TW202409164A - Laminated body including a glass substrate and a laminated resin layer - Google Patents

Abstract

An object of the present invention is to provide a laminated body in which peeling failures of a peelable resin layer is unlikely to occur. The laminated body includes a glass substrate and a laminated resin layer arranged on the glass substrate. The laminated resin layer includes an intermediate resin layer and a peelable resin layer starting from the side of the glass substrate. A peripheral area where the laminated resin layer is not placed exists on a surface of the laminated resin layer side on the glass substrate. The length of a long side of the glass substrate is 400 mm or more, and the length of a short side of the glass substrate is 320 mm or more. In at least one corner of the glass substrate, a distance from a vertex of the corner to a position closest to the laminated resin layer is 4 mm or more.

Description

Laminated body

The present invention relates to a laminate.

Electronic devices such as solar cells (PV), liquid crystal panels (LCD), organic EL (Electro Luminescence) panels (OLED), and receiving sensor panels that sense electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. are becoming thinner and lighter. As a result, substrates such as polyimide substrates used in electronic devices are also becoming thinner. If the strength of the substrate is insufficient due to the thinning, the substrate's handling properties may be reduced, causing problems in the steps of forming components for electronic devices on the substrate.

Therefore, recently, in order to improve the handling property of the substrate, a technology for using a laminated body of a polyimide substrate arranged on a supporting substrate has been proposed (Patent Document 1). More specifically, Patent Document 1 discloses that a polyimide varnish can be applied on a cured layer of a thermosetting resin composition to form a resin varnish cured film (equivalent to a polyimide layer), and precision components can be arranged on the resin varnish cured film. [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2018-193544

[The problem that the invention aims to solve]

Before the polyimide varnish is coated on the cured body layer of the thermosetting resin composition of Patent Document 1 to form a cured resin varnish film, PET (polyethylene terephthalate, polyethylene terephthalate) is sometimes provided on the cured body layer of the thermosetting resin composition. Processing of laminates of releasable resin layers such as ethylene terephthalate (ethylene terephthalate) films. The present inventors studied a technique of using a glass substrate (support substrate) having a releasable resin layer when obtaining a polyimide film formed of the above-mentioned polyimide varnish. When preparing a releasable glass substrate, it was discovered that when the glass substrate is large, there is a releasable problem such as difficulty in peeling off the releasable resin layer.

The subject of the present invention is to provide a laminated body that is not prone to poor peeling of the peelable resin layer. [Technical means for solving the problem]

The inventors of the present invention have conducted intensive research and found that the above-mentioned problems can be solved by the following structure. (1) A laminated body 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, a peripheral area where the laminated resin layer is not disposed exists on the surface of the laminated resin layer side of the glass substrate, 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 in at least one corner of the glass substrate, the distance X from the vertex of the corner to the laminated resin layer at the closest position is 4 mm or more.

(2) A laminate as in (1), wherein the shortest distance Y between a point on one side of the glass substrate and the laminate resin layer at the closest position is greater than 1 mm. (3) A laminate as in (1) or (2), wherein the distance X is less than 21 mm. (4) A laminate as in any one of (1) to (3), wherein the distance Y is less than 15 mm. (5) A laminate as in any one of (1) to (4), wherein the laminate resin layer is located at a position P1 closest to the vertex of one corner of the glass substrate and a position P2 closest to the vertex of a corner adjacent to one corner of the glass substrate, and the laminate resin layer is located on the side of the glass substrate closer to the straight line connecting the positions P1 and P2. (6) A laminate as in 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) A laminate as in (2), wherein at least one of the distances Y at the four sides of the glass substrate is different. (8) A laminate as described in any one of (1) to (7), wherein the laminate resin layer is divided into a plurality of regions. (9) A laminate as described in any one of (1) to (8), wherein the intermediate resin layer is composed of a silicone resin. (10) A laminate as described in any one of (1) to (9), wherein the exfoliative resin layer is composed of polyethylene terephthalate. (11) A laminate as described in any one of (1) to (10), wherein the thickness of the glass substrate is 0.2 to 1 mm. (12) A laminate as described in any one of (1) to (11), wherein the Young's modulus of the glass substrate is 100 GPa or less. [Effect of the Invention]

According to the present invention, a laminated body can be provided which is less likely to cause poor peeling of the peelable resin layer.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are illustrative for describing the present invention and are not limited to the embodiments shown below. In addition, various changes and substitutions can be made to the following embodiments without departing from the scope of the present invention. The numerical range expressed by "～" refers to the range including the numerical values written before and after "～" as the lower limit and upper limit.

It was found that a characteristic point of the laminated body of the present invention is that it has a glass substrate and a laminated resin layer arranged on the glass substrate. The laminated resin layer has an intermediate resin layer and a peelable resin layer from the glass substrate side. The laminated resin layer on the glass substrate On the surface of the side, there is a peripheral area where the laminated resin layer is not arranged. The length of the long side of the glass substrate is more than 400 mm, and the length of the short side of the glass substrate is more than 320 mm. In at least one corner of the glass substrate, from The distance X from the vertex of the corner portion to the laminated resin layer at the closest position is 4 mm or more, thereby suppressing peeling defects of the peelable resin layer. In this way, the desired effect is obtained.

＜Laminated body＞ FIG. 1 is a schematic cross-sectional view showing the first example of the laminated body according to the embodiment of the present invention, and FIG. 2 is a schematic plan view showing the first example of the laminated body according to the embodiment of the present invention. As shown in FIG. 1 , the laminated body 10 has a glass substrate 12 and 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. The 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 super elliptical shape when viewed from the normal direction of the surface 12 a of the glass substrate 12 .

The release resin layer 18 is peeled off from the laminate 10, and a polyimide layer (not shown) is formed on the intermediate resin layer 16. The glass substrate 12 functions as a supporting substrate, and when viewed in the normal direction of the surface 12a on the laminate resin layer 14, the outer shape is, for example, a quadrilateral. The laminate 10 is shown in FIG. 2 , and the length _L1 of the long side 12b of the glass substrate 12 is greater than 400 mm, and the length _L2 of the short side 12c of the glass substrate 12 is greater than 320 mm. The glass substrate 12 is larger than the laminated resin layer 14, and there is a peripheral region 13 where the laminated resin layer 14 is not disposed on the surface 12a of the glass substrate 12 on the laminated resin layer 14 side. The surface 12a of the peripheral region 13 of the glass substrate 12 is exposed. In the laminated body 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 laminated resin layer 14 at the closest position is 4 mm or more. In such a laminate 10, even if the laminate 10 is heated during transportation or autoclave processing, the glass substrate 12 can be prevented from warping, and peeling failures such as difficulty in peeling the peelable resin layer 18 are unlikely to occur.

The glass substrate 12 is sometimes chamfered at the outer edge. In this case, the vertex 12e of the corner 12d is sometimes also an arc with a predetermined radius of curvature. When the corner 12d is an arc, the direct portion of each side of the glass substrate 12 is extended in the extension direction of each side, and the point where the extension lines of the two adjacent sides intersect is the virtual vertex. The line obtained by connecting the virtual vertices that are diagonally opposite to each other in the glass substrate 12 is the virtual diagonal line. The point where the virtual diagonal line intersects with the arc is the vertex. In addition, the corner 12d of the glass substrate 12 is sometimes cut like an orientation plane. In this case, as with the above-mentioned arc, the point where the edge (not shown) formed after cutting the corner intersects with the above-mentioned virtual diagonal line is the vertex.

In the laminated body 10, the distance X from the vertex 12e of the corner portion 12d to the laminated resin layer 14 at the closest position 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 area where the laminated resin layer 14 is provided with respect to the surface 12 a of the glass substrate 12 becomes wider. Furthermore, the distance X from the vertex 12e of the corner portion 12d to the laminated resin layer 14 at the closest position does not need to be the same in all four corner portions 12d of the glass substrate 12. The distance X may be different in at least one of the four corners 12d of the glass substrate 12, or may be different in all. Furthermore, for example, it may be configured such that two of the four corner portions 12d are paired with the remaining two corner portions, and the distance X between the two pairs may be different. The laminated body 10 is preferably such that the smallest distance Y among the distances from the point P on one side of the glass substrate 12 to the laminated resin layer 14 at the closest position is 1 mm or more. It is preferable that the minimum distance Y is 15 mm or less because the area where the laminated resin layer 14 is provided with respect to the surface 12 a of the glass substrate 12 becomes wider. Furthermore, among the four sides of the glass substrate 12, the smallest distance Y among the distances from a point on one side to the laminated resin layer 14 at the closest position can be at least 1 may be different, or all of them may be different. In this case, the laminated resin layer 14 is disposed close to at least one of the four sides. In this way, the laminated resin layer 14 is not limited to being disposed on the surface 12 a of the glass substrate 12 so that the peripheral area 13 around the laminated resin layer 14 is evenly distributed. The laminated resin layer 14 may be disposed close to one side.

As shown in FIG. 2 , in the laminated body 10 , the position P1 of the laminated resin layer 14 closest to the apex 12 e of one corner 12 d of the glass substrate 12 is set, and the position P1 is the position P1 closest to the one corner 12 d of the glass substrate 12 . The position P2 of the laminated resin layer 14 closest to the vertex 12e of the adjacent corner portion 12d is preferably located closer to the side of the glass substrate 12 than the straight line Lp connecting the position P1 and the position P2. That is, the laminated resin layer 14 has a region 14d on the side of the glass substrate 12 relative to the straight line Lp. As shown in FIG. 2 , the straight line Lp exists on both the long side 12b side and the short side 12c side. In the laminated resin layer 14, the straight line Lp on the long side 12b side has a region 14d close to the long side 12b side of the glass substrate 12. In addition, in the laminated resin layer 14, the straight line Lp on the short side 12c side has a region 14d close to the short side 12c side of the glass substrate 12. When the peelable resin layer 18 of the laminated body 10 is peeled off and a polyimide layer (not shown) is formed on the glass substrate 12 and the intermediate resin layer 16, if the connection position P1 and the position P2 are connected as described above, It is preferable that the straight line Lp is close to the long side 12b side or the short side 12c side of the glass substrate 12 when the laminated resin layer 14 is present. This can suppress the deterioration of the polyimide layer during high-temperature heating and make the polyimide layer less prone to cracks. . In this case, the outer shape of the laminated resin layer 14 when viewed from the normal direction of the surface 12 a of the glass substrate 12 is a quadrangle (see FIG. 3 ), and preferably the outer shape of the laminated resin layer 14 is as shown in FIG. 2 . Furthermore, in the laminated resin layer 14, when the region 14d is present, the distance X and the distance Y satisfy the relationship of distance X>distance Y×1.4.

The shape of the laminated resin layer 14 of the laminated body 10 is not particularly limited if it satisfies the above-mentioned distance X, and may be a quadrilateral. When the laminated body 10a is observed from the normal direction of the surface 12a of the laminated resin layer 14 side of the glass substrate 12 as shown in FIG3, the shape may also be a rectangle. Furthermore, FIG3 is a schematic top view of the second example of the laminated body of the embodiment of the present invention. In FIG3, the same symbols are marked for the same components as the laminated body 10 shown in FIG1 and FIG2, and their detailed description is omitted.

FIG. 4 is a schematic top view of the third example of the laminated body of the embodiment of the present invention. In FIG. 4 , the same symbols are assigned to the same components as the laminated body 10 shown in FIG. 1 and FIG. 2 , and detailed description thereof is omitted. The laminated body 10b shown in FIG. 4 is different from the laminated body 10 shown in FIG. 1 and FIG. 2 in that the laminated resin layer 14 is divided into a plurality of regions. Otherwise, the laminated body 10b has the same structure as the laminated body 10 shown in FIG. 1 and FIG. 2 . The laminated resin layer 14 of the laminated body 10b is provided at a position half the length of the long side 12b, and is divided into two regions 15a and 15b by a straight groove 19 extending along the short side 12c. The two regions 15a and 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. There is no laminated resin layer 14 in the groove 19, and the surface 12a of the glass substrate 12 is exposed. The length of the long side 12b of the groove 19 in the extending direction, that is, the width Z of the groove 19, for example, can also be wider than the above-mentioned distance Y. The groove 19 is formed by, for example, cutting and removing the laminated resin layer 14 using a cutter or a laser. In addition, the laminated resin layer 14 can be arranged at intervals to provide the groove 19. Furthermore, the laminate resin layer 14 is divided into two regions, but the number of divisions is not limited to 2, and may be, for example, 3 to 240. The two regions 15a and 15b are not limited to being the same in shape and size, and at least one of the shapes or sizes may be different. The laminate resin layer 14 may be divided by a linear groove 19 that is provided at a position half the length of the short side 12c and extends along the long side 12b, rather than being limited to a linear groove 19 that extends along the long side 12b.

Even when the shape of the laminated resin layer 14 shown in FIG. 3 is a quadrilateral when observed in the normal direction of the surface 12a on the laminated resin layer 14 side of the glass substrate 12, the laminated resin layer 14 can be divided into a plurality of regions. Specifically, it can also be divided into two regions 15a and 15b by the groove 19, as in the laminated resin layer 14 of the laminated body 10c shown in FIG. 5. Furthermore, FIG. 5 is a schematic top view of the fourth example of the laminated body of the embodiment of the present invention. In FIG. 3, the same symbols are marked for the same components as the laminated body 10 shown in FIG. 1 and FIG. 2, and their detailed description is omitted.

Hereinafter, each member constituting the above-mentioned laminated body will be described in detail. (Glass base board) The glass substrate is a member that supports and reinforces the laminated resin layer 14 and functions as a supporting substrate. As the glass constituting the glass substrate, alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high-oxide silica glass, and other oxide-based glasses containing silicon oxide as the main component are preferred. As the oxide-based glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferred. More specifically, the glass substrate may include a glass substrate including alkali-free borosilicate glass (trade name "AN100" manufactured by AGC Co., Ltd.). The manufacturing method of a glass substrate is usually obtained by melting a glass raw material and shaping the molten glass into a plate shape. This forming method may be a general one, and examples thereof include a float method, a melting method, and a trough down-draw method. The shape of the glass substrate is not particularly limited, but from the viewpoint of processing such as transportation and transfer, when viewed from the normal direction of the surface 12 a of the glass substrate 12 on the side of the laminated resin layer 14 , the outer shape is preferably a quadrangular shape. When the shape of the glass substrate is a quadrilateral, the long and short sides of the glass substrate can be of different lengths, and the long and short sides of the glass substrate can also be of the same length.

The glass substrate is preferably non-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, damage caused by contact with peripheral components when the glass substrate is transported can be suppressed. The Young's modulus of the glass substrate is preferably 65 GPa or more. If the Young's modulus of the glass substrate is 65 GPa or more, damage caused by contact with peripheral components when the glass substrate is transported can be suppressed. The thickness Dt of the glass substrate (see FIG. 1) is preferably 0.2 to 1 mm. The thickness Dt of the above-mentioned glass substrate is a value obtained by measuring the thickness of any 10 points of the glass substrate 12 and arithmetically averaging them.

(Build-up resin layer) The build-up resin layer 14 is provided as the intermediate resin layer 16 and the release resin layer 18 as described above. For example, after the release resin layer 18 is peeled off, a polyimide layer (not shown) is formed on the glass substrate 12 and the intermediate resin layer 16.

[Middle resin layer] The intermediate resin layer 16 is formed on the surface 12a of the glass substrate 12. The intermediate resin layer 16 is a film used to prevent the polyimide layer (not shown) disposed thereon from peeling off. Examples of the material of the intermediate resin layer 16 include acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin. Alternatively, several types of resins may be mixed to form the intermediate resin layer 16 . Among them, from the viewpoint of heat resistance or peelability, as the material of the intermediate resin layer 16, silicone resin or polyimide silicone resin is preferred, silicone resin is more preferred, and condensation-hardening type resin is more preferred. Silicone resin formed from silicone. The intermediate resin layer 16 made of silicone resin is called a silicone resin layer. Hereinafter, the form in which the intermediate resin layer 16 is a silicone resin layer will be described in detail.

The silicone resin refers to a resin containing a predetermined organosiloxy group unit, and is usually obtained by hardening curable silicone. Hardening silicone is classified into addition-hardening silicone, condensation-hardening silicone, ultraviolet-hardening silicone, and electron-beam hardening silicone according to its hardening mechanism, and any of them can be used. Among them, condensation-hardening silicone is preferred. As the condensation-hardening silicone, a hydrolyzable organosilane compound as a monomer or a mixture thereof (monomer mixture), or a partially hydrolyzed condensate (organic silane compound) obtained by subjecting a monomer or a monomer mixture to a partial hydrolysis-condensation reaction can be preferably used. polysiloxane). By using this condensation-hardening silicone, a hydrolysis/condensation reaction (sol-gel reaction) proceeds to form a silicone resin.

The intermediate resin layer 16 is preferably formed using a curable composition containing curable silicone. In addition to curable silicone, the curable composition may also contain a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, a metal compound, etc. Examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanide series metals, bismuth (Bi), aluminum (Al), and tin (Sn). The content of the metal compound is not particularly limited and can be adjusted appropriately.

The middle resin layer 16 preferably has a hydroxyl group. The hydroxyl group is generated by cutting a portion of the Si-O-Si bonds of the silicone resin constituting the middle resin layer 16. In addition, when a condensation reaction type silicone is used, the hydroxyl group becomes the hydroxyl group of the middle resin layer 16.

After peeling off a resin substrate, the thickness of the intermediate resin layer 16 is preferably 1 μm or more in order to have excellent burying properties when a glass supporting substrate is laminated on the side of the resin substrate without an intermediate layer. Preferably it is above 6 μm. From the aspects of processing cost and process throughput, 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 further preferably 12 μm or less. Furthermore, excellent foreign matter filling performance means that even if foreign matter exists between the glass substrate 12 and the intermediate resin layer 16 , the foreign matter is filled by the intermediate resin layer 16 . If the embedding ability of foreign matter is excellent, convex portions caused by foreign matter are less likely to occur in the intermediate resin layer 16 . According to this situation, if the foreign matter filling property is excellent, a polyimide layer is formed on the intermediate resin layer 16 as described above, and when a member for an electronic device is formed on the polyimide layer, it is possible to suppress defects caused by protrusions. Risks such as wire breakage in components used in electronic devices. The thickness of the intermediate resin layer 16 is obtained by measuring the thickness of the intermediate resin layer 16 at any position above 5 points using a non-contact surface quality measuring device "PF-60" manufactured by Mitaka Optoelectronics Co., Ltd. and averaging the results. .

[Releasable resin layer] The peelable resin layer 18 is disposed on the intermediate resin layer 16 and protects the intermediate resin layer 16 . The peelable resin layer 18 is made of, for example, polyimide resin, polyester resin (for example, polyethylene terephthalate, polyethylene naphthalate), polyolefin resin (for example, polyethylene, polypropylene), Or polyurethane resin. Among them, from the viewpoint of easy availability, the resin constituting the releasable resin layer 18 is preferably polyester resin, and more preferably polyethylene terephthalate.

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

The release resin layer may further have a close contact layer on the surface of the intermediate resin layer 16. As the close contact layer, a well-known adhesive layer may be used. As the adhesive constituting the adhesive layer, for example, (meth) acrylic adhesive, silicone adhesive, and urethane adhesive may be exemplified. In addition, the close contact layer may also be composed of resin, and as the resin, for example, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth) acrylic resin, butyral resin, polyurethane resin, and polystyrene elastomer may be exemplified. In order to reduce the peeling force when peeling the release resin layer, the surface roughness (Ra) of the intermediate resin layer 16 of the release resin layer is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 15 nm or less. In addition, in order to maintain the close contact between the release resin layer and the intermediate resin layer, Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more. The surface roughness (Ra) is measured using the non-contact surface/layer cross-section shape measurement system "VertscanR3300-lite" manufactured by Mitsubishi Chemical Systems Co., Ltd.

<Manufacturing method of laminated body> The manufacturing method of laminated body is not particularly limited, and a well-known method can be cited as an example. For example, a method of forming an intermediate resin layer 16 in a predetermined area on a glass substrate 12 and then forming a release resin layer 18 on the intermediate resin layer 16 can be cited as an example. The manufacturing sequence of each layer is described in detail below.

First, the intermediate resin layer 16 is formed in a predetermined area on the glass substrate 12 . The method for forming the intermediate resin layer 16 can be appropriately selected according to the material of the intermediate resin layer 16 . For example, when forming a silicone resin layer as the intermediate resin layer 16, the above-mentioned curable composition containing curable silicone is applied to a predetermined area on the glass substrate 12, and the coating film is heated. method.

Among them, when a silicone resin layer is used as the intermediate resin layer 16, in the case of excellent productivity, the following method can be cited as an example: prepare a transfer film (laminated film) having a temporary support and a pre-drive film disposed on the temporary support to become a silicone resin layer after heat treatment, make the pre-drive film in the transfer film adhere to a predetermined position on the glass substrate 12, and actually heat treat the laminate having the obtained glass substrate 12, the pre-drive film, and the temporary support. The silicone resin layer is formed by actually applying heat treatment. The above sequence is described in detail below.

In the above, first, a transfer film including a precursor film that becomes a silicone resin layer after heat treatment and a PET film that becomes a releasable resin layer is prepared. On the transfer film, a precursor film is formed on the PET film. The transfer film precursor film is bonded to a predetermined position on the glass substrate 12 to obtain a laminated base. After the above-mentioned transfer film is bonded to the glass substrate 12, the obtained laminated base body may also be washed with an alkaline detergent. In addition, after washing with alkaline detergent, you can also use pure water to rinse if necessary. Furthermore, after rinsing with pure water, an air knife can also be used to remove the water if necessary.

When heat treatment is used to form the silicone resin layer, it is preferably carried out while applying pressure. Specifically, it is preferred to use an autoclave to carry out the heat treatment and the pressure treatment. The heating temperature during the heat treatment is preferably 50 to 350°C, more preferably 55 to 300°C, and further preferably 60 to 250°C. The heating time is preferably 10 to 60 minutes, more preferably 20 to 40 minutes. The pressure during the pressure treatment is preferably 0.5 to 1.5 MPa, more preferably 0.8 to 1.0 MPa.

In addition, the heat treatment may be performed a plurality of times. When the heat treatment is performed a plurality of times, the respective heating conditions can also be changed.

Next, in the laminate base, the PET film (peelable resin layer 18) and the silicone resin layer (intermediate resin layer 16) are cut into predetermined sizes from the PET film side of the transfer film to form a laminate. Moreover, 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. In addition, after the transfer film is attached to the glass substrate, the transfer film may be cut into a predetermined size. When forming a laminated body having grooves 19 as shown in FIG. 4 , the transfer film is cut into a predetermined size in the laminated base, and then the transfer film is cut from the PET film side to form grooves 19 . Alternatively, after the transfer film is cut into a predetermined size, the transfer film of the predetermined size may be separated into intervals between the grooves 19 and attached to the glass substrate. Moreover, even when forming the laminated body having the groove 19 as shown in FIG. 4 , the transfer film may be cut into a predetermined size after being attached to the glass substrate. [Example]

Hereinafter, the present invention will be specifically described based on the examples, but the present invention is not limited to these examples. Hereinafter, Examples 1 to 4 are comparative examples, and Examples 5 to 13 are embodiments.

(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 to react for 12 hours to obtain a crude reaction solution. The obtained crude reaction solution was cooled to 25°C, and then washed three times with water (300 g). Trimethylsilyl chloride (70 g) was added to the washed crude reaction solution, and the mixture was stirred at 25°C for 20 minutes, and then heated to 50°C to react for 12 hours. The obtained crude reaction solution was cooled to 25°C, and then washed three times with water (300 g). The crude reaction liquid after washing was distilled under reduced pressure to remove toluene, and after forming a slurry state, it was dried overnight in a vacuum dryer to obtain a curable silicone 1 as a white organic polysiloxane compound. The curable silicone 1 has a molar ratio of M unit and T unit of 13:87, all organic groups are methyl groups, and the average OX group number is 0.02. The M unit refers to an organic silaneoxy unit represented by (R)3SiO _1/2 , and the T unit refers to an organic silaneoxy unit represented by RSiO _3/2 . R in each formula represents a hydrogen atom or an organic group. The average OX group number represents the number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom on average.

(Preparation of curable composition) Curing silicone 1 (20 g), zirconium octanoate compound ("ORGATIX ZC-200", manufactured by Matsumoto Fine Chemical Co., Ltd.) (0.16 g) as a metal compound, 2-ethylhexanoic acid (III) (manufactured by Alfa Aesar, metal content 12% by mass) (0.17 g), and Isoper G (manufactured by Tonen Genera Oil Co., Ltd.) (19.7 g) as a solvent were mixed, and the obtained mixed solution was filtered using a filter with a pore size of 0.45 μm to obtain curable composition 1.

(Production of laminated film) As a release film to be the peelable resin layer, a PET film (manufactured by Toyobo Co., Ltd., Toyobo Ester (registered trademark) film HPE (high density polyethylene), thickness 50 μm) was prepared, and the prepared hardened film was applied to the surface of the film. The silicone resin layer was formed by heating Composition 1 at 140° C. for 10 minutes using a hot plate. On the coated silicone resin layer, a PET film (manufactured by Toyobo Co., Ltd., Toyobo Ester (registered trademark) film HPE, thickness 50 μm) was bonded as a protective film to obtain a release film and silicone resin layer (middle The laminated film 1 is formed by laminating layers) and protective films in sequence. The thickness of the obtained laminated film 1 was 110 μm.

(Cutting of laminated film) Insert the PET film side of the release film of the laminated film 1 into the cutter and cut it into 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). Thereby, the outer shape of the laminated resin layer is formed into a quadrangular shape. In Example 1, a cutter was used to cut into a size of 400×320 mm. Furthermore, the laminated film 1 was placed on a stamping machine (hydraulic cutting machine manufactured by TAMARI Machinery Co., Ltd., device name "TP-12801000×100TON"), and the knife was made from a Thomson knife with a blade width of 0.5 mm and a blade angle of 30 degrees. Group (398×318 mm corner R6.2 mm, 458×728 mm corner R6.2 mm, 910×720 mm corner R0.1 mm, 910×724 mm corner R0.1 mm, 918×728 mm Angle R6.2 mm, angle R4.8 mm of 920×730 mm) is incident from the PET film side of the release film, cutting off the laminated film 1. Thereby, the outer shape of the laminated resin layer is formed into a super elliptical shape with four corners formed by curved lines. Here, the angle R represents the radius of curvature of the four-cornered curve constituting the outer shape of the laminated resin layer. In addition, as a method of cutting the laminated resin layer, the method of using a cutter is called a cutter method. In addition, as a cutting method of the laminated resin layer, the method using a stamping machine is called a stamping method.

(Production of a laminated substrate with one laminated film arranged in a glass substrate) Equivalent to Examples 1 to 12 in Table 1 below. A glass substrate "AN Wizus" (support substrate, Young's modulus 85 GPa) of 920×730 mm, 0.5 mm thick or 400×320 mm, 0.5 mm thick, with corner and edge chamfers washed with a water-based glass cleaner ("PK-LCG213" manufactured by Parker Corporation) and then washed with pure water is laminated to a PET film with a silicone resin layer of laminated film 1 formed by peeling off a protective film, to produce a laminated body in which a glass substrate, a silicone resin layer, and a PET film are arranged in sequence. Furthermore, during the above bonding, the glass substrate, the silicone resin layer, and the PET film are bonded in such a manner that the distance between the side (edge) 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 become the relationship of Example 1 shown in Table 1 below. Examples 1 and 7 use the above-mentioned 400×320 mm, 0.5 mm thick glass substrate. Examples 2 to 6 and Examples 8 to 13 use the above-mentioned 920×730 mm, 0.5 mm thick glass substrate.

(Production of a laminated substrate with two laminated films on a glass substrate) This corresponds to Example 13 in Table 1 below. A 920 × 730 mm, 0.5 mm thick glass substrate "AN Wizus" (support substrate) with corner and edge chamfers, which was washed with a water-based glass cleaner and then washed with pure water, and the protective film was peeled off After laminating the 458×728 mm PET film with the silicone resin layer of the laminated film 1 formed on it, another 458×728 mm PET film with the silicone resin layer of the laminated film 1 formed on it was peeled off. For film lamination, two silicone resin layers and PET films are placed on a glass substrate to create a laminate in which the glass substrate, silicone resin layer, and PET film are placed in sequence. Furthermore, during the above lamination, the distance along the long sides of the two laminated films 1 with the protective films peeled off is larger than the distance between the side surfaces (edges) of the glass substrate and the laminated films 1 with the protective films peeled off.

(Heating of laminated substrate) The obtained laminated body was arranged so that the glass substrate was in contact with the heating plate, and after heating at 60°C for 30 minutes, the laminated body was left to stand in a clean room environment (room temperature 23°C, humidity 55%) for 1 day.

<Examples 2 to 12> During the above lamination, the glass substrate, the silicone resin layer and the PET film (laminated film 1 after the protective film is peeled off) are laminated in a manner such that the distance between the side (edge) 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 become the relationship of Examples 2 to 12 shown in Table 1 below. Except for this, a laminated body is obtained in the same order as in Example 1.

In Example 2, the laminated film 1 was cut into a size of 920×730 mm using a cutter. In Example 3, the laminated film 1 was cut into a size of 920×730 mm (angle R 4.8 mm) using a punching machine. In Example 4, the laminated film 1 was cut into a size of 918×728 mm using a cutter. In Example 5, the laminated film 1 was cut into a size of 918×728 mm (angle R6.2 mm) using a punching machine. In Example 6, the laminated film 1 was cut into a size of 914.4×724.4 mm using a cutter. In Example 7, the laminated film 1 was cut into a size of 398×318 mm (angle R6.2 mm) using a punching machine.

In Example 8, the laminated film 1 was cut into a size of 912×722 mm using a cutter. In Example 9, the laminated film 1 was cut into a size of 910×720 mm (corner R0.1 mm) using a punch press. In Example 10, the laminated film 1 was cut into a size of 890×700 mm using a cutter. In Example 11, the laminated film 1 was cut into a size of 880×690 mm using a cutter. In Example 12, the laminated film 1 was cut into a size of 910×724 mm (corner R0.1 mm) using a punch press. In Example 12, during the above bonding, more specifically, the silicone resin layer and the PET film (laminated film 1 after the protective film is peeled off) are bonded to the glass substrate (920×730 mm) in such a way that the distance Y on the short side 12c (see FIG. 2) is 5 mm, and the distance Y on the long side 12b (see FIG. 2) is 1 mm and 5 mm.

<Example 13> In Example 13, the laminated film 1 was cut into a size of 458×728 mm (corner R6.2 mm) using a punch press to obtain two silicone resin layers and a PET film. In Example 13, during the above-mentioned lamination, two silicone resin layers and a PET film (laminated film 1 after the protective film was peeled off) were laminated to the glass substrate in such a manner that the distance between the side surface 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 became the relationship of Example 13 in Table 1. In Example 13, the two silicone resin layers and the PET film were laminated with a gap formed between them. Furthermore, the groove is set in the middle of the long side of the glass substrate 12 so that the width of the groove is 2 mm.

＜Evaluation of warpage＞ The laminate including the glass substrate, silicone resin layer, and PET film was placed on the stone platen in such a manner that the glass substrate was in contact with the stone platen, and a thickness gauge (manufactured by Affinity Measurement Co., Ltd., thickness gauge D 65) was used. mm 25 piece set (product name)) to measure the gap between the glass substrate and the stone plate at the corner of the laminate. Evaluate the largest gap amount (warp amount) among the four corners. Also, attach Scotch Tape (Scotch Mending tape width "810-1-18D" manufactured by 3M Co., Ltd.) to the corners of the PET film, and pull and peel the PET film. The laminated body is placed under a fluorescent lamp, and based on the light reflection state of the silicone resin layer, the presence or absence of defects after peeling is visually observed. A: The maximum warpage is less than 0.2 mm, and no post-peel defects will occur. B: The maximum warpage is more than 0.2 mm, and defects after peeling are produced

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

(Formation of polyimide layer) The PET film of the laminate of Examples 5 and 6 including the glass substrate, silicone resin layer, and PET film was peeled off, and heated at 250° C. for 30 minutes in an atmospheric environment using a clean oven. Next, after corona treatment was performed on the silicone resin layer, a colorless polyimide varnish ("Neopulim H230" manufactured by Mitsubishi Gas Chemical Co., Ltd.) was applied and then heated at 80° C. for 20 minutes using a hot plate. Then, an inert gas oven was used to heat 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 sequence. (Formation of silicon nitride layer) Secondly, a plasma CVD (Chemical Vapor Deposition) device was used to form a silicon nitride layer with a thickness of 100 nm on the entire surface of the polyimide layer of the laminated sample.

<Heat resistance evaluation> The laminated samples based on Examples 5 and 6 were subjected to a heat resistance test by heating at 420°C for 1 hour in a nitrogen environment. The appearance of the laminated samples after the heat resistance test was visually confirmed to evaluate whether cracks were generated in the polyimide layer closer to the edge of the glass substrate than the straight line connecting 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. A: Cracks were generated B: No cracks were generated In addition, the heat resistance evaluation was performed only on Examples 5 and 6 among Examples 1 to 13. Therefore, for the remaining examples 1 to 4 and examples 7 to 13, the "Heat Resistance Evaluation" column in Table 1 is marked as "-".

[Table 1] Size of glass substrate (mm) How to cut the laminated resin layer Dimensions of laminated resin layer (mm) Angle R (mm) The number of laminated resin layers relative to the glass substrate DistanceX (mm) Distance Y (mm) Distance between laminated resin layers (mm) Warpage assessment Effective area ratio of substrate Heat resistance evaluation Warpage(mm) Peelability example 1 400×320 Cutter method 400×320 - 1 0.0 0.0 - 0.21 B A - Example 2 920×730 Cutter method 920×730 - 1 0.0 0.0 - 0.21 B A - Example 3 920×730 Stamping method 920×730 4.8 1 2.0 0.0 - 0.2 B A - Example 4 920×730 Cutter method 918×728 - 1 1.4 1.0 - 0.2 B A - Example 5 920×730 Stamping method 918×728 6.2 1 4.0 1.0 - 0.17 A A A Example 6 920×730 Cutter method 914.4×724.4 - 1 4.0 2.8 - 0.16 A A B Example 7 400×320 Stamping method 398×318 6.2 1 4.0 1.0 - 0.16 A A - Example 8 920×730 Cutter method 912×722 - 1 5.6 4.0 - 0.13 A A - Example 9 920×730 Stamping method 910×720 0.1 1 7.1 5.0 - 0.1 A A - Example 10 920×730 Cutter method 890×700 - 1 21.0 15.0 - 0.07 A A - Example 11 920×730 Cutter method 880×690 - 1 28.0 20.0 - 0.06 A B - Example 12 920×730 Stamping method 910×724 0.1 1 5.1 1.0 - 0.1 A A - Example 13 920×730 Stamping method 458×728 6.2 2 4.0 1.0 2 0.15 A A -

Comparison of Examples 1 to 4 and Examples 5 to 13 shows that if the distance X from the apex of the corner of the glass substrate to the laminated resin layer at the closest position is 4 mm or more, post-peeling defects are less likely to occur. From the comparison of Examples 1 to 10, Examples 12 to 13 and Example 11, it can be seen that if the distance X from the vertex of the corner of the glass substrate to the laminated resin layer at the closest position is 21 mm or less, the distance If the minimum distance Y between the above point and the closest laminated resin layer is 15 mm or less, the effective area increases. Comparing Example 5 and Example 6, it can be seen that in Example 5, the position P1 of the laminated resin layer closest to the vertex of one corner of the glass substrate is connected to the position P1 of the laminated resin layer, and the position P1 of the laminated resin layer is located at the corner adjacent to one corner of the glass substrate. The straight line at the position P2 where the vertex of the portion is closest to the laminated resin layer is closer to the side of the glass substrate where the laminated resin layer exists, so cracks are less likely to occur.

The present invention has been described in detail with reference to specific embodiments, but it is understood that various modifications or changes can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2022-132515 filed on August 23, 2022, the contents of which are incorporated herein by reference.

10: laminate 10a: laminate 10b: laminate 10c: laminate 12: glass substrate 12a: surface 12b: long side 12c: short side 12d: corner 12e: vertex 13: peripheral area 14: laminate resin layer 14a: surface 14d: area 15a: area 15b: area 16: intermediate resin layer 18: release resin layer 19: groove Dt: thickness _L1 : length _L2 : length Lp: straight line P: point P1: position P2: position X: distance Y: distance Z: width

FIG. 1 is a schematic cross-sectional view showing the first example of the laminated body of the embodiment of the present invention. FIG. 2 is a schematic top view showing the first example of the laminated body of the embodiment of the present invention. FIG. 3 is a schematic top view showing the second example of the laminated body of the embodiment of the present invention. FIG. 4 is a schematic top view showing the third example of the laminated body of the embodiment of the present invention. FIG. 5 is a schematic top view showing the fourth example of the laminated body of the embodiment of the present invention.

10: Laminated body

12: Glass substrate

12a: Surface

12b: Long side

12c: Short side

12d: Corner

12e: Vertex

13: Peripheral area

14:Laminated resin layer

14d:Area

L ₁ : Length

L ₂ : Length

Lp: straight line

P:point

P1: Location

P2: Location

X: distance

Y: distance

Claims (12)

A laminated body 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 releasable resin layer from the side of the glass substrate, a peripheral area where the laminated resin layer is not disposed exists on the surface of the glass substrate on the side of the laminated resin layer, 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 vertex of the corner to the laminated resin layer at the closest position is 4 mm or more. The laminated body of claim 1, wherein the smallest distance Y among the distances from a point on one side of the glass substrate to the laminated resin layer at the closest position is 1 mm or more. Such as the laminated body of claim 1, wherein the distance X is 21 mm or less. Such as the laminated body of claim 2, wherein the distance Y is 15 mm or less. The laminated body according to any one of claims 1 to 4, wherein the position P1 of the laminated resin layer closest to the apex of one corner of the glass substrate is the position P1 of the laminated resin layer, and the position P1 is the position P1 of the corner of the glass substrate. The position P2 where the apex of the adjacent corner portion is closest to the laminated resin layer is located closer to the side of the glass substrate than the straight line connecting the positions P1 and P2. The laminated body according to any one of claims 1 to 4, wherein at least one of the distances X at the four corners of the glass substrate is different. The laminated body of claim 2, wherein at least one of the distances Y on each of the four sides of the glass substrate is different. A laminate as claimed in any one of claims 1 to 4, wherein the laminate resin layer is divided into a plurality of regions. A laminate as claimed in any one of claims 1 to 4, wherein the intermediate resin layer is composed of silicone resin. The laminated body according to any one of claims 1 to 4, wherein the peelable resin layer is composed of polyethylene terephthalate. The laminate of any one of claims 1 to 4, wherein the thickness of the glass substrate is 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.