layer 114 is sufficiently washed and laminated in an environment with a high degree of cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16, which is preferable.

In addition, after laminating | stacking the glass substrate 16, you may perform a pre-annealing process (heat processing) as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 114 can be improved and an appropriate peel strength (y) can be obtained. Misalignment of members is less likely to occur, and the productivity of electronic devices is improved.
The conditions for the pre-annealing process are appropriately selected according to the type of the silicone resin layer 114 used, but the peel strength (y) between the glass substrate 16 and the silicone resin layer 114 is more appropriate. From this point, it is preferable to perform heat treatment at 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or longer (preferably 5 to 30 minutes).

By performing the above processing, the glass substrate 16 is disposed on the silicone resin layer 114 so as to follow the shape of the surface of the silicone resin layer 114 having the convex portions 30. The glass substrate 16 has a convex portion 32 at a position directly above the convex portion 30 of the silicone resin layer 114 on the second surface 16b opposite to the silicone resin layer 114 side.
The filtered center line undulation of the second surface 16b having the convex portions 32 of the glass substrate 16 in the obtained laminated article 40 is the same as the filtered center line undulation of the surface 114a having the convex portions 30 of the silicone resin layer 114. In many cases, the values are almost the same.

(Polishing process)
The polishing step is a step of polishing the second surface of the glass substrate in the laminated article obtained in the laminating step. In addition, as shown in FIG. 4C, the polishing is performed by filtering center line waviness of the second surface 16b having the convex portions 32 of the glass substrate 16 while leaving the convex portions 32 of the second surface 16b of the glass substrate 16. It implements so that X may become smaller than the waviness centerline wave | undulation of the surface 114a which has the convex part 30 of the silicone resin layer 114. FIG. That is, in the glass laminate 110 obtained by the polishing treatment, the filtered center line undulation X of the second surface 16b having the convex portions 32 of the glass substrate 16 is the surface having the convex portions 30 of the silicone resin layer 114. It becomes smaller than the wavy centerline undulation of 114a. In particular, the difference between the filtered centerline waviness Y of the second surface 16b having the convex portions 32 of the glass substrate 16 and the filtered centerline waviness Y of the surface 14a having the convex portions 30 of the resin layer 14 described above. It is preferable to carry out the polishing so that the above occurs.

The method of polishing is not particularly limited, and a known method can be adopted. For example, mechanical polishing (physical polishing) or chemical polishing (chemical polishing) can be used. For mechanical polishing, use a sand blasting method in which ceramic abrasive grains are blown and ground, a polishing process using a lapping sheet or a grindstone, a chemical mechanical polishing (CMP) method using a combination of abrasive grains and a chemical solvent, etc. Can do.
As chemical polishing (sometimes referred to as wet etching), a method of polishing the surface of a glass substrate using a chemical solution can be used.
Among these, chemical mechanical polishing is preferable because it is easy to control polishing. In addition, as abrasive grains used in chemical mechanical polishing, known abrasive grains such as cerium oxide can be used.
The glass laminated body mentioned above can be obtained by passing through the said grinding | polishing process.

(Glass laminate)
The glass laminate of the present invention can be used for various applications, for example, manufacturing electronic parts such as display panel, PV, thin film secondary battery, and semiconductor wafer having a circuit formed on the surface, which will be described later. Applications are listed.
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<Glass substrate with member and method for producing the same>
In this invention, the glass substrate with a member (glass substrate with a member for electronic devices) containing a glass substrate and the member for electronic devices is manufactured using the laminated body mentioned above.
Although the manufacturing method of this glass substrate with a member is not specifically limited, From the point which is excellent in productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the said glass laminated body, and the laminated body with an electronic device member is used. A method in which the produced and obtained laminate with a member for electronic devices is separated into a glass substrate with a member and a support substrate with a resin layer by using the glass substrate side interface of the resin layer as a release surface is preferable.
Hereinafter, the step of forming a member for an electronic device on the glass substrate in the glass laminate and manufacturing the laminate with the member for an electronic device is a member forming step, from the laminate with the member for an electronic device to the glass substrate side of the resin layer The step of separating the glass substrate with a member and the support substrate with a resin layer using the interface as a release surface is called a separation step.
The materials and procedures used in each process are described in detail below.

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate in the glass laminated body obtained in the said lamination process (on the surface on the opposite side to the resin layer side of a glass substrate).
First, the electronic device member used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

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

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

(Process procedure)
The manufacturing method of the laminated body with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of component of the member for electronic devices, on the 2nd surface of the glass substrate of a glass laminated body, An electronic device member is formed.
In addition, the member for electronic devices is not all the members finally formed on the 2nd surface of a glass substrate (henceforth "all members"), but a part of all members (henceforth "partial member"). It may be. The glass substrate with a partial member peeled from the resin layer can be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the member for electronic devices may be formed in the peeling surface (1st surface) in the glass substrate with all the members peeled from the resin layer. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate from the laminate with all members. Furthermore, it can also assemble using two laminated bodies with all members, and can peel a 2 support substrate from a laminated body with all members after that, and can manufacture the glass substrate with a member which has two glass substrates.

  For example, taking the case of manufacturing an OLED as an example, in order to form an organic EL structure on the surface opposite to the resin layer side of the glass substrate of the glass laminate (second surface of the glass substrate), Form an electrode, deposit a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface on which a transparent electrode is formed, form a back electrode, seal using a sealing plate, etc. Various layers are formed and processed. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

Further, for example, when manufacturing a TFT-LCD, a metal formed by a general film formation method such as a CVD method or a sputtering method using a resist solution on the second surface of the glass substrate of the glass laminate. A TFT forming process for forming a thin film transistor (TFT) by patterning a film and a metal oxide film, and a color filter (CF) using a resist solution on the second surface of the glass substrate of another glass laminate. ) Forming step, and a lamination step of laminating the laminate with TFT obtained in the TFT formation step and the laminate with CF obtained in the CF formation step.
In the TFT forming process and the CF forming process, a TFT or CF is formed on the second surface of the glass substrate by using a well-known photolithography technique or etching technique. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd surface of a glass substrate as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.
In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other using a sealing agent (for example, an ultraviolet curable sealing agent for cell formation). Thereafter, a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

(Separation process)
The separation step is a glass substrate (a glass substrate with a member) on which an electronic device member is laminated, with the interface between the resin layer and the glass substrate as a release surface, from the laminate with the electronic device member obtained in the member forming step, This is a step of separating a support substrate with a resin layer and obtaining a glass substrate with a member including a member for electronic devices and a glass substrate.
When the member for electronic devices on the glass substrate at the time of peeling is a part of formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate after separation.

The method for peeling the glass substrate and the support substrate is not particularly limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate and the resin layer, and after peeling is given, a mixed fluid of water and compressed air is sprayed to peel off. Can do. Preferably, it is placed on a surface plate so that the support substrate of the laminate with the electronic device member is on the upper side and the electronic device member side is on the lower side, and the electronic device member side is vacuum-adsorbed on the surface plate (on both sides) In this state, the blade is first inserted into the glass substrate-resin layer interface. After that, the support substrate side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. As a result, an air layer is formed on the interface between the resin layer and the glass substrate and on the cohesive failure surface of the resin layer, and the air layer spreads over the entire interface and cohesive failure surface, and the support substrate can be easily peeled off.
Moreover, a support substrate can be laminated | stacked with a new glass substrate, and the glass laminated body of this invention can be manufactured.

  When separating a glass substrate with a member from a laminate with a member for electronic devices, by controlling the spraying with an ionizer and the humidity, the pieces of the silicone resin layer are more likely to be electrostatically adsorbed to the glass substrate with a member. Can be suppressed.

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

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

  EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples.

In the following Examples and Comparative Examples, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.2 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., manufactured by Asahi Glass Co., Ltd.) The name “AN100”) was used. Further, as a support substrate, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.5 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) It was used.

<Example 1>
First, the surface of the support substrate was cleaned by cleaning in the order of an alkaline aqueous solution and pure water.
Next, a solution X, which will be described later, is applied onto the first surface of the support substrate with a die coater (application speed: 40 mm / s, discharge amount: 8 ml), and a layer containing uncured crosslinkable organopolysiloxane (cured) Curable silicone composition layer) was provided on a support substrate to obtain a support substrate with a curable layer (coating amount 20 g / m ² ).
Thereafter, it was cured by heating in the atmosphere at 220 ° C. for 24 minutes to obtain a silicone resin layer having a thickness of 8 μm.
A plurality of convex portions were confirmed on the exposed surface (surface opposite to the support substrate side) of the obtained silicone resin layer. Further, the filtered center line waviness (filtered center line waviness Y) of the exposed surface of the silicone resin layer was 0.185 μm.

(Solution X)
As a component (A), linear vinylmethylpolysiloxane (“VDT-127”, viscosity 700-800 cP (centipoise) at 25 ° C .: made by Amax, mol% of vinyl group in 1 mol of organopolysiloxane: 0.325), Linear methylhydropolysiloxane (“HMS-301” as component (B), viscosity 25-35 cP (centipoise) at 25 ° C .: manufactured by Amax Co., Ltd .: number of hydrogen atoms bonded to silicon atoms in one molecule: 8) Are mixed so that the molar ratio (hydrogen atom / vinyl group) of all vinyl groups and hydrogen atoms bonded to all silicon atoms is 0.9, and the component (C ) 1 part by mass of a silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by the following formula (1) It was.
HC≡C—C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ Formula (1)
Next, a platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) such that the platinum metal concentration is 100 ppm in terms of platinum with respect to the total amount of component (A), component (B), and component (C). ) Was added to obtain a mixed liquid of the organopolysiloxane composition. Furthermore, 150 parts by mass of IP solvent 2028 (initial boiling point: 200 ° C., manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts by mass of the obtained mixed liquid to obtain a mixed solution.

Next, after cleaning the surface of the glass substrate that comes into contact with the silicone resin layer with pure water cleaning, UV cleaning, etc., the silicone resin layer forming surface of the support substrate and the glass substrate are bonded together by a vacuum press at room temperature. A laminated article having a silicone resin layer was obtained.
On the exposed surface (surface opposite to the silicone resin layer side) of the glass substrate in the obtained laminated article, a plurality of convex portions were confirmed. In addition, the convex part of the glass substrate was located just above the convex part of a silicone resin layer. Further, the value of the filtered center line waviness of the exposed surface of the glass substrate was substantially the same as the value of the filtered center line waviness of the surface having the convex portions of the silicone resin layer.

Next, the exposed surface of the glass substrate of the obtained laminated article was polished using an Oscar-type polishing machine to obtain a glass laminate. As the polishing liquid, a cerium oxide polishing solution having an average particle diameter of cerium oxide particles of 1.1 μm and a content of cerium oxide particles of 4% by mass was used. A suede material was used as the polishing pad. The polishing conditions were as follows: the supply amount of the polishing liquid was 1.4 liters / minute, the polishing pressure was 100 gf / cm ² , the rotation speed of the lower surface plate was 386 rpm, and the polishing time was 300 seconds.
Convex portions remain on the exposed surface (second surface) of the glass substrate after polishing, and the filtered center line waviness of the exposed surface of the glass substrate after polishing treatment is caused by the surface of the surface having the convex portions of the silicone resin layer. It was smaller than the wavy centerline swell. More specifically, the filtered center line waviness (filtered center line waviness X) of the exposed surface of the glass substrate after the polishing treatment was 0.130 μm. The difference between the filtered centerline waviness Y and the filtered centerline waviness X was 0.050 μm.
Moreover, in the glass laminate, the peel strength at the interface between the silicone resin layer and the support substrate was greater than the peel strength at the interface between the glass substrate and the silicone resin layer.

Next, the glass laminate was heat-treated at 350 ° C. for 60 minutes in a nitrogen atmosphere and cooled to room temperature. As a result, the glass laminate was separated from the support substrate and the glass substrate, and the silicone resin layer was foamed and whitened. No change was observed.
Then, after vacuum-adsorbing the exposed surface of the glass substrate in the glass laminate subjected to the polishing treatment to the surface plate, the glass substrate and the silicone resin layer at one corner portion of the four corner portions of the glass substrate A stainless steel knife having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the interface between the glass substrate and the silicone resin layer. And after adsorbing a support substrate with 24 vacuum suction pads, it raised in order from the suction pad near the corner part which inserted the blade. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap. As a result, it was possible to separate the glass substrate whose surface was polished on the surface plate from the glass laminate.
When the surface of the separated glass substrate that had been subjected to the polishing treatment was visually confirmed, no defects or the like were confirmed.

<Example 2>
In this example, an LCD was produced using the glass laminate produced in Example 1.
Two glass laminates are prepared. First, a molybdenum film is formed by sputtering on the second surface of a glass substrate that has been subjected to polishing treatment in one glass laminate, and then gated by etching using photolithography. An electrode was formed. Next, on the second surface side of the glass substrate provided with the gate electrode by plasma CVD, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are further formed in this order, and then molybdenum is formed by sputtering. Then, the gate insulating film, the semiconductor element portion, and the source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by forming a silicon nitride film on the second surface side of the glass substrate by a plasma CVD method, an indium tin oxide film is formed by a sputtering method, and etching using a photolithography method is performed. Thus, a pixel electrode was formed. Next, a polyimide resin solution was applied on the second surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminated body is called glass laminated body A1.
Next, a chromium film was formed by sputtering on the second surface of the glass substrate on which the other glass laminate had been subjected to polishing, and a light-shielding layer was formed by etching using photolithography. Next, a color resist was further applied by a die coating method on the second surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second surface side of the glass substrate by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid was applied by die coating on the second surface of the glass substrate provided with the counter electrode, and columnar spacers were formed by photolithography and thermal curing. Next, a polyimide resin solution was applied on the second surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. Next, the sealing resin liquid is drawn in a frame shape on the second surface side of the glass substrate by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two sheets are used using the glass laminate A1 described above. The glass substrate was bonded to the second surface side of the glass substrate, and a laminate having an LCD panel was obtained by ultraviolet curing and thermal curing. Hereinafter, the laminate having the LCD panel is referred to as a laminate B2 with a panel.
Next, LCD panel B (corresponding to an electronic device) composed of a substrate on which a TFT array is formed and a substrate on which a color filter is formed is peeled off from both sides of the laminated body B2 with a panel in the same manner as in Example 1. Got.
When an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region. Further, even when driven in a high temperature and high humidity environment (80 ° C., 80% RH), display unevenness was not recognized.

<Example 3>
In this example, an electronic paper was produced using the glass laminate produced in Example 1.
A molybdenum film was formed by sputtering on the second surface of the glass substrate in the glass laminate, and a gate electrode was formed by etching using a photolithography method. Next, on the second surface side of the glass substrate provided with the gate electrode by plasma CVD, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are further formed in this order, and then molybdenum is formed by sputtering. Then, the gate insulating film, the semiconductor element portion, and the source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by forming a silicon nitride film on the second surface side of the glass substrate by a plasma CVD method, an indium tin oxide film is formed by a sputtering method, and etching using a photolithography method is performed. Thus, a pixel electrode was formed.
Next, indium tin oxide was formed by sputtering on the surface (first main surface) of a separately prepared glass plate, and a counter electrode was formed by etching using photolithography. Next, an adhesive resin liquid in which microcapsules were further dispersed was applied on the first main surface of the glass plate by printing. In the microcapsules, white particles made of titanium oxide and black particles made of carbon black were dispersed in silicone oil in a wall film made of a composite film of gum arabic and gelatin having an average diameter of 50 micrometers. What was enclosed in the state was used. The white particles of titanium oxide were positively charged, while the black particles of carbon black were negatively charged.
Next, the surface on the second surface side of the glass substrate in the glass laminate provided with the pixel electrodes by the above procedure and the surface on the first main surface side of the glass plate coated with the adhesive resin liquid are bonded together. It was. By the above procedure, an electronic paper panel with a supporting substrate (a laminate with an electronic device member) was obtained.
Subsequently, the support substrate with a resin layer was peeled off in the same manner as in Example 1 to obtain an electronic paper panel (corresponding to an electronic device, hereinafter referred to as panel B).
When an IC driver was connected to the manufactured panel B and driven, display unevenness was not observed in the driving region.

<Examples 4 to 12>
A glass laminate was produced according to the same procedure as in Example 1, except that the heat curing, coating speed or discharge rate, and / or polishing treatment conditions during production of the silicone resin layer were appropriately changed. In the glass laminate obtained in each example, the filtered center line waviness of the exposed surface of the glass substrate after the polishing treatment was smaller than the filtered center line waviness of the surface having the convex portion of the silicone resin layer. .
Table 1 below shows the filtered center line waviness (filtered center line waviness X) of the exposed surface of the glass substrate after the polishing treatment in the glass laminate obtained in each example, and the exposed surface of the silicone resin layer. The filtered center line undulation (filtered center line undulation Y) and the difference between the filtered center line undulation X and the filtered center line undulation Y are represented.

  In any of the glass laminates, the peel strength at the interface between the silicone resin layer and the support substrate was greater than the peel strength at the interface between the glass substrate and the silicone resin layer.

Moreover, when the glass laminated body of each Example was heat-processed at 350 degreeC under nitrogen atmosphere for 60 minutes and it cooled to room temperature, isolation | separation of the support substrate of a glass laminated body of each Example and a glass substrate, or a silicone resin layer No change in appearance such as foaming or whitening was observed.
Furthermore, according to the procedure similar to Example 1, when the glass substrate in the glass laminated body of each Example by which the said heat processing was performed was isolate | separated using the suction pad, in any glass laminated body, it fixed. The glass substrate on which the polishing treatment was performed on the board could be separated from the glass laminate.
When the surface of the separated glass substrate that had been subjected to the polishing treatment was visually confirmed, no defects or the like were confirmed.

Furthermore, instead of the glass laminate described in Example 1, each of the glass laminates obtained in each Example was used to produce an LCD panel according to the same procedure as in Example 2 above. Even in the LCD panel, display unevenness was not recognized.
Moreover, when each of the glass laminates obtained in each Example was used instead of the glass laminate described in Example 1 and an electronic paper panel was produced according to the same procedure as in Example 3 above, No display unevenness was observed in the electronic paper panel.

DESCRIPTION OF SYMBOLS 12 Support substrate 14 Resin layer 16 Glass substrate 18 Support substrate with resin layer 30,32 Convex part 34 Concave part 40 Laminated article 100,110 Glass laminated body 114 Silicone resin layer

Claims (12)

A support substrate; a resin layer disposed on the support substrate and having a convex portion on a surface opposite to the support substrate side; and the resin so as to follow a shape of the surface of the resin layer having the convex portion. A glass laminate having a glass substrate disposed on a layer, wherein the peel strength at the interface between the support substrate and the resin layer is greater than the peel strength at the interface between the resin layer and the glass substrate,
The glass substrate has a convex portion at a position directly above the convex portion of the resin layer on the surface opposite to the resin layer side,
The glass laminated body in which the filtering centerline wave | undulation X of the surface which has the said convex part of the said glass substrate is smaller than the filtering centerline wave | undulation Y of the surface which has the said convex part of the said resin layer.   The glass laminated body of Claim 1 whose thickness of the said glass substrate is 0.3 mm or less.   The glass laminate according to claim 1 or 2, wherein a filtered centerline waviness Y of the surface having the convex portion of the resin layer is more than 0.040 µm and 1.00 µm or less.   The glass laminate according to any one of claims 1 to 3, wherein a filtered centerline waviness Y of the surface having the convex portion of the resin layer is more than 0.040 µm and 0.20 µm or less.   The glass laminated body of any one of Claims 1-4 whose difference of the said filter centerline waviness Y and the said filter centerline waviness X is 0.005-0.80 micrometer.   The glass laminate according to any one of claims 1 to 5, wherein a difference between the filtered center line undulation Y and the filtered center line undulation X is 0.005 to 0.080 µm.   The glass laminated body of any one of Claims 1-6 whose thickness of the said resin layer is 2-100 micrometers.   The glass laminate according to any one of claims 1 to 7, wherein the resin layer is a silicone resin layer. The silicone resin layer is a layer obtained by curing a crosslinkable organopolysiloxane,
The glass laminate according to claim 8, wherein the crosslinkable organopolysiloxane includes an organoalkenyl polysiloxane having an alkenyl group and an organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom.   The glass laminated body of any one of Claims 1-9 whose said support substrate is a glass plate. It is a manufacturing method of the glass layered product according to any one of claims 1 to 10,
A support substrate; a resin layer disposed on the support substrate and having a convex portion on a surface opposite to the support substrate side; and the resin so as to follow a shape of the surface of the resin layer having the convex portion. Polishing the surface of the glass substrate in a laminated article that is disposed on a layer and has a glass substrate having a convex portion at a position immediately above the convex portion on the resin layer on the surface opposite to the resin layer side And having a process of
The polishing center line waviness X of the surface of the glass substrate having the convex portion is the center of wave filtration center line waviness of the resin layer while leaving the convex portion on the surface of the glass substrate. The manufacturing method of the glass laminated body implemented so that it may become smaller than Y. The member formation process which forms the member for electronic devices on the surface of the glass substrate in the glass laminated body of any one of Claims 1-10, and obtains the laminated body with the member for electronic devices,
A separation step of removing the support substrate and the support substrate with a resin layer including the resin layer from the laminate with the electronic device member to obtain an electronic device having the glass substrate and the electronic device member. Device manufacturing method.