JP7279840B1 - laminate - Google Patents

Abstract

Kind Code: A1 A laminate is provided in which peeling failure of a peelable resin layer is less likely to occur. A laminate has a glass substrate and a laminated resin layer disposed on the glass substrate, and the laminated resin layer has an intermediate resin layer and a peelable resin layer from the glass substrate side. , the surface of the glass substrate on the side of the laminated resin layer has a peripheral region where the laminated resin layer is not arranged, the length of the long side of the glass substrate is 400 mm or more, and the length of the short side of the glass substrate is 320 mm. As described above, in at least one corner of the glass substrate, the distance X from the apex of the corner to the closest laminated resin layer is 4 mm or more. [Selection drawing] Fig. 2

Description

The present invention relates to laminates.

Electronic devices such as solar cells (PV); liquid crystal panels (LCD); organic EL panels (OLED); receiving sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible light rays, infrared rays, etc. are becoming thinner and lighter. are doing. Along with this, substrates such as polyimide substrates used in electronic devices are becoming thinner. If the strength of the substrate is insufficient due to the thinning, the handleability of the substrate is lowered, and problems may occur in the process of forming electronic device members on the substrate.

Therefore, recently, in order to improve the handleability of the substrate, a technique using a laminate in which a polyimide substrate is arranged on a support substrate has been proposed (Patent Document 1). More specifically, in Patent Document 1, a polyimide varnish is applied on a thermosetting resin composition cured body layer to form a resin varnish cured film (corresponding to a polyimide layer), and a resin varnish cured film is coated with It is disclosed that precision elements can be placed.

JP 2018-193544 A

Polyimide varnish is applied on the cured thermosetting resin composition layer of Patent Document 1, and before forming a resin varnish cured film, a PET (polyethylene terephthalate) film or the like is applied on the cured thermosetting resin composition layer. In some cases, a laminate provided with a peelable resin layer is handled.
The present inventors have studied a technique of using a glass substrate (support substrate) having a peelable resin layer when obtaining a polyimide film formed from the polyimide varnish. When preparing a peelable glass substrate, when the glass substrate is large, it has been found that there is a problem with peelability such as difficulty in peeling the peelable resin layer.

An object of the present invention is to provide a laminate in which peeling failure of a peelable resin layer is less likely to occur.

As a result of intensive studies, the inventors have found that the above-described problems can be solved by the following configuration.
(1) Having a glass substrate and a laminated resin layer disposed on the glass substrate, the laminated resin layer having an intermediate resin layer and a peelable resin layer from the glass substrate side, and laminating the glass substrate The surface on the resin layer side has a peripheral area where the laminated resin layer is not arranged, the length of the long side of the glass substrate is 400 mm or more, the length of the short side of the glass substrate is 320 mm or more, and the glass substrate A layered product, wherein a distance X from a vertex of at least one corner of the substrate to the closest layered resin layer is 4 mm or more.

(2) The laminate according to (1), wherein the minimum distance Y of distances from a point on one side of the glass substrate to the closest laminated resin layer is 1 mm or more.
(3) The laminate according to (1) or (2), wherein the distance X is 21 mm or less.
(4) The laminate according to any one of (1) to (3), wherein the distance Y is 15 mm or less.
(5) The position P1 of the laminated resin layer closest to the vertex of one corner of the glass substrate and the position P2 of the laminated resin layer closest to the vertex of the corner adjacent to one corner of the glass substrate, The laminate according to any one of (1) to (4), wherein the laminated resin layer is present on the side of the glass substrate with respect to the straight line connecting the positions P1 and P2.
(6) The laminate according to any one of (1) to (5), wherein at least one of the distances X at the four corners of the glass substrate is different.
(7) The laminate according to (2), wherein at least one of the distances Y on each of the four sides of the glass substrate is different.
(8) The laminate according to any one of (1) to (7), wherein the laminated resin layer is divided into a plurality of regions.
(9) The laminate according to any one of (1) to (8), wherein the intermediate resin layer is composed of a silicone resin.
(10) The laminate according to any one of (1) to (9), wherein the peelable resin layer is made of polyethylene terephthalate.
(11) The laminate according to any one of (1) to (10), wherein the glass substrate has a thickness of 0.2 to 1 mm.
(12) The laminate according to any one of (1) to (11), wherein the glass substrate has a Young's modulus of 100 GPa or less.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which the peeling resin layer is hard to produce the peeling defect can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows the 1st example of the laminated body of embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic plan view which shows the 1st example of the laminated body of embodiment of this invention. FIG. 4 is a schematic plan view showing a second example of the laminate according to the embodiment of the invention; FIG. 5 is a schematic plan view showing a third example of the laminate according to the embodiment of the invention; FIG. 10 is a schematic plan view showing a fourth example of the laminate according to the embodiment of the invention;

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are exemplifications for explaining the present invention, and are not limited to the embodiments shown below. Various modifications and replacements can be made to the following embodiments without departing from the scope of the present invention.
A numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits.

A feature of the laminate of the present invention is that it has a glass substrate and a laminated resin layer disposed on the glass substrate, and the laminated resin layer comprises an intermediate resin layer and a peelable resin layer from the glass substrate side. The surface of the glass substrate on the side of the laminated resin layer has a peripheral area where the laminated resin layer is not arranged, the length of the long side of the glass substrate is 400 mm or more, and the length of the short side of the glass substrate is 320 mm or more, and in at least one corner of the glass substrate, the distance X from the apex of the corner to the closest laminated resin layer is 4 mm or more, so that the detachable resin layer is detached. It is known that it is possible to suppress This provides the desired effect.

<Laminate>
FIG. 1 is a schematic cross-sectional view showing a first example of the laminate according to the embodiment of the invention, and FIG. 2 is a schematic plan view showing the first example of the laminate according to the embodiment of the invention.
As shown in FIG. 1, the laminated body 10 has a laminated resin layer 14 arranged on the glass substrate 12 . The laminated resin layer 14 has an intermediate resin layer 16 and a peelable resin layer 18 from the glass substrate 12 side. An intermediate resin layer 16 is provided on the surface 12a of the glass substrate 12, and the intermediate resin layer 16 and the peelable resin layer 18 are laminated. In the laminated resin layer 14, the intermediate resin layer 16 and the peelable resin layer 18 have the same size. The laminated resin layer 14 has, for example, a superelliptical outer shape when viewed from the normal direction of the surface 12a of the glass substrate 12 .

The peelable resin layer 18 is peeled off from the laminate 10 and a polyimide layer (not shown), for example, is formed on the intermediate resin layer 16 . The glass substrate 12 functions as a support substrate, and when viewed from the normal direction of the surface 12a on the side of the laminated resin layer 14, the outer shape is, for example, a square.
In the laminate 10, as shown in FIG. 2, the length _L1 of the long side 12b of the glass substrate 12 is 400 mm or more, and the length _L2 of the short side 12c of the glass substrate 12 is 320 mm or more.
The glass substrate 12 is larger than the laminated resin layer 14, and the surface 12a of the glass substrate 12 on the laminated resin layer 14 side has a peripheral region 13 where the laminated resin layer 14 is not arranged. The surface 12a of the peripheral region 13 of the glass substrate 12 is exposed.
In the laminate 10, in at least one corner 12d of the glass substrate 12, the distance X from the vertex 12e of the corner 12d to the closest laminated resin layer 14 is 4 mm or more.
In such a laminate 10, even if the laminate 10 is heated during transportation or autoclave treatment, warping of the glass substrate 12 is suppressed, and peeling defects such as difficulty in peeling the peelable resin layer 18 are less likely to occur.

The glass substrate 12 may have a chamfered outer edge. In this case, the vertex 12e of the corner 12d may also be an arc having a predetermined radius of curvature. When the corner portion 12d is an arc, the direct portion of each side of the glass substrate 12 is extended in the extending direction of each side, and the point where the extension lines of the two adjacent sides intersect is defined as a virtual vertex. Of these virtual vertices, a line obtained by connecting virtual vertices that are diagonally opposite each other on the glass substrate 12 is defined as a virtual diagonal line. The vertex is the intersection of the virtual diagonal line and the circular arc.
Further, the corner 12d of the glass substrate 12 may be corner-cut like an orientation flat. In this case, as in the case of the circular arc described above, the vertex is the point at which the corner-cut formed side (not shown) and the virtual diagonal line described above intersect.

In the laminate 10, the distance X from the vertex 12e of the corner 12d to the closest laminated resin layer 14 is preferably 21 mm or less, more preferably 10 mm or less. It is preferable that the distance X is 21 mm or less, because the region where the laminated resin layer 14 is provided on the surface 12a of the glass substrate 12 is widened.
Note that the distance X from the vertex 12e of the corner 12d to the closest laminated resin layer 14 does not need to be the same for the four corners 12d of the glass substrate 12. FIG. At least one of the four corners 12d of the glass substrate 12 may differ from the distance X described above, or all may differ from each other. Further, for example, two corners and the remaining two corners of the four corners 12d may be paired, and the distance X may be different between the two pairs.
In the laminated body 10, it is preferable that the minimum distance Y of the distances from the point P on one side of the glass substrate 12 to the closest laminated resin layer 14 is 1 mm or more.
It is preferable that the minimum distance Y is 15 mm or less, because the region where the laminated resin layer 14 is provided with respect to the surface 12a of the glass substrate 12 is widened.
In the four sides of the glass substrate 12, the minimum distance Y among the distances from a point on one side to the closest laminated resin layer 14 is at least one of the four sides of the glass substrate 12. one may be different, or all may be different. In this case, the laminated resin layer 14 is arranged close to at least one of the four sides. As described above, the laminated resin layer 14 is not limited to being arranged on the surface 12a of the glass substrate 12 so that the peripheral region 13 around the laminated resin layer 14 is uniform. They may be placed close to each other.

As shown in FIG. 2, in the laminate 10, the position P1 of the laminated resin layer 14 closest to the vertex 12e of one corner 12d of the glass substrate 12 and the corner adjacent to the one corner 12d of the glass substrate 12 Position P2 of the laminated resin layer 14 closest to the vertex 12e of the portion 12d is preferably located on the side of the glass substrate 12 from the straight line Lp connecting the positions P1 and P2. That is, the laminated resin layer 14 has a region 14d on the side of the glass substrate 12 with respect to the straight line Lp.
The straight line Lp described above exists on both the long side 12b side and the short side 12c side as shown in FIG. In the laminated resin layer 14, a region 14d exists on the long side 12b side of the glass substrate 12 with respect to the straight line Lp on the long side 12b side. Further, in the laminated resin layer 14, a region 14d exists on the short side 12c side of the glass substrate 12 with respect to the straight line Lp on the short side 12c side.
When the peelable resin layer 18 of the laminate 10 is peeled off and a polyimide layer (not shown) is formed on the glass substrate 12 and the intermediate resin layer 16, as described above, from the straight line Lp connecting the positions P1 and P2, When the laminated resin layer 14 is present on the long side 12b side or the short side 12c side of the glass substrate 12, deterioration of the polyimide layer is suppressed during high temperature heating, and cracks are less likely to occur in the polyimide layer, which is preferable.
For this reason, the outer shape of the laminated resin layer 14 shown in FIG. 2 is preferable to the outer shape of the laminated resin layer 14 when viewed from the normal direction of the surface 12a of the glass substrate 12 is a square (see FIG. 3).
In addition, when the laminated resin layer 14 has the region 14d, the distance X and the distance Y satisfy the relationship of distance X>distance Y×1.4.

The outer shape of the laminated resin layer 14 of the laminate 10 is not particularly limited as long as it satisfies the distance X described above, and may be rectangular. Like the laminated body 10a shown in FIG. The outer shape may be rectangular when viewed from the normal direction of the side surface 12a.
In addition, FIG. 3 is a schematic plan view showing a second example of the laminate according to the embodiment of the present invention. In FIG. 3, the same components as those of the laminate 10 shown in FIGS. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.

FIG. 4 is a schematic plan view showing a third example of the laminate according to the embodiment of the invention. In FIG. 4, the same components as those of the laminate 10 shown in FIGS. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.
The laminate 10b shown in FIG. 4 differs from the laminate 10 shown in FIGS. 1 and 2 in that the laminated resin layer 14 is divided into a plurality of regions. It has the same configuration as the laminate 10 shown in FIG.
The laminated resin layer 14 of the laminated body 10b is provided at a position half the length of the long side 12b and divided into two regions 15a and 15b by a linear groove 19 extending along the short side 12c. . The two regions 15a, 15b have the same shape and size.
The groove 19 extends from the surface 14a of the laminated resin layer 14 to the surface 12a of the glass substrate 12. The groove 19 has no laminated resin layer 14, and the surface 12a of the glass substrate 12 is exposed.
The length in the extending direction of the long side 12b of the groove 19, that is, the width Z of the groove 19 may be wider than the distance Y described above, for example.
The groove 19 is formed by cutting and removing the laminated resin layer 14 using a cutter or laser, for example. Further, the grooves 19 may be provided in the laminated resin layers 14 with a space therebetween.
Also, although the laminated resin layer 14 is divided into two regions, the number of divisions is not limited to 2, but may be 3 to 240, for example.
The two regions 15a and 15b are not limited to having the same shape and size, and at least one of the shape and size may be different.
It is not limited to the linear groove 19 extending along the short side 12c. The laminated resin layer 14 may be divided.

Even if the shape of the laminated resin layer 14 shown in FIG. 3 is a square when viewed from the normal direction of the surface 12a of the glass substrate 12 on the laminated resin layer 14 side, the laminated resin layer 14 is divided into a plurality of regions. may Specifically, like the laminated resin layer 14 of the laminated body 10c shown in FIG.
FIG. 5 is a schematic plan view showing a fourth example of the laminate according to the embodiment of the invention. In FIG. 3, the same components as those of the laminate 10 shown in FIGS. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.

Below, each member which comprises the said laminated body is explained in full detail.
(glass substrate)
The glass substrate is a member that supports and reinforces the laminated resin layer 14, and functions as a support substrate.
As the glass constituting the glass substrate, alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide glasses containing silicon oxide as a main component are preferable. As the oxide glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
More specifically, the glass substrate includes a glass substrate made of non-alkali borosilicate glass (trade name “AN100” manufactured by AGC Inc.).
A method for producing a glass substrate is generally obtained by melting glass raw materials and forming the molten glass into a plate shape. Such a molding method may be a general one, and examples thereof include a float method, a fusion method, and a slot down-draw method.
The shape of the glass substrate is not particularly limited, but from the viewpoint of handling such as transportation and transfer, when viewed from the normal direction of the surface 12a of the glass substrate 12 on the side of the laminated resin layer 14, the outer shape is preferably rectangular. .
When the glass substrate has a rectangular outer shape, the long sides and short sides of the glass substrate may have different lengths, or the long sides and short sides of the glass substrate may have the same length.

Preferably, the glass substrate is not flexible. The Young's modulus of the glass substrate is preferably 100 GPa or less. The Young's modulus of the glass substrate is a value measured by an ultrasonic pulse method. If the Young's modulus of the glass substrate is 100 GPa or less, breakage due to contact with peripheral members during transportation of the glass substrate can be suppressed. The Young's modulus of the glass substrate is 65 GPa or more, and if the Young's modulus is 65 GPa or more, breakage due to contact with peripheral members during transportation of the glass substrate can be suppressed.
The thickness Dt (see FIG. 1) of the glass substrate is preferably 0.2 to 1 mm. The thickness Dt of the glass substrate is a value obtained by measuring the thickness of the glass substrate 12 at arbitrary 10 points and arithmetically averaging them.

(Laminated resin layer)
The laminated resin layer 14 includes the intermediate resin layer 16 and the peelable resin layer 18 as described above. For example, after peeling the peelable resin layer 18 , a polyimide layer (not shown) is formed on the glass substrate 12 and the intermediate resin layer 16 .

[Intermediate resin layer]
The intermediate resin layer 16 is formed on the surface 12 a of the glass substrate 12 .
The intermediate resin layer 16 is a film for preventing peeling of a polyimide layer (not shown) placed thereon.
Examples of materials for the intermediate resin layer 16 include acrylic resins, polyolefin resins, polyurethane resins, polyimide resins, silicone resins, polyimide silicone resins, and fluorine resins. Also, the intermediate resin layer 16 can be formed by mixing several kinds of resins.
Among them, silicone resins and polyimide silicone resins are preferable as the material of the intermediate resin layer 16 in terms of heat resistance and peelability, silicone resins are more preferable, and silicone resins formed from condensation curing silicone are more preferable. The intermediate resin layer 16 made of silicone resin is called a silicone resin layer.
Below, the form in which the intermediate resin layer 16 is a silicone resin layer will be described in detail.

A silicone resin is a resin containing a predetermined organosiloxy unit, and is usually obtained by curing a curable silicone. Curable silicones are classified into addition-curing silicones, condensation-curing silicones, UV-curing silicones, and electron beam-curing silicones according to their curing mechanisms, and any of them can be used. Among them, condensation-curing silicone is preferred.
Condensation-curable silicones include hydrolyzable organosilane compounds that are monomers or mixtures thereof (monomer mixtures), or partially hydrolyzed condensates (organopolysiloxanes) obtained by partially hydrolyzing and condensing monomers or monomer mixtures. can be preferably used.
A silicone resin can be formed by proceeding a hydrolysis/condensation reaction (sol-gel reaction) using this condensation-curable silicone.

The intermediate resin layer 16 is preferably formed using a curable composition containing curable silicone.
The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when an addition-reactive silicone is used as the curable silicone), a leveling agent, a metal compound, and the like. Examples of metal elements contained in metal compounds include 3d transition metals, 4d transition metals, lanthanide metals, bismuth (Bi), aluminum (Al), and tin (Sn). The content of the metal compound is not particularly limited and is adjusted as appropriate.

The intermediate resin layer 16 preferably has hydroxy groups. A portion of the Si--O--Si bonds that constitute the silicone resin of the intermediate resin layer 16 may be broken to reveal hydroxy groups. Moreover, when condensation reaction type silicone is used, its hydroxy group can become the hydroxy group of the intermediate resin layer 16 .

The thickness of the intermediate resin layer 16 is 1 .mu.m because it is excellent in embedding foreign matter when a support substrate made of glass is laminated on the side of the intermediate layer on which the resin substrate is not arranged after peeling off one of the resin substrates. 6 μm or more is preferable, and 6 μm or more is more preferable. The upper limit of the thickness of the intermediate resin layer 16 is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 12 μm or less in terms of processing cost and process tact.
It should be noted that excellent foreign matter embedding property means that even if foreign matter exists between the glass substrate 12 and the intermediate resin layer 16 , the foreign matter is embedded by the intermediate resin layer 16 . If the embedding property of foreign matter is excellent, the intermediate resin layer 16 is less likely to have protrusions due to foreign matter. From this, when the polyimide layer is formed on the intermediate resin layer 16 as described above, and the electronic device member is formed on the polyimide layer, when the foreign matter embedding property is excellent, the protrusions in the electronic device member This reduces the risk of wire disconnection, etc.
The thickness of the intermediate resin layer 16 is determined by measuring the thickness of the intermediate resin layer 16 at five or more arbitrary positions using a non-contact surface texture measuring device "PF-60" manufactured by Mitaka Kohki Co., Ltd. is the arithmetic mean of

[Peelable resin layer]
The peelable resin layer 18 is arranged on the intermediate resin layer 16 and protects the intermediate resin layer 16 .
The peelable resin layer 18 is composed of, for example, polyimide resin, polyester resin (eg, polyethylene terephthalate, polyethylene naphthalate), polyolefin resin (eg, polyethylene, polypropylene), or polyurethane resin. Among them, polyester resin is preferable, and polyethylene terephthalate is more preferable as the resin constituting the peelable resin layer 18 because of easy availability.

The thickness of the peelable resin layer is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 50 μm or more, in order to reduce the influence of external force. The upper limit of the thickness of the peelable resin layer is preferably 500 µm or less, more preferably 300 µm or less, and even more preferably 100 µm or less.

The peelable resin layer may further have an adhesion layer on the surface on the intermediate resin layer 16 side.
A known adhesive layer can be used as the adhesive layer. Examples of adhesives constituting the adhesive layer include (meth)acrylic adhesives, silicone adhesives, and urethane adhesives.
Further, the adhesion layer may be made of a resin, and examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, and butyral resin. , polyurethane resins, and polystyrene elastomers.
The surface roughness (Ra) of the peelable resin layer on the intermediate resin layer 16 side is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 15 nm or less, because the peeling force when peeling the peelable resin layer is reduced. preferable. Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more, so that the peelable resin layer and the intermediate resin layer can be kept in close contact with each other. The surface roughness (Ra) is measured using a non-contact surface/layer profile measuring system "Vertscan R3300-lite" manufactured by Mitsubishi Chemical Systems Corporation.

<Method for manufacturing laminate>
A method for manufacturing the laminate is not particularly limited, and known methods may be used.
For example, there is a method of forming the intermediate resin layer 16 in a predetermined area on the glass substrate 12 and then forming the peelable resin layer 18 on the intermediate resin layer 16 .
The manufacturing procedure for each layer will be described in detail below.

First, an intermediate resin layer 16 is formed in a predetermined area on the glass substrate 12 .
As for the method of forming the intermediate resin layer 16 , an optimum method is appropriately selected depending on the material of the intermediate resin layer 16 . For example, when forming a silicone resin layer as the intermediate resin layer 16, the above-described curable composition containing curable silicone is applied to a predetermined region on the glass substrate 12, and the coating is subjected to heat treatment. method.

Among them, when a silicone resin layer is used as the intermediate resin layer 16 and the productivity is excellent, a transfer film ( Laminated film) is prepared, the precursor film in the transfer film is attached to a predetermined position on the glass substrate 12, and the obtained glass substrate 12, the precursor film, and the laminate having the temporary support A method of heat-treating is exemplified. A silicone resin layer is formed by performing heat treatment.
The above procedure will be described in detail below.

In the above, first, a transfer film having a precursor film that becomes a silicone resin layer after heat treatment and a PET film that becomes a peelable resin layer is prepared. The transfer film has a precursor film formed on a PET film. The precursor film of the transfer film is attached to a predetermined position on the glass substrate 12 to obtain a laminated substrate.
After bonding the transfer film to the glass substrate 12, the obtained laminated substrate may be washed with an alkaline detergent. Also, after cleaning with an alkaline detergent, the substrate may be rinsed with pure water, if necessary. Furthermore, after rinsing with pure water, if necessary, the water may be drained with an air knife.

The heat treatment for forming the silicone resin layer is preferably carried out while applying pressure. Specifically, heat treatment and pressure treatment are preferably performed using an autoclave.
The heating temperature for the heat treatment is preferably 50 to 350°C, more preferably 55 to 300°C, even more preferably 60 to 250°C. The heating time is preferably 10 to 60 minutes, more preferably 20 to 40 minutes.
The pressure for pressurization is preferably 0.5 to 1.5 MPa, more preferably 0.8 to 1.0 MPa.

Further, the heat treatment may be performed multiple times. When the heat treatment is performed multiple times, the heating conditions may be changed for each.

Next, in the laminated substrate, the PET film (releasable resin layer 18) and the silicone resin layer (intermediate resin layer 16) are cut into a predetermined size from the PET film side of the transfer film to form a laminate.
Further, for example, after cutting the transfer film into a predetermined size, the transfer film of a predetermined size may be attached to the glass substrate. Alternatively, after the transfer film is attached to the glass substrate, the transfer film may be cut into a predetermined size.
When forming a laminate having grooves 19 shown in FIG. 4, after cutting the transfer film into a predetermined size in the laminated substrate, the transfer film is further cut from the PET film side to form the grooves 19 .
Alternatively, after cutting the transfer film into a predetermined size, the transfer film of a predetermined size may be pasted on the glass substrate with an interval to form the groove 19 .
Moreover, even when forming a laminate having the grooves 19 shown in FIG. 4, the transfer film may be cut into a predetermined size after being attached to the glass substrate.

EXAMPLES The present invention will be specifically described below with reference to examples, etc., but the present invention is not limited to these examples. Hereinafter, Examples 1 to 4 are comparative examples, and Examples 5 to 13 are examples.

(Preparation of curable silicone)
Triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25°C for 20 minutes and then heated to 60°C for 12 hours to react. A reaction crude liquid was obtained.
After cooling the obtained reaction crude liquid to 25° C., the reaction crude liquid was washed with water (300 g) three times. Chlorotrimethylsilane (70 g) was added to the washed reaction crude liquid, and the mixture was stirred at 25° C. for 20 minutes, then heated to 50° C. and reacted for 12 hours. After cooling the obtained reaction crude liquid to 25° C., the reaction crude liquid was washed with water (300 g) three times.
Toluene was distilled off under reduced pressure from the washed reaction crude liquid, and the resulting slurry was dried overnight in a vacuum dryer to obtain curable silicone 1, which is a white organopolysiloxane compound.
Curable silicone 1 had a molar ratio of M units to T units of 13:87, all organic groups were methyl groups, and the average number of OX groups was 0.02. M unit means an organosiloxy unit represented by (R)3SiO _1/2 , T unit means an organosiloxy unit represented by RSiO _3/2 , and R in each formula represents a hydrogen atom or an organic group. show. The average number of OX groups is a numerical value representing the average number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom.

(Preparation of curable composition)
Curable silicone 1 (20 g), a zirconium octoate compound (“Orgatics ZC-200”, manufactured by Matsumoto Fine Chemical Co., Ltd.) (0.16 g) as a metal compound, and cerium (III) 2-ethylhexanoate (Alfa Aesar company, metal content 12% by mass) (0.17 g), and Isoper G (manufactured by TonenGeneral Sekiyu K.K.) (19.7 g) as a solvent. A curable composition 1 was obtained by filtering using a filter.

(Production of laminated film)
Prepare a PET film (manufactured by Toyobo Co., Ltd., Toyobo Ester (registered trademark) film HPE (high density polyethylene), thickness 50 μm) as a release film that will be the release resin layer, and prepare a curable composition on the surface of this film. 1 and heated at 140° C. for 10 minutes using a hot plate to form a silicone resin layer.
As a protective film on the applied silicone resin layer, a PET film (manufactured by Toyobo Co., Ltd., Toyobo Ester (registered trademark) film HPE, thickness 50 μm) is laminated, and a release film, silicone resin layer (intermediate layer) and protection A laminated film 1 was obtained in which the films were laminated in this order. The thickness of the obtained laminated film 1 was 110 μm.

(Cutting of laminated film)
A cutter is inserted from the PET film side of the release film of the laminated film 1, and the desired size (400 × 320 mm, 880 × 690 mm, 890 × 700 mm, 912 × 722 mm, 914.4 × 724.4 mm, 918 × 728 mm, 920 ×730 mm). As a result, the outer shape of the laminated resin layer is formed into a quadrangle.
In Example 1, a cutter was used to cut into a size of 400×320 mm.
In addition, the laminated film 1 was placed in a punching machine (Hydraulic cutting machine manufactured by Tamari Kiko Co., Ltd., device name “TP-12801000 × 100 TON”), and a blade made of a Thomson blade with a blade width of 0.5 mm and a blade angle of 30 degrees. Mold (398 × 318 mm corner R 6.2 mm, 458 × 728 mm corner R 6.2 mm, 910 × 720 mm corner R 0.1 mm, 910 × 724 mm corner R 0.1 mm, 918 × 728 mm corner R 6.2 mm, 920 × 730 mm (R 4.8 mm) was incident from the PET film side of the release film, and the laminated film 1 was cut. As a result, the outer shape of the laminated resin layer is formed into a superelliptical shape with four curved corners. Here, the angle R indicates the radius of curvature of the curved lines forming the four corners of the outer shape of the laminated resin layer.
As a method for cutting the laminated resin layer, a method using a cutter is called a cutter method. As a method for cutting the laminated resin layer, a method using a punching machine is called a punching method.

(Preparation of a laminated substrate in which one laminated film is arranged in a glass substrate)
It corresponds to Examples 1 to 12 in Table 1 below.
After washing with a water-based glass cleaning agent (“PK-LCG213” manufactured by Parker Corporation), the corners and sides of 920 × 730 mm and a thickness of 0.5 mm or 400 × 320 mm and a thickness of 0.5 mm were washed with pure water. A chamfered glass substrate "AN Wizus" (support substrate, Young's modulus 85 GPa) and a PET film formed with a silicone resin layer of the laminated film 1 from which the protective film has been peeled are bonded together, and the glass substrate , a silicone resin layer, and a PET film were arranged in this order. In the lamination, the distance between the side surface (side) of the glass substrate, the silicone resin layer, and the PET film, and the distance between the corner of the glass substrate, the silicone resin layer, and the PET film are shown in Table 1 below. The glass substrate, the silicone resin layer, and the PET film were laminated so as to have the relationship shown in Example 1.
Example 1 used the glass substrate of 400×320 mm and thickness of 0.5 mm described above.
Examples 2 to 13 used the above glass substrates of 920×730 mm and 0.5 mm thickness.

(Preparation of a laminated substrate in which two laminated films are arranged in a glass substrate)
This corresponds to Example 13 in Table 1 below.
After washing with a water-based glass cleaning agent, the glass substrate "AN Wizus" (supporting substrate) of 920 × 730 mm, 0.5 mm thick, with chamfered corners and sides was washed with pure water, and the protective film was peeled off. After laminating the laminated film 1 of 458 × 728 mm with the PET film on which the silicone resin layer was formed, another protective film of 458 × 728 mm was peeled off to form the silicone resin layer of the laminated film 1. The two PET films were laminated, and a silicone resin layer and two PET films were arranged on a glass substrate to prepare a laminate in which the glass substrate, the silicone resin layer and the PET film were arranged in this order. In addition, during the lamination, the distance along the long side of the laminated film 1 from which the two protective films are peeled is the side surface (side) of the glass substrate and the laminated film 1 from which the protective film is peeled. greater than the distance of

(Heating of laminated substrate)
The obtained laminate was placed so that the glass substrate and the hot plate were in contact with each other, heated at 60° C. for 30 minutes, and then allowed to stand for 1 day in a clean room environment (room temperature 23° C., humidity 55%). let me

<Examples 2 to 12>
At the time of lamination, the distance between the side surface (side) of the glass substrate and the silicone resin layer and the PET film and the distance between the corner of the glass substrate and the silicone resin layer and the PET film are shown in Table 1 below. A laminate was obtained according to the same procedure as in Example 1, except that the glass substrate, the silicone resin layer and the PET film (laminated film 1 from which the protective film was peeled) were laminated so that the relationship of 12 was obtained. .

In Example 2, laminated film 1 was cut into a size of 920×730 mm using a cutter. In Example 3, the laminate film 1 was cut into a size of 920×730 mm (corner radius 4.8 mm) using a punching machine.
In Example 4, laminated film 1 was cut into a size of 918×728 mm using a cutter. In Example 5, laminated film 1 was cut into a size of 918×728 mm (corner radius 6.2 mm) using a punch.
In Example 6, laminated film 1 was cut into a size of 914.4×724.4 mm using a cutter. In Example 7, laminated film 1 was cut into a size of 398×318 mm (corner radius 6.2 mm) using a punch.

In Example 8, laminated film 1 was cut into a size of 912×722 mm using a cutter. In Example 9, laminated film 1 was cut into a size of 910×720 mm (corner radius 0.1 mm) using a punch.
In Example 10, laminated film 1 was cut into a size of 890×700 mm using a cutter. In Example 11, laminated film 1 was cut into a size of 880×690 mm using a cutter.
In Example 12, laminated film 1 was cut into a size of 910×724 mm (corner radius 0.1 mm) using a punch. In Example 12, during the bonding, more specifically, the distance Y on the short side 12c (see FIG. 2) of the glass substrate (920×730 mm) is 5 mm, and the distance on the long side 12b (see FIG. 2) The silicone resin layer and the PET film (laminated film 1 from which the protective film was peeled off) were bonded to the glass substrate so that Y was 1 mm and 5 mm.

<Example 13>
In Example 13, laminated film 1 was cut into a size of 458×728 mm (corner radius 6.2 mm) using a puncher to obtain two silicone resin layers and a PET film.
In Example 13, the distance between the side surface of the glass substrate, the silicone resin layer and the PET film, and the distance between the corner of the glass substrate and the silicone resin layer and the PET film are adjusted to Example 13 in Table 1 during the lamination. Two silicone resin layers and a PET film (laminated film 1 from which the protective film was peeled off) were bonded to the glass substrate so that the relationship of . In Example 13, the two silicone resin layers and the PET film were laminated with a gap therebetween so that a groove could be formed between them. The groove was provided in the middle of the long side of the glass substrate 12, and the width of the groove was 2 mm.

<Evaluation of warpage>
A laminate composed of a glass substrate, a silicone resin layer, and a PET film is placed on a granite plate so that the glass substrate and the granite plate are in contact with each other, and the glass substrate and the granite plate at the corners of the laminate are separated. was measured using a thickness gauge (manufactured by Shinwa Kiseki Co., Ltd., thickness gauge D 65 mm, 25 pieces (product name)). Among the four corners, the maximum gap amount (warp amount) was evaluated. A scotch tape (scotch mending tape width "810-1-18D" manufactured by 3M Co., Ltd.) was attached to the corners of the PET film, and the PET film was pulled up and peeled off. The laminate was placed under a fluorescent lamp, and the presence or absence of defects after peeling was visually observed based on the light reflection state of the silicone resin layer.
A: The maximum amount of warp is less than 0.2 mm, and no defect occurs after peeling. B: The maximum amount of warp is 0.2 mm or more, and the defect occurs after peeling.

<Evaluation of substrate effective area ratio>
The ratio of the area of the glass substrate to the area of the silicone resin layer and the PET film was calculated and evaluated.
A: Substrate effective area ratio is greater than 90.5% B: Substrate effective area ratio is 90.5% or less

(Formation of polyimide layer)
The glass substrate, the silicone resin layer, and the PET films of the laminates of Examples 5 and 6, which consist of the PET films, were peeled off and heated at 250° C. for 30 minutes in an air atmosphere using a clean oven. Next, after the silicone resin layer was subjected to corona treatment, a colorless polyimide varnish (“Neoplim H230” manufactured by Mitsubishi Gas Chemical Company, Inc.) was applied and then heated at 80° C. for 20 minutes using a hot plate. Subsequently, using an inert gas oven, it was heated at 400° C. for 30 minutes in a nitrogen atmosphere (curing step) to prepare a laminated sample having a glass substrate, a silicone resin layer, and a polyimide layer (thickness: 7 μm) in this order.
(Formation of silicon nitride layer)
Next, using a plasma CVD (Chemical Vapor Deposition) apparatus, a silicon nitride layer having a thickness of 100 nm was formed on the entire surface of the polyimide layer of the laminated sample.

<Heat resistance evaluation>
A heat resistance test was performed on the laminate samples based on Examples 5 and 6 by heating at 420° C. for 1 hour under a nitrogen atmosphere. Visually check the appearance of the laminated sample after the heat resistance test, and in the polyimide layer, the position P1 of the laminated resin layer closest to the vertex of one corner of the glass substrate and the corner adjacent to one corner of the glass substrate It was evaluated whether or not a crack occurred on the side of the glass substrate relative to the straight line connecting the apex of the part and the position P2 of the laminated resin layer closest to it.
A: Crack occurred B: Crack did not occur Note that, among Examples 1 to 13, only Examples 5 and 6 were evaluated for heat resistance. For this reason, the remaining Examples 1 to 4 and Examples 7 to 13 are marked with "-" in the "Heat resistance evaluation" column of Table 1.

From the comparison between Examples 1 to 4 and Examples 5 to 13, it was found that if the distance X from the apex of the corner of the glass substrate to the closest laminated resin layer is 4 mm or more, defects are less likely to occur after peeling. rice field.
From a comparison between Examples 1 to 10 and Examples 12 to 13 and Example 11, the distance X from the vertex of the corner of the glass substrate to the closest laminated resin layer is 21 mm or less, and the distance X is 21 mm or less, and on one side of the glass substrate. It was found that the effective area is improved if the minimum distance Y among the distances from the point to the laminated resin layer at the closest position is 15 mm or less.
From the comparison between Examples 5 and 6, Example 5 is the position P1 of the laminated resin layer closest to the vertex of one corner of the glass substrate and the position P1 of the laminated resin layer closest to the vertex of the corner adjacent to one corner of the glass substrate. It was found that cracks are less likely to occur because the laminated resin layer exists on the side of the glass substrate rather than the straight line connecting the adjacent position P2 of the laminated resin layer.

Reference Signs List 10, 10a, 10b, 10c Laminate 12 Glass substrate 12a Surface 12b Long side 12c Short side 12d Corner 12e Vertex 13 Peripheral area 14 Laminated resin layer 14a Surface 14d Area 15a Area 15b Area 16 Intermediate resin layer 18 Releasable resin layer 19 Groove Dt Thickness Lp Line P1, P2 Position X Distance Y Distance Z Width

Claims (11)

Having a glass substrate and a laminated resin layer disposed on the glass substrate,
The laminated resin layer has an intermediate resin layer and a peelable resin layer from the glass substrate side,
The surface of the glass substrate on the side of the laminated resin layer has a peripheral area where the laminated resin layer is not arranged,
The length of the long side of the glass substrate is 400 mm or more,
The length of the short side of the glass substrate is 320 mm or more,
In at least one corner of the glass substrate, the distance X from the apex of the corner to the closest laminated resin layer is 4 mm or more,
The laminated body , wherein the laminated resin layer is divided into a plurality of regions . 2. The laminate according to claim 1, wherein a minimum distance Y of distances from a point on one side of the glass substrate to the closest position to the laminated resin layer is 1 mm or more. 2. The laminate according to claim 1, wherein said distance X is 21 mm or less. 2. The laminate according to claim 1, wherein said distance Y is 15 mm or less. A position P1 of the laminated resin layer closest to the vertex of one corner of the glass substrate, and a position P2 of the laminated resin layer closest to the vertex of the corner adjacent to the one corner of the glass substrate. 5. The laminate according to any one of claims 1 to 4, wherein the laminated resin layer is present on the side of the glass substrate with respect to a straight line connecting the positions P1 and P2. The laminate according to any one of claims 1 to 4, wherein at least one of the distances X at each of the four corners of the glass substrate is different. 3. The laminate according to claim 2, wherein at least one of the distances Y on each of the four sides of the glass substrate is different. The laminate according to any one of claims 1 to 4, wherein the intermediate resin layer is made of a silicone resin. The laminate according to any one of claims 1 to 4, wherein the peelable resin layer is made of polyethylene terephthalate. The laminate according to any one of claims 1 to 4, wherein the glass substrate has a thickness of 0.2 to 1 mm. The laminate according to any one of claims 1 to 4, wherein the Young's modulus of the glass substrate is 100 GPa or less.

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