JPWO2015174216A1 - COMPOSITE, LAMINATE, ELECTRONIC DEVICE, AND METHOD FOR PRODUCING THEM - Google Patents

Abstract

An object of this invention is to provide the composite body etc. which can suppress that a crack propagates to the effective area | region of a glass sheet, when bending deformation, an edge part cutting | disconnection, etc. are performed. The present invention is a composite comprising a glass sheet and a specific resin layer, wherein the resin layer has a thickness of 1 to 100 μm, a Young's modulus in a specific region is 100 MPa or more, and The 180 degree peel strength with respect to a glass sheet is 1 N / 25 mm or more, Furthermore, the said glass sheet is related with the composite_body | complex characterized by having a specific sacrifice groove | channel.

Description

  The present invention comprises a composite having a resin layer on a glass sheet, a laminate formed by laminating a second glass sheet on the resin layer of the composite, and an element formed on the composite or laminate glass sheet. It relates to the technical field of electronic devices.

In recent years, electronic devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) are becoming thinner and lighter. As one method for reducing the thickness and weight of an electronic device, a substrate used for the electronic device has been made thinner.
In addition, by using a thin glass substrate (glass sheet), practical use of an electronic device having flexibility is expected.

However, the glass sheet has insufficient strength and may be cracked when bent.
On the other hand, for example, Patent Document 1 proposes a composite formed by adhering a resin layer to a glass sheet. With such a composite, even if the composite is bent and deformed and a tensile stress is generated on the surface of the glass sheet to be bonded to the resin layer, the tensile stress is reduced by the resin layer and the crack of the glass sheet is suppressed. it can.

International Publication No. 2012/166343

  However, according to the study by the present inventors, even if it is a composite, there is a case where a sufficient strength improvement effect cannot be obtained at the end of the glass sheet or in the vicinity thereof.

  A composite formed by adhering a resin layer to a glass sheet can improve the in-plane strength of the glass sheet. However, the resin layer is not formed on the end portion of the main surface of the glass sheet, and the end portion is bare. Therefore, even if it is a composite, the intensity | strength of the edge part of a glass sheet or its vicinity cannot fully improve. Further, since the end portion of the glass sheet is exposed, chipping or the like that is the starting point of cracking is likely to occur during handling. Further, although greatly influenced by the processing method (cutting method), the glass sheet generally has a lower strength at the end portion and in the vicinity thereof than in the surface.

  Therefore, when the composite is bent and deformed, cracks are likely to occur at the end of the glass sheet or in the vicinity thereof. When a crack occurs at the end or in the vicinity thereof, the crack propagates into the glass sheet according to the applied stress. If this crack propagates to the effective area in the glass sheet surface, it becomes a defect.

Although chamfering is performed in order to prevent such a crack at the end portion and the vicinity thereof, it is difficult to sufficiently prevent the crack at the end portion and the vicinity thereof even if the chamfering is performed.
Moreover, when the glass sheet is thin, it is difficult to chamfer itself.

  An object of the present invention is to solve such problems of the prior art. That is, a composite in which a resin layer is bonded to a glass sheet, and a laminate in which the composite is bonded to the glass sheet, and the end of the glass sheet or the vicinity thereof is subjected to bending deformation or cutting of the end. An object of the present invention is to provide a composite and a laminate that can prevent the crack from propagating to an effective region within the glass surface, and an electronic device that uses this composite or laminate.

In order to achieve such an object, the gist of the present invention relates to the following <1> to <9>.
<1> A composite comprising a glass sheet and a resin layer bonded to one surface of the glass sheet,
The resin layer has a thickness of 1 to 100 μm, a Young's modulus in a region of 0 to 0.5 μm in the normal direction from the interface with the glass sheet is 100 MPa or more, and 180 ° with respect to the glass sheet. The peel peel strength is 1 N / 25 mm or more, and
The said glass sheet has a sacrifice groove | channel extended along the edge part of the said glass sheet at least in the adhesive surface with the said resin layer, The composite_body | complex characterized by the above-mentioned.

<2> The glass sheet has two sacrificial grooves extending in the same direction, and an effective area between the two sacrificial grooves,
And a second sacrificial groove extending along an end of the second effective region inside the effective region and outside the second effective region. The complex according to <1> above.
<3> The composite according to <1> or <2>, wherein the sacrificial groove has a groove that does not penetrate the glass sheet.
<4> The composite according to any one of <1> to <3>, wherein the sacrificial groove has a through groove penetrating the glass sheet.

<5> A laminate in which a second glass sheet is bonded to the resin layer of the composite according to any one of <1> to <4>.

<6> An electronic device having an element on the surface of the glass sheet of the composite according to any one of <1> to <4> or the glass sheet of the laminate according to <5>.

<7> forming a sacrificial groove extending along the edge of the glass sheet;
A resin layer having a Young's modulus of 100 MPa or more and a thickness of 1 to 100 μm in a region where the distance in the normal direction from the interface with the glass sheet is 0 to 0.5 μm on the surface on which the sacrificial grooves of the glass sheet are formed Is formed with an adhesive strength of 1 N / 25 mm or more at 180 ° peel peel strength.

<8> A method for producing a laminate in which a second glass sheet is laminated and bonded to the resin layer of the composite obtained by the production method according to <7>.

<9> Electronic device for forming an element on a glass sheet of a composite obtained by the production method according to <7> or a glass sheet of a laminate obtained by the production method according to <8> Manufacturing method.

According to the present invention, in a composite in which a resin layer is bonded to a glass sheet, and a laminate in which a glass sheet is laminated on the composite, the glass sheet has a resin layer and a specific sacrificial groove, whereby bending deformation occurs. Even if the end portion of the glass sheet or its vicinity is cracked by cutting the end portion or the like, it is possible to suppress the propagation of the crack to the effective region inside the glass sheet at least on the joint surface with the resin layer.
Therefore, according to the present invention, it is possible to obtain an appropriate composite and laminate, and an electronic device for forming an element in the composite or laminate, which do not have a defect of glass sheet cracking.

1A and 1B are diagrams conceptually illustrating an example of the composite of the present invention, in which FIG. 1A is a side view and FIG. 1B is a plan view. FIGS. 2A to 2C are side views conceptually showing another example of the composite of the present invention. 3A and 3B are conceptual diagrams for explaining another example of the composite of the present invention. FIG. 4 is a side view conceptually showing an example of the laminate of the present invention. FIG. 5 is a plan view conceptually showing another example of the composite of the present invention.

  Hereinafter, the composite, laminate and electronic device of the present invention, and methods for producing them will be described in detail based on preferred examples shown in the accompanying drawings. In the present specification, “wt%” and “mass%” and “part by weight” and “part by mass” have the same meaning.

1A and 1B conceptually show an example of the composite of the present invention produced by the production method of the present invention. 1A is a side view (a view seen from the surface direction of the main surface), and FIG. 1B is a plan view (a view seen from the direction orthogonal to the main surface). FIG. 1B is a view of the composite 10 as viewed from the upper side (resin layer 14 side) in FIG.
As shown in FIGS. 1A and 1B, the composite 10 includes a glass sheet 12 and a resin layer 14 formed on one surface (one main surface (front surface)) of the glass sheet 12. Further, four sacrificial grooves 16 extending along the end of the glass sheet 12 are formed on the surface of the glass sheet 12 facing the resin layer 14.

  As the glass of the glass sheet 12 that becomes the substrate (base material) of the composite 10, various known glasses can be used. Specific examples include soda lime glass and alkali-free glass. Moreover, the glass sheet 12 can use what was manufactured by well-known methods, such as a float glass process, a fusion method, and a redraw method.

The thickness of the glass sheet 12 may be a thickness according to the application of the composite 10 (laminated body 50).
Here, the composite 10 of the present invention is used for manufacturing electronic devices such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED) as an example. These electronic devices are required to be thinner and lighter. In order to reduce the thickness and weight of the electronic device, it is advantageous that the glass sheet 12 is thinner.
In addition, as will be described later, in the composite 10 of the present invention, even when the glass sheet 12 is thin, cracks generated at the end portion and in the vicinity thereof are propagated to the in-plane effective region even when being bent and deformed. Can be suppressed. That is, the composite 10 of the present invention is suitably used for applications that require flexibility, such as OLED substrates that require flexibility.
Considering the above points, the thickness of the glass sheet 12 is preferably 100 μm or less, more preferably 75 μm or less, and particularly preferably 50 μm or less.

Moreover, the thickness of the glass sheet 12 should just be more than the thickness which can ensure required intensity | strength according to the use of the composite_body | complex 10. FIG.
Specifically, the thickness of the glass sheet 12 is preferably 1 μm or more, and more preferably 10 μm or more.

Prior to the formation of the resin layer 14, the glass sheet 12 may be subjected to a surface treatment for the purpose of improving the adhesive strength of the resin layer 14.
Examples of the surface treatment include primer treatment, ozone treatment, and plasma etching treatment. Examples of the primer include a silane coupling agent. Examples of the silane coupling agent include amino silanes, epoxy silanes, alkoxy silanes, silazanes and the like.

In the composite 10 of the present invention, on the surface facing the resin layer 14 of the glass sheet 12 (the surface to which the resin layer 14 is bonded), in the vicinity of the four sides of the rectangular glass sheet 12, in the same direction as each side. Four sacrificial grooves 16 are formed extending, that is, along the edge of the glass sheet 12. Accordingly, in FIG. 1A, the two sacrificial grooves 16 shown in the drawing extend in the direction perpendicular to the paper surface, and the remaining two sacrificial grooves not shown in the drawing extend in the lateral direction of the paper surface.
The sacrificial groove 16 is a groove formed outside the effective area of the glass sheet 12 that is appropriately set according to the application of the composite 10. That is, in FIG. 1B, the outside of the four sacrificial grooves 16 of the glass sheet 12 is an ineffective area, and the effective area is set inside the area surrounded by the four sacrificial grooves 16. .
The effective area is, for example, an element (device) formation area in manufacturing an electronic device using the composite 10 as a mother board. Therefore, a plurality of elements corresponding to one electronic device are formed independently of each other in the effective region.

The composite 10 of the present invention has a glass sheet 12, a sacrificial groove 16 formed on the glass sheet 12, and a surface of the glass sheet 12 on which at least the sacrificial groove 16 is formed, with a peel peel strength of 1 N / 25 mm. A resin layer 14 having a thickness of 1 to 100 μm and a Young's modulus of 100 MPa or more in a region where the distance in the normal direction from the interface with the glass sheet 12 is 0 to 0.5 μm, formed with the above adhesive force. Have.
The composite 10 of the present invention has the sacrificial groove 16 and such a resin layer 14, so that it is cracked at the end of the glass sheet 12 or in the vicinity thereof when bent or deformed. Even if (cracks) occur, the propagation (progress) of the cracks can be suppressed by the sacrificial grooves 16. Therefore, even if the composite body 10 is cracked at the end portion or in the vicinity thereof, it is possible to suppress the crack from being propagated to the effective region of the glass sheet 12 and becoming a defect.

As described above, according to the composite formed by forming the resin layer 14 on the surface of the glass sheet 12, it is possible to prevent the glass sheet 12 from being cracked due to bending deformation or the like of the composite.
However, the resin layer 14 may not be formed in the vicinity of the end portion on the main surface of the glass sheet 12, and the strength of the end portion and the vicinity thereof is lower than that of the glass sheet 12 in the plane.
Therefore, when the composite is bent and deformed, or when the end portion is cut, cracks are likely to occur at the end portion and in the vicinity thereof. When a crack occurs at the end or in the vicinity thereof, the crack propagates into the glass sheet according to the applied stress. If this crack propagates to the effective area in the glass sheet surface, it becomes a defect.

In contrast, in the composite 10 of the present invention, the resin layer 14 has a predetermined rigidity and thickness, and is formed on the main surface of the glass sheet 12 with a predetermined adhesive force. A sacrificial groove 16 is provided on the surface facing the resin layer 14 (surface on which the resin layer 14 is bonded) and outside the effective region.
Therefore, even when the composite 10 is bent and deformed so that the resin layer 14 side is convex, cracks are generated at the end portions and the vicinity thereof, and even if this crack propagates to the inner surface side, the cracks caused by the sacrificial grooves 16 The propagation of cracks and the crack spreading effect of the resin layer 14 can suppress the propagation of cracks at the position of the sacrificial grooves 16 (the propagation of cracks can be cut off by the sacrificial grooves 16). Therefore, the composite 10 of the present invention can suppress the cracks at the ends and the vicinity thereof from propagating to the effective region of the glass sheet 12 and becoming defects.

As described above, the sacrificial groove 16 is formed outside the effective area of the glass sheet 12.
1A and 1B, all the sacrificial grooves 16 corresponding to the four sides of the glass sheet 12 are formed so as to extend over the entire area of the glass sheet 12 (formed in a lattice pattern). However, various other configurations can be used. For example, the sacrificial groove may be formed in a rectangular shape surrounding the effective area. Alternatively, a sacrificial groove that extends over the entire area of the glass sheet 12 and a sacrificial groove that ends at a position that intersects with another sacrificial groove may be mixed.
The sacrificial groove 16 is preferably formed at a position closer to the end of the glass sheet 12 in that the effective area can be set wider.

What is necessary is just to set the width | variety of the sacrificial groove | channel 16 suitably the width | variety which can suppress propagation of a crack according to the thickness of the glass sheet 12, the magnitude | size of a main surface, a forming material, etc.
According to the study by the present inventors, the width of the sacrificial groove 16 is preferably 100 μm or less, and more preferably 10 μm or less. Further, if the sacrificial groove 16 has a width (opening) equal to or larger than the atomic level, a sufficient effect can be obtained. Specifically, the width of the sacrificial groove 16 may be 1 nm or more.
By making the width of the sacrificial groove 16 in the above range, it is preferable in that the propagation of the crack of the glass sheet 12 can be suitably suppressed, and the crack of the glass sheet 12 starting from the sacrificial groove 16 can be suitably prevented.

The depth of the sacrificial groove 16 may be set as appropriate in accordance with the thickness of the glass sheet 12, the forming material, the required strength, and the like so that the propagation of cracks can be suppressed.
According to the study by the present inventors, the depth of the sacrificial groove 16 is preferably 5 μm or more, and more preferably 10 μm or more.
Setting the depth of the sacrificial groove 16 to 5 μm or more is preferable in that the propagation of cracks in the glass sheet 12 can be suitably suppressed.

There is no upper limit to the depth of the sacrificial groove. That is, like the sacrificial groove 20 of the composite body 10 a conceptually shown in FIG. 2A, the sacrificial groove may be a through groove that penetrates the glass sheet 12.
In general, the elements constituting the electronic device are formed on the surface of the glass sheet 12. Therefore, according to the sacrificial groove 16 that does not penetrate the glass sheet 12 like the sacrificial groove 16 shown in FIG. 1A, the gas barrier effect of the glass sheet 12 can be obtained for the elements constituting the electronic device. .
On the other hand, the sacrificial groove formed through the glass sheet 12 like the sacrificial groove 20 shown in FIG. 2A is only when the composite 10a is bent and deformed so that the resin layer 14 side is convex. However, even if the composite 10a is bent and deformed so that the resin layer 14 side is concave, cracks are generated at the ends and in the vicinity thereof, and even if this crack propagates to the inner surface side, the propagation of the cracks is prevented in the sacrificial groove 20. Can be suppressed by position.

In addition to the sacrificial grooves, various configurations can be used.
Each of the forms shown in FIGS. 2B and 2C is a form in which sacrificial grooves having a depth that does not penetrate the glass sheet 12 are formed on both surfaces of the glass sheet 12.
In FIG. 2B, the sacrificial groove 24a is formed on one surface of the glass sheet 12, the sacrificial groove 24b is formed on the other surface of the glass sheet 12, and the sacrificial grooves extending in the depth direction are not connected to each other. Shows a form in which the position of the sacrificial groove is slightly shifted.
FIG. 2C shows that the sacrificial groove 26a is formed on one surface of the glass sheet 12, the sacrificial groove 26b is formed on the other surface of the glass sheet 12, and the sacrificial groove when the glass sheet 12 is viewed in plan view. 26A and 26B, the sacrifice groove 26b is in the same position. However, the depth of each groove is made shallow so that the sacrifice groove 26a and the sacrifice groove 26b are not connected.
Furthermore, as the sacrificial groove, a groove that does not penetrate the glass sheet 12 and a through groove may be mixed.
In addition, when the resin layer 14 is formed only on one surface of the glass sheet 12 with or without the sacrificial groove, the surface of the glass sheet 12 on which the resin layer 14 is not formed is The element formation surface of the electronic device of the present invention is usually covered with an interlayer insulating film, a protective film, or the like in a state of being an electronic device.

In the composite 10 shown in FIGS. 1A and 1B, sacrificial grooves 16 are formed corresponding to all four sides of the rectangular glass sheet 12.
However, in the composite of the present invention, the sacrificial groove should correspond to at least one side of the glass sheet 12 and extend along the side (end) in the same direction as the side. Good. That is, the composite (laminate) of the present invention only needs to have one or more sacrificial grooves extending along the edge of the glass sheet. If there is at least one sacrificial groove extending along the edge of the glass sheet, the crack generated from the end and the vicinity thereof is on the inner side (opposite to the end where the crack occurred). Propagation can be prevented.
The sacrificial groove does not necessarily need to be parallel to the end (side) of the glass sheet.
In the composite of the present invention, the sacrificial groove is preferably formed to extend in the same direction as at least two opposite sides (a pair of opposite sides) of the glass sheet 12.
For example, when the composite 10 is used for an application in which the composite 10 is curved only in the longitudinal direction (up and down direction in FIG. 1B) (curved by extending the apex in the short direction), FIG. ) May be provided with only two sacrificial grooves 16 extending in the vertical direction (in FIG. 1A, the direction orthogonal to the paper surface). Conversely, when the composite 10 is used for an application in which it is curved only in the short direction (lateral direction in FIG. 1), two sacrificial grooves extending in the lateral direction in FIG. 1 (B). It may have only 16.

The composite of the present invention can also be used for manufacturing electronic devices using so-called roll-to-roll (hereinafter referred to as RtoR).
RtoR is a roll of a long substrate to be processed, rolled out, and the substrate to be processed is sent out from the roll and conveyed in the longitudinal direction to perform a predetermined process. It is a manufacturing method wound in a shape. For example, as conceptually shown in FIG. 3 (A), the substrate 30 to be processed is fed from a substrate roll 30R formed by winding a long substrate 30 into a roll shape, and the longitudinal direction ( While being conveyed in the direction of the arrow in FIG. 3A, the resist layer forming apparatus 32 continuously applied the resist solution and dried (or further heat treated) to form a resist layer, thereby forming the resist layer. The processed base material 34 is wound into a roll shape to obtain a processed base material roll 34R.

The long composite 33 of the present invention corresponding to such RtoR has a width direction (longitudinal direction) of the surface facing the resin layer 36 of the glass sheet 35 as conceptually shown in FIG. Sacrificial grooves 38 extending in the longitudinal direction are provided on both outer sides of the effective area in the direction orthogonal to the longitudinal direction.
In RtoR, the wound composite is subjected to stress that is pulled in the longitudinal direction. However, by having the sacrificial grooves 38 extending in the longitudinal direction on both outer sides in the width direction of the effective region, the stress can cause cracks at the end of the glass sheet and in the vicinity thereof and propagate in the inner surface direction. Since propagation can be suppressed in the sacrificial groove 38, it is possible to suppress cracks from reaching the effective region existing inside the sacrificial groove 38.

  When the composite of the present invention is used for the production by RtoR, when individual effective regions in the longitudinal direction are known, in addition to the sacrificial grooves 38 on both sides in the width direction, it corresponds to each effective region. Thus, sacrificial grooves extending in the width direction may be formed at intervals in the longitudinal direction, and the sacrificial grooves may be formed so as to surround individual effective regions.

In the composite 10 of the present invention, various known methods for forming the grooves in the sheet-like glass can be used as the method for forming the sacrificial grooves.
As a method for forming the sacrificial groove, for example, there are various scribe line forming methods for cutting glass, such as a scribe line forming method using a glass cutter such as a wheel cutter, a scribe line forming method using a laser beam, and the like. Is available.

Here, the effect of stopping the propagation of cracks by the sacrificial groove is better obtained as the strength of the sacrificial groove (sacrificial groove wall) is higher. That is, the smaller the chipping of the sacrificial grooves, the micro cracks, etc., the higher the effect of suppressing the propagation of cracks by the sacrificial grooves.
Therefore, it is preferable to form the sacrificial groove by a method capable of obtaining a sacrificial groove with high strength and less chipping and microcracks.
As an example, the method described in WO2003 / 013816 is exemplified. In this sacrificial groove forming method, the laser beam is continuously irradiated so as to form a laser beam spot below the softening point of the glass sheet 12 along the sacrificial groove to be formed while following the laser beam spot. While cooling along the sacrificial groove, the sacrificial groove is formed by setting the side near the cooling position of the laser beam spot to the maximum energy intensity.
Examples of other methods include a method of forming a sacrificial groove with a laser beam having an ultrashort pulse with a short pulse width, a method of forming a sacrificial groove so as to melt a glass sheet with a laser beam, and the like.

A resin layer 14 is formed on the surface (main surface) of the glass sheet 12.
As described above, the sacrificial groove is formed at least on the surface of the glass sheet 12 facing the resin layer 14. In other words, the resin layer 14 is formed at least on the formation surface of the sacrificial groove of the glass sheet 12.
1A and 1B, the resin layer 14 is provided only on one side of the glass sheet 12, but in the composite of the present invention, the resin layer 14 is provided on both sides of the glass sheet 12. May be provided. In this case, sacrificial grooves are formed on both surfaces of the glass sheet 12.

The resin layer 14 is a layer (film) made of various resin materials. In the composite shown in FIGS. 1A and 1B, etc., the resin layer 14 is formed of one layer. However, if the total thickness is 1 to 100 μm, the resin layer 14 has a plurality of layers. May be formed. Moreover, when forming the resin layer 14 by multiple layers, all the layers may be formed with the same material and the layer which consists of a different material may be mixed. Furthermore, when forming the resin layer 14 with multiple layers, the thickness of each layer may be the same or different.
In addition, although the composite shown by FIG. 1 (A) and (B) etc. has formed the resin layer 14 on the whole surface of the glass sheet 12, sufficient area corresponding to the size and shape of the composite to manufacture. If it has, the resin layer 14 does not need to be formed in the whole surface of the glass sheet 12. FIG.
However, in the composite of the present invention, even when the resin layer 14 does not cover the entire surface of the glass sheet 12, the resin layer 14 is always formed so as to cover the sacrificial groove, and cracks propagate to the effective region and cause defects. Can be suppressed.

Here, in the composite 10 of the present invention, the resin layer 14 has a thickness of 1 to 100 μm, and a Young's modulus in a region where the distance in the normal direction from the interface with the glass sheet 12 is 0 to 0.5 μm is 100 MPa. That's it. Further, the resin layer 14 is adhered to the surface of the glass sheet 12 with an adhesive strength of 180 N peel peel strength of 1 N / 25 mm or more.
As described above, the composite 10 of the present invention has a sacrificial groove formed in the glass sheet 12 and has such a resin layer 14 so that the composite 10 is bent and deformed with the resin layer 14 side convex. In such a case, a crack is generated at the end of the glass sheet 12 or in the vicinity thereof, and even if this crack propagates to the inner surface side, the resin layer 14 suppresses the spread of the crack. This can suppress the propagation of cracks.

If the thickness of the resin layer 14 is less than 1 μm, the effect of having the resin layer 14 cannot be obtained, and cracks generated at the edge of the glass sheet 12 or in the vicinity thereof propagate beyond the sacrificial groove to the inner surface. As a result, the resin layer 14 is also torn and separated simultaneously with the progress of cracks from the end portion and the vicinity thereof.
On the other hand, when the thickness of the resin layer 14 exceeds 100 μm, it is impossible to obtain the composite 10 having good flexibility, and it is difficult to cope with the reduction in thickness and weight.

  Further, the thickness of the resin layer 14 is preferably 10 to 50 μm in that the effect of stopping the propagation of cracks by the sacrificial grooves can be obtained more suitably, and the composite 10 having good flexibility can be obtained.

The resin layer 14 is a region whose distance in the normal direction (direction perpendicular to the interface) from the interface with the glass sheet 12 is 0 to 0.5 μm (that is, a region having a thickness of 0.5 μm or less on the glass sheet 12 side). The Young's modulus (hereinafter, also simply referred to as “Young's modulus of the resin layer 14”) is 100 MPa or more.
If the Young's modulus of the resin layer 14 is less than 100 MPa, the cracks generated at the end of the glass sheet 12 and the vicinity thereof propagate to the inner surface beyond the sacrificial groove, or simultaneously with the progress of the cracks from the end and the vicinity. 14 also tears and separates.

  The Young's modulus of the resin layer 14 is preferably 1000 MPa or more in that the effect of suppressing the propagation of cracks by the sacrificial grooves can be more suitably obtained.

  There is no limitation on the upper limit of the Young's modulus of the resin layer 14. Here, in consideration of not lowering flexibility (not improving bending rigidity), the Young's modulus of the resin layer 14 is preferably 50000 MPa or less, and more preferably 10000 MPa or less.

The Young's modulus of the resin layer 14 may be measured by a method based on JIS K 7127 (1999).
In addition, when the resin layer 14 (region having a thickness of 0.5 μm or less on the glass sheet 12 side) is composed of a plurality (n) of layers, the Young's modulus E (Young's modulus E) of the resin layer 14 is as follows. What is necessary is just to calculate by Formula (1).
E = Σ (E _k × I _k ) / I (1)
E _k ; Young's modulus of k-th layer material I _k ; k-th layer cross-sectional second moment k; integer of 1 to n I; thickness of resin layer 14 on glass sheet 12 side 0 to 0.5 μm As is apparent from the sectional second moment of the region (1), even when the resin layer 14 is bonded to the glass sheet 12 with an adhesive, and the adhesive is softer than the resin layer 14, the adhesive layer If the thickness is sufficiently thin (for example, 100 nm or less), the Young's modulus of the resin layer 14 is 100 MPa or more.

In the production method of the present invention, the resin layer 14 is bonded to the glass sheet 12 with an adhesive strength of 1 N / 25 mm or more with 180 ° peel peel strength (hereinafter also simply referred to as “adhesive strength of the resin layer 14”).
When the adhesive strength of the resin layer 14 is less than 1 N / 25 mm, cracks generated at the edge of the glass sheet 12 or in the vicinity thereof propagate to the inner surface beyond the sacrifice groove, or the resin layer 14 peels around the sacrifice groove. Inconvenience occurs.

  The adhesive strength of the resin layer 14 is preferably 3 N / 25 mm or more, and more preferably 5 N / 25 mm or more in that the effect of propagation of cracks by the sacrificial grooves can be more suitably obtained.

  Moreover, there is no limitation in the upper limit of the adhesive force of the resin layer 14.

  In addition, what is necessary is just to measure the adhesive force (180 degree peel peel strength) of the resin layer 14 based on JISK6854 (1999).

The resin layer 14 can be formed of various known resin materials (polymer materials). For example, any of a thermoplastic resin and a thermosetting resin may be used.
Examples of the thermosetting resin include polyimide (PI) and epoxy (EP).
Examples of the thermoplastic resin include polyamide (PA), polyamideimide (PAI), polyetheretherketone (PEEK), polybenzimidazole (PBI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone ( Examples thereof include PES), cyclic polyolefin (COP), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), acrylic (PMMA), and urethane (PU).
The resin layer 14 may be formed of a photocurable resin, and may be a copolymer or a mixture.

An electronic device manufacturing process in which the composite 10 (laminated body 50) is used may include a process involving heat treatment. Therefore, the heat resistant temperature (continuous usable temperature) of the resin material forming the resin layer 14 is preferably 100 ° C. or higher.
Examples of the resin having a heat resistant temperature of 100 ° C. or higher include polyimide (PI), epoxy (EP), polyamide (PA), polyamideimide (PAI), polyetheretherketone (PEEK), polybenzimidazole (PBI), polyethylene terephthalate ( PET, polyethylene naphthalate (PEN), polyethersulfone (PES), cyclic polyolefin (COP), polycarbonate (PC), polyvinyl chloride (PVC), acrylic (PMMA), urethane (PU), etc. .

The resin layer 14 may be formed of only a resin material, or may contain a filler or the like.
Examples of the filler include fibrous or non-fibrous fillers such as plates, scales, granules, irregular shapes, and crushed products.
Specifically, glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers , Alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica, calcium carbonate, glass beads, Glass flake, glass microballoon, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate, metal powder, metal flake, metal ribbon, metal oxide, carbon powder, graphite, carbon flake, scaly Bon, such as carbon nanotubes is exemplified. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. The type of glass fiber or carbon fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from long fiber type, short fiber type chopped strand, milled fiber, and the like. Moreover, the resin layer 14 may be comprised with the woven fabric and nonwoven fabric which were impregnated with resin.

  The resin forming the resin layer 14 may enter the sacrificial groove and completely fill the sacrificial groove, or may penetrate into the sacrificial groove and partially fill the sacrificial groove, or may be completely sacrificed. It is not necessary to enter the groove.

The resin layer 14 may be formed by a known method corresponding to the material for forming the resin layer 14.
For example, the resin layer 14 may be formed by applying a liquid composition (coating material) containing a component that becomes the resin layer 14 to the surface of the glass sheet 12 on which the sacrificial grooves are formed, and curing it.
Alternatively, the resin layer 14 may be formed by attaching a resin film (resin sheet) to be the resin layer 14 to the surface of the glass sheet 12 on which the sacrificial grooves are formed. Adhesion of the resin film to be the resin layer 14 to the glass sheet 12 may be performed by a known method according to the forming material of the resin layer 14 such as pressure bonding, thermocompression bonding, and reduced pressure thermocompression bonding.
In addition, when sticking a resin film on the glass sheet 12 and forming the resin layer 14, you may adhere | attach a resin film on the glass sheet 12 using an adhesive agent as needed. In this case, the adhesive layer is also regarded as a part of the resin layer 14, and the resin layer 14 including a plurality of layers including the adhesive layer needs to satisfy conditions such as Young's modulus.
Moreover, the resin layer 14 forms a layer (film) made of a precursor of a resin material to be the resin layer 14 on the surface of the glass sheet 12, and the layer made of this precursor is subjected to heat treatment, electron beam irradiation, ultraviolet irradiation. The resin layer 14 made of a target resin material may be obtained by performing the above-described process. In this method of forming the resin layer 14, the precursor layer may be formed by applying a liquid composition on the surface of the glass sheet 12 and drying (or further curing), or the glass sheet 12. It may be formed by attaching a film-like material to the surface (adhesive may be used if necessary).

In FIG. 4, an example of the laminated body of this invention is shown notionally.
A laminated body 50 of the present invention shown in FIG. 4 is obtained by laminating and bonding a second glass sheet 52 to the resin layer 14 of the composite body 10 composed of the glass sheet 12 and the resin layer 14 described above. That is, the laminate 50 is a laminate of the composite 10.

In the laminated body 50, the glass of the 2nd glass sheet 52 can utilize well-known various glass like the above-mentioned glass sheet 12, Furthermore, what was manufactured by the well-known method can be utilized.
In addition, when the manufactured laminated body 50 is utilized for the use which performs the process accompanied by heating, such as heat processing, the 2nd glass sheet 52 is formed with the material with a small difference of a linear expansion coefficient with the glass sheet 12. It is preferable that the glass sheet 12 is formed of the same material.

The thickness of the second glass sheet 52 may be a thickness according to the use of the laminate 50 to be manufactured. Therefore, the thickness of the second glass sheet 52 may be the same as that of the glass sheet 12, or may be thicker or thinner than the glass sheet 12.
As an example, the laminated body 50 is used for manufacturing electronic devices such as PV, LCD, and OLED using the composite 10 (glass sheet 12) as a substrate (substrate on which elements are formed (element substrate)). In this case, the second glass sheet 52 functions as a support base (carrier substrate) that supports the composite 10 in which elements are formed on the glass sheet 12 and enables proper handling. Therefore, in this case, the thickness of the second glass sheet 52 is preferably 0.2 to 1 mm, and more preferably 0.4 to 0.7 mm.

As the method for adhering the second glass sheet 52 to the resin layer 14 of the composite 10 in the laminate 50, various known methods corresponding to the material for forming the resin layer 14 can be used.
As an example, a method using an adhesive, a method using pressure bonding, a method using thermocompression bonding, a method using reduced pressure thermocompression bonding, and the like are exemplified.
In addition, the 2nd glass sheet 52 may be surface-treated before the lamination | stacking to the resin layer 14 for the purpose of the improvement of the adhesive force, etc. Examples of the surface treatment of the second glass sheet 52 include various surface treatments exemplified above in the description of the glass sheet 12.

In addition, when using the laminated body 50 for manufacture of OLED etc., when using the 2nd glass sheet 52 as a support base material, the 2nd glass sheet 52 is peeled from the resin layer 14 finally. .
Therefore, in this case, the resin layer 14 and the second glass sheet 52 can be peeled off from the resin layer 14 and the second glass sheet 52 as necessary while securing a sufficient adhesive force. It may be glued.

The composite 10 (laminated body 50 shown in FIG. 4) shown in FIGS. 1A and 1B forms a sacrificial groove 16 outside the effective area according to the effective area set on the inner surface of the glass sheet 12. doing.
In the composite of the present invention, a plurality or a single second effective region corresponding to the formation region of each electronic device (its element) is further set in the effective region set on the inner surface of the glass sheet 12. Thus, a second sacrificial groove may be formed on the surface on which the sacrificial groove 16 is formed, corresponding to at least one of the second effective regions.
FIG. 5 shows a plan view of an example thereof.

Similar to the composite 10, the composite 40 shown in FIG. 5 is formed by laminating a resin layer 14 on a glass sheet 12. Further, a sacrificial groove 16 is formed on the outer surface of the effective region on the surface of the glass sheet 12 facing the resin layer 14, as in the composite 10.
In the composite 40, six second effective regions a to f indicated by alternate long and short dash lines are set in the effective region surrounded by the sacrificial groove 16.
The second effective area is an area corresponding to one electronic device. That is, in the manufacture of an electronic device, an element that becomes one electronic device is formed in the second effective region. Therefore, after the element is formed in the second effective regions a to f, the complex 40 is cut along a cutting line indicated by a two-dot chain line, for example.

The composite 40 further has a second sacrificial groove 42a to surround the second effective region on the outer side of the glass sheet 12 facing the resin layer 14 in correspondence with the second effective regions a to f. 42f is formed. The second sacrificial grooves 42a to 42f are formed between the cutting line and the second effective region.
The second sacrificial grooves 42a to 42f are basically the same as the sacrificial groove 16 except that they correspond to the second effective area set in the effective area.
That is, the composite according to the present invention has two sacrificial grooves extending in the same direction, and an effective area between the two sacrificial grooves, and further, a second effective area inside the effective area. And a second sacrificial groove extending along the end of the second effective region inside the effective region and outside the second effective region.

As described above, the resin layer 14 has a predetermined rigidity and thickness, and is bonded to the glass sheet 12 with a predetermined adhesive force. In addition, in a state where the complex 40 is cut along a cutting line, the original second effective region becomes an effective region in each cut complex. Further, a second sacrificial groove extending along the end of the second effective region is formed outside the second effective region.
Therefore, the cut glass sheet 12 and the resin layer 14 that become a substrate (element substrate) of the electronic device even when the composite 40 is cut at the cutting line (two-dot chain line) to form individual electronic devices. Is a composite of the present invention in which a sacrificial groove is formed outside the effective region.
Therefore, at the time of cutting, due to bending deformation with the resin layer 14 protruding in the process after cutting and use of the electronic device, cracking occurs at the end of the glass sheet 12 and the vicinity thereof, and the crack is directed toward the inner surface. Propagation of cracks in the sacrificial grooves (original second sacrificial grooves) is suppressed, and cracks can be prevented from reaching the effective area (original second effective area).

In the composite 40 shown in FIG. 5, each second effective region is surrounded by a rectangular sacrificial groove.
However, in the composite of the present invention, the second sacrificial groove corresponding to the second effective region also corresponds to at least one side of the second effective region along the side (end). It may be formed extending in the direction. That is, the second sacrificial groove only needs to have one or more extending along the end of the second effective region. If there is at least one second sacrificial groove extending along the end of the second effective region, cracks generated from the end of the cut composite or the vicinity thereof are inside the second sacrificial groove. Propagation can be prevented.
Further, the second sacrificial groove is not necessarily parallel to the end (side) of the second effective region.
In the composite of the present invention, the second sacrificial groove corresponding to the second effective region is also preferably formed corresponding to at least two opposing sides (a pair of opposing sides) of the second effective region.
For example, when the element formed in the second effective region a is used for an application in which bending deformation is performed only in the vertical direction in FIG. 5, the second sacrificial groove formed corresponding to the second effective region a. The number 42a may be only two that extend in the vertical direction in FIG. 5 and that are formed across the second effective region a in the horizontal direction in FIG.
Further, when the element formed in the second effective region c is used for an application in which bending deformation is performed only in the lateral direction in FIG. 5, the second sacrificial groove formed corresponding to the second effective region c. The number 42c may be only two that extend in the horizontal direction in FIG. 5 and are formed with the second effective region c sandwiched in the vertical direction in FIG.

  In the composite of the present invention, when the second effective area is set and the second sacrificial groove is formed corresponding to the second effective area, all the second effective areas are rectangular as shown in FIG. It may be surrounded by a sacrificial groove. Alternatively, the second sacrificial groove may be formed only on one opposing two sides in all the second effective regions. Alternatively, the second effective region surrounded by the rectangular second sacrificial groove and the second effective region in which the second sacrificial groove is formed only on one opposing two sides may be mixed.

In the composite of the present invention, when the second effective region is set, it is preferable to form the second sacrificial grooves corresponding to all the second effective regions.
However, even if the second effective region is set, the composite of the present invention may not form the second sacrificial groove at all, or may include the second effective region in which the second sacrificial groove is formed, The second effective region where the two sacrificial grooves are not formed may be mixed.

Further, as in the example shown in FIG. 5, if the second sacrificial groove does not enter the second effective region even if each second sacrificial groove is extended, the second sacrificial groove is formed similarly to the sacrificial groove 16. The glass sheet 12 may be formed so as to extend over the entire area.
That is, the second sacrificial groove may also be formed in a lattice shape like the sacrificial groove 16. In this case, one second sacrificial groove corresponds to a plurality of second effective regions.

The composite body 40 having the second sacrificial groove shown in FIG. 5 may also be formed by laminating and bonding a second glass sheet to the resin layer 14.
At this time, the element is usually formed on the surface of the glass sheet 12 in the state of a laminate. Thereafter, the second glass sheet is peeled from the composite 40 (resin layer 14). During the peeling, the composite 40 is deformed by bending the resin layer 14 into a convex shape. However, in the composite 40, the resin layer 14 has a predetermined rigidity and thickness, is bonded to the glass sheet 12 with a predetermined adhesive force, and the sacrificial groove 16 is formed outside the effective region. Therefore, even if a crack occurs in the end portion of the glass sheet 12 or in the vicinity thereof and propagates in the inner surface direction, the propagation of the crack is suppressed by the sacrificial groove 16, and the crack can be suppressed from reaching the effective region. In addition, regarding this effect, the laminated body 50 shown in FIG. 4 is also the same.
After peeling the 2nd glass sheet 52 from the composite 40, it is cut | disconnected by a cutting line (two-dot chain line), and it is set as each electronic device. Here, even in the state of individual electronic devices, as described above, the substrate of this electronic device is the composite of the present invention. Therefore, when the electronic device is used, even if the resin layer 14 is bent and deformed to cause a crack at the end of the glass sheet 12 or in the vicinity thereof, even if the crack propagates toward the inner surface, The propagation of cracks can be suppressed, and cracks in the effective area can be suppressed.

The electronic device of the present invention is obtained by forming an element on the glass sheet 12 of the composite or laminate of the present invention.
Examples of the electronic device of the present invention include LCD, OLED, PV, thin film secondary battery, and electronic paper.

The following electronic device will be described by taking the composite 10 as an example, but the same applies to the composite 40 and the laminate 50.
In the composite 40, the following elements are formed in the second effective regions a to f. Further, as described above, in the composite 10 and the laminated body 50 as well, usually, using this as a mother board, a plurality of or a single element that is an electronic device is formed independently of each other in the effective region.

  In the following electronic device, each element (each layer (each film) constituting the element) may be formed by a known method.

An LCD (liquid crystal display) as an electronic device of the present invention includes a TFT substrate, a CF substrate, a liquid crystal layer, and the like.
The TFT substrate is obtained by patterning TFT elements (thin film transistor elements) on the glass sheet 12 of the composite 10. The CF substrate is obtained by patterning color filter elements on a glass sheet 12 of another composite 10. The liquid crystal layer is formed between the TFT substrate and the CF substrate.

An OLED (organic EL panel) as an electronic device of the present invention includes, as an example, a composite 10, a transparent electrode, an organic layer, a reflective electrode, a sealing plate, and the like.
A transparent electrode is formed on the glass sheet 12 of the composite 10, an organic layer is formed thereon, a reflective electrode is formed thereon, a reflective electrode is formed thereon, and a bottom emission type organic EL element Is configured. The organic layer includes at least a light emitting layer, and includes a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer as necessary. For example, the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in this order from the anode side. The organic EL element may be a top emission type.

As an example, the PV (solar cell) as the electronic device of the present invention includes the composite 10, a transparent electrode, a silicon layer, a reflective electrode, a sealing plate, and the like.
A transparent electrode is formed on the glass sheet 12 of the composite 10, a silicon layer is formed thereon, a reflective electrode is formed thereon, and a silicon-type solar cell element is formed and sealed on the reflective electrode A board is placed. The silicon layer includes, for example, a p layer (p-type doped layer), an i layer (light absorption layer), an n layer (n-type doped layer), and the like from the anode side.
The PV may be a compound type, a dye sensitized type, a quantum dot type, or the like.

As an example, the thin film secondary battery as the electronic device of the present invention includes the composite 10, a transparent electrode, an electrolyte layer, a current collecting layer, a sealing layer, a sealing plate, and the like.
A transparent electrode is formed on the glass sheet 12 of the composite 10, an electrolyte layer is formed thereon, a current collecting layer is formed thereon, a sealing layer is formed thereon, and a thin film secondary battery element is formed It is comprised and a sealing board is arrange | positioned on a sealing layer.
The thin film secondary battery element is a lithium ion type, but may be a nickel hydrogen type, a polymer type, a ceramic electrolyte type, or the like.

The electronic paper as the electronic device of the present invention includes, as an example, the composite 10, the TFT layer, a layer containing an electrical engineering medium (for example, microcapsule), a transparent electrode, a front plate, and the like.
A TFT layer is formed on the glass sheet 12 of the composite 10, a layer containing an electrical engineering medium is formed thereon, a transparent electrode is formed thereon, and an electronic paper element is formed. A face plate is arranged.
The electronic paper element may be any of a microcapsule type, an in-plane type, a twist ball type, a particle movement type, an electronic jet type, and a polymer network type.

  As mentioned above, although the composite_body | complex, laminated body, electronic device, and its manufacturing method of this invention were demonstrated in detail, this invention is not limited to the above-mentioned example, In the range which does not deviate from the summary of this invention, various Of course, improvements and changes may be made.

  Hereinafter, specific examples of the present invention will be shown, and the present invention will be described in more detail.

[Example 1]
As the glass sheet, a non-alkali glass plate (AN100 manufactured by Asahi Glass Co., Ltd.) having a thickness of 100 μm and 150 × 100 mm was prepared.
First, as a pretreatment, a glass sheet is cleaned with pure water cleaning and UV cleaning, and then a 0.1 wt% solution of aminopropyltrimethoxysilane (KBM903) in isopropyl alcohol as a solvent is spun in order to improve the adhesive strength. The glass sheet was applied by coating (10 seconds at 2000 rpm) and dried at 80 ° C. for 10 minutes to perform silane coupling treatment of the glass sheet.
A sacrificial groove parallel to the long side having a width of 1 μm and a depth of 10 μm was formed at a position 5 mm inside the long side of one surface of the pretreated glass sheet. The sacrificial groove was formed by a CO ₂ laser.

On the other hand, a polyamic acid solution for coating was prepared by the following method.
Paraphenylenediamine (10.8 g, 0.1 mol) was dissolved in N, N-dimethylacetamide (198.6 g) and stirred at room temperature. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (29.4 g, 0.1 mol) was added to this over 1 minute, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution having a solid content concentration of 20% by mass containing a polyamic acid having a repeating unit represented by 1) and / or formula (2-2) was obtained.

This polyamic acid solution was applied to the formation surface of the sacrificial groove of the glass sheet by a spin coating method (2000 rpm) to form a coating film. Then, the coating film was dried by heating in the air at 60 ° C. for 10 minutes and further in the air at 120 ° C. for 10 minutes, and a polyamic acid film was formed on the surface of the glass sheet.
Further, by heating in the atmosphere at 350 ° C. for 1 hour, a composite having a 25 μm thick resin layer made of polyimide is produced on the surface of the glass sheet on which the polyamic acid is imidized to form the sacrificial grooves. did.

About the produced composite_body | complex, the adhesive force (180 degree peel peel strength) of the resin layer was measured with the universal testing machine (made by Shimadzu Corporation). As a result, the adhesive strength of the resin layer was 12 N / 25 mm.
Further, the Young's modulus of the resin layer (Young's modulus in a region where the distance in the normal direction from the interface with the glass sheet is 0 to 0.5 μm) was measured according to JIS K 7127 (1999). As a result, the Young's modulus of the resin layer 14 was 5 GPa. The Young's modulus was measured by peeling off the resin layer from the produced composite. When the resin layer could not be peeled from the composite, the glass sheet was melted with hydrofluoric acid to obtain a measurement resin layer.

After polishing the end face of the composite thus produced with sand paper, the composite was bent at two points in the normal direction of the sacrificial groove with the resin layer side convex until the end of the glass sheet was cracked.
After the crack was generated, a crack that propagated 5 mm or more inward from the sacrificial groove was confirmed. As a result, the crack which propagated 5 mm or more to the inner surface side from the sacrificial groove was not recognized (no damage).

[Example 2]
A composite was produced in the same manner as in Example 1 except that the resin layer was changed to PES (polyether sulfonic acid) and having a thickness of 20 μm.
The resin layer made of PES was formed as follows. First, PES (Sumitomo Chemical Co., Ltd., 5003P) was dissolved in N-methylpyrrolidone at 20% by mass to prepare a PES solution. This PES solution was applied to a glass sheet by a spin coating method (2000 rpm) to form a coating film. Then, the coating film was dried by heating in the air at 130 ° C. for 1 hour to form a PES film. In this example, the glass sheet was not subjected to silane coupling treatment.
When the composite was produced, the adhesive strength and Young's modulus of the resin layer were measured in the same manner as in Example 1. As a result, the adhesive strength was 5.4 N / 25 mm, and the Young's modulus was 2.4 GPa.
When the composite was bent at two points in the same manner as in Example 1 and cracks were confirmed, no cracks propagated 5 mm or more from the sacrificial grooves were found (no damage).

[Comparative Example 1]
A composite was manufactured in the same manner as in Example 1 except that the solid content concentration of the polyamic acid solution was 10% by mass and the thickness of the resin layer was 0.5 μm.
When the composite was produced, the adhesive strength and Young's modulus of the resin layer were measured in the same manner as in Example 1. As a result, the adhesive strength was 10 N / 25 mm or more. However, since the resin layer was torn, an accurate value could not be measured. The Young's modulus was 5 GPa.
When the composite was bent at two points in the same manner as in Example 1 and cracks were confirmed, cracks propagated 5 mm or more from the sacrificial grooves were observed (damaged).

[Comparative Example 2]
A composite was produced in the same manner as in Example 1 except that the resin layer was changed to a silicone resin having a thickness of 16 μm.
Formation of the resin layer made of silicone resin was performed as follows. Solvent-free addition reaction type silicone for release paper (Shin-Etsu Silicone, KNS-320A. Mixture of organoalkenylpolysiloxane and organohydrogenpolysiloxane) 100 parts by mass and platinum-based catalyst (Shin-Etsu Silicone CAT-PL- 56) A mixture with 2 parts by mass was applied to a glass sheet by a spin coating method (2000 rpm) to form a coating film. Thereafter, the coating film was dried by heating in the atmosphere at 180 ° C. for 30 minutes to form a silicone resin film. In this example, the glass sheet was not subjected to silane coupling treatment.
When the composite was produced, the adhesive strength and Young's modulus of the resin layer were measured in the same manner as in Example 1. As a result, the adhesive strength was 2.7 N / 25 mm, and the Young's modulus was 0.003 GPa.
When the composite was bent at two points in the same manner as in Example 1 and cracks were confirmed, cracks propagated 5 mm or more from the sacrificial grooves were observed (damaged). Moreover, the elongation of the resin layer also occurred.

[Comparative Example 3]
A composite was produced in the same manner as in Example 1 except that the glass sheet was not subjected to silane coupling treatment.
When the composite was produced, the adhesive strength and Young's modulus of the resin layer were measured in the same manner as in Example 1. As a result, the adhesive strength was 0.1 N / 25 mm, and the Young's modulus was 5 MPa.
When the composite was bent at two points in the same manner as in Example 1 and cracks were confirmed, cracks propagated 5 mm or more from the sacrificial grooves were observed (damaged). In addition, the resin layer also floated.

[Comparative Example 4]
A glass sheet on which no resin layer was formed was bent at two points in the same manner as in Example 1 to confirm cracking.
As a result, a crack propagated 5 mm or more from the sacrificial groove was observed (with damage). Moreover, scattering of glass fragments also occurred.

[Comparative Example 5]
A composite was produced in the same manner as in Example 1 except that no sacrificial groove was formed on the glass sheet. Therefore, the adhesive strength of the resin layer is 12 N / 25 mm, and the Young's modulus is 5 MPa.
When the composite was bent at two points in the same manner as in Example 1 and cracks were confirmed, cracks that occurred from the end of the glass sheet and propagated to the other end were observed.
The above results are summarized in the following table.

As shown in the above examples, it has a sacrificial groove, has a resin layer thickness of 1 to 100 μm, an adhesive strength (180 ° peel strength) of 1 N / 25 mm or more, and a Young's modulus of 100 MPa or more. According to the composite, even if a crack occurs at the end of the glass sheet by two-point bending, since this crack can suppress propagation (edge cutting) in the sacrificial groove, there is no crack propagating 5 mm or more inside the sacrificial groove. A high quality composite could be produced.
In contrast, Comparative Example 1 in which the resin layer is thin, Comparative Example 2 in which the Young's modulus of the resin layer is low, Comparative Example 3 in which the adhesive strength of the resin layer is low, and Comparative Example 4 having no resin layer are two points. Cracks generated by bending propagated and cracks of 5 mm or more were generated inside the sacrificial grooves. Moreover, in the comparative example 5 which does not have a sacrificial groove | channel, when a crack generate | occur | produces, the progress of a crack did not stop and the crack which propagated from one edge part of the glass sheet to the other edge part occurred. Furthermore, in Comparative Example 1 in which the resin layer is thin, the resin layer is torn, in Comparative Example 2 in which the Young's modulus of the resin layer is low, the resin layer is stretched, and in Comparative Example 3 in which the adhesive strength of the resin layer is low, the resin layer is floated, In Comparative Example 4 having no resin layer, glass fragments were scattered.
From the above results, the effects of the present invention are clear.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on May 14, 2014 (Japanese Patent Application No. 2014-1000071), the contents of which are incorporated herein by reference.

  The present invention can be suitably used for manufacturing various electronic devices.

10, 10a, 10b, 10c, 33, 40 Composite 12, 35 Glass sheet 14, 36 Resin layer 16, 20, 24a, 24b, 26a, 26b, 38 Sacrificial groove 30 Substrate 30R Substrate roll 32 Resist layer forming apparatus 34 treated substrate 34R treated substrate roll 50 laminated body 52 second glass sheet 42a, 42b, 42c, 42d, 42e, 42f second sacrificial groove A end

Claims (9)

A composite comprising a glass sheet and a resin layer bonded to one surface of the glass sheet,
The resin layer has a thickness of 1 to 100 μm, a Young's modulus in a region of 0 to 0.5 μm in the normal direction from the interface with the glass sheet is 100 MPa or more, and 180 ° with respect to the glass sheet. The peel peel strength is 1 N / 25 mm or more, and
The said glass sheet has a sacrifice groove | channel extended along the edge part of the said glass sheet at least in the adhesive surface with the said resin layer, The composite_body | complex characterized by the above-mentioned. The glass sheet has two sacrificial grooves extending in the same direction, and an effective area between the two sacrificial grooves,
And a second sacrificial groove extending along an end of the second effective region inside the effective region and outside the second effective region. The composite according to claim 1.   The composite according to claim 1, wherein the sacrificial groove has a groove that does not penetrate the glass sheet.   The composite according to any one of claims 1 to 3, wherein the sacrificial groove has a through groove that penetrates the glass sheet.   The laminated body which adhere | attached the 2nd glass sheet on the resin layer of the composite_body | complex of any one of Claims 1-4.   The electronic device which has an element on the surface of the glass sheet of the composite_body | complex of any one of Claims 1-4, or the glass sheet of the laminated body of Claim 5. Forming a sacrificial groove extending along the edge of the glass sheet;
A resin layer having a Young's modulus of 100 MPa or more and a thickness of 1 to 100 μm in a region where the distance in the normal direction from the interface with the glass sheet is 0 to 0.5 μm on the surface on which the sacrificial grooves of the glass sheet are formed Is formed with an adhesive strength of 1 N / 25 mm or more at 180 ° peel peel strength.   The manufacturing method of the laminated body which laminate | stacks and adhere | attaches a 2nd glass sheet on the resin layer of the composite_body | complex obtained with the manufacturing method of Claim 7.   The manufacturing method of the electronic device which forms an element in the glass sheet of the composite_body | complex obtained by the manufacturing method of Claim 7, or the laminated glass sheet obtained by the manufacturing method of Claim 8.

Images