KR20170059395A - Cutting method for glass laminate - Google Patents

Abstract

The present invention is to provide a method for cutting a glass laminate in which a remaining amount of a resin layer is reduced compared with the conventional method. The present invention relates to a method for cutting a glass laminate laminated with a first glass plate and a second glass plate thinner than the first glass plate by interposing the resin layer. The method for cutting a glass laminate of the present invention includes a step of irradiating the glass laminate with laser light, and the pulsefluorescence F[J/mm^2] and the wrap rate [%] L of the laser light satisfy the following formulas: formula (A), F >= 3, and formula (B), F > -0.09 L + 11.8. Here, L = (D0 - v / f) / D0 * 100, D0 is a condensing diameter (mm) of the pulse of the laser light, v is the cutting speed (mm/s), and f is an oscillation frequency (Hz) of the laser light.

Description

TECHNICAL FIELD [0001] The present invention relates to a cutting method for a glass laminate,

The present invention relates to a method of cutting a glass laminate.

Conventionally, a glass plate has been used as a substrate for an organic EL display panel, but recently, a resin plate such as polyimide has been used. The resin plate is excellent in flexibility compared to the glass plate, and it is easy to make curved organic EL display panel. Such an organic EL panel is used in a smart phone or a television in which a display surface is curved.

On the other hand, since the resin plate has a lower gas barrier property than the glass plate, there is a problem that moisture or oxygen permeates from the outside air to deteriorate the element. Therefore, in order to solve such a problem, it has been studied to use a composite made by forming a resin film on a glass thin plate as an organic EL panel. For example, Patent Document 1 discloses a composite used as a glass substitute substrate for a flexible display including a cage-like silsesquioxane resin and a glass plate.

However, since such a composite is formed by forming a resin film on a very thin glass plate, its rigidity is low and it is easily deformed by its own weight. In manufacturing the organic EL display panel, a glass laminate is formed by bonding a supporting glass to the composite to secure its rigidity, and the panel is manufactured using the glass laminate. The supporting glass is temporarily used in the manufacture of the panel, and is peeled off after the manufacture of the panel.

Japanese Patent Application Laid-Open No. 2013-107354 Japanese Patent Application Laid-Open No. 2015-78106

However, when an electronic device such as an organic EL display panel is manufactured using such a glass laminate, a problem may arise in cutting the glass laminate.

As a conventional method of cutting a composite, it is known to use a cutter wheel as shown in Patent Document 2. The cutter wheel forms a scribe line on the surface of the glass plate and then applies a load to the glass plate to cut the glass plate from the scribe line as a starting point.

However, when a resin layer having a high fracture toughness value such as polyimide is used as the resin layer, a part of the resin layer may be connected without cutting even if the glass sheet is cut.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a cutting method of a glass laminate in which the remaining amount of cut of the resin layer is reduced.

An embodiment of the present invention is a method for cutting a glass laminate in which a first glass plate and a second glass plate thinner than the first glass plate are laminated via a resin layer, Wherein the pulse fluorescence F [J / mm ² ] and the overlap ratio [%] L of the laser light satisfy the following formulas (A) and (B).

F? 3 ... The formula (A)

F > -0.09 L + 11.8 ... The formula (B)

(Mm), v is the cutting speed (mm / s), and f is the oscillation frequency (Hz) of the laser light, where L = .

In another aspect of the present invention, the resin layer is a layer containing polyimide.

In another aspect of the present invention, the laser light is laser light by a CO ₂ laser.

In another aspect of the present invention, the thickness of the first glass plate is 0.1 mm or more and 1.1 mm or less.

In another aspect of the present invention, the thickness of the second glass plate is 0.03 mm or more and 0.3 mm or less.

In another aspect of the present invention, the thickness of the resin layer is 0.1 占 퐉 or more and 100 占 퐉 or less.

The present invention can provide a cutting method of a glass laminate in which the remaining amount of cut of the resin layer is reduced compared with the conventional method.

1 is a side view showing one embodiment of a cutting apparatus according to the present invention.
2 is a top view showing a state in which the glass laminate is cut.
Fig. 3 (a) is a cross-sectional view showing one embodiment of the composite, Fig. 3 (b) is a partially broken sectional view of one embodiment of the composite, and Fig. 3 Sectional view.
4 is a flow chart showing an example of a process from the production of the polyamic acid solution to the cutting of the laminate.
Fig. 5 is an explanatory diagram for explaining the overlap rate.
6 is a graph showing the relationship between the pulse-fluence and the overlap ratio in the examples and comparative examples.

Next, one embodiment of the present invention will be described.

Fig. 1 shows one embodiment of a cutting apparatus according to the present invention. The cutting apparatus 20 has an XY stage 21, a nozzle 22, a transfer optical system 23, and a laser oscillator 24 as main components. The nozzle 22 is a nozzle having a condensing lens in a metal housing and a tube 22a for introducing the assist gas AG to the nozzle 22 is connected to the side of the housing. The laser oscillator 24 is a laser oscillator such as a CO ₂ laser, a Yttrium Aluminum Garnet (YAG) laser, an excimer laser or a copper deposition laser. In cutting the glass laminate, the use of a CO ₂ laser is preferable.

The glass laminate 10 is obtained by bonding a supporting glass (carrier glass) 13 in a peelable state to a composite made by forming a resin layer 12 on the main surface of a glass plate 11. It should be noted that the object to be cut in the present invention includes a complex.

When the glass laminate 10 is to be cut, the glass laminate 10 is placed on the XY stage 21, and the nozzle 22 is arranged above the glass laminate 10. The glass laminate 10 may be supported by the support glass (carrier glass) 13 or may be mounted on the XY stage 21 with the glass plate 11 facing downward. A condenser lens is provided in the nozzle 22 to match the focal point FS of the laser beam LB with a desired depth of the glass laminate 10. [ Then, the glass laminate 10 can be cut by irradiating the laser beam LB while moving the XY stage 21. At the time of irradiating the laser beam LB, the assist gas AG is simultaneously sprayed onto the cut portion, whereby the molten resin or glass can be blown off, and the cut portion can be prevented from being re-bonded by the molten glass or the like. The kind of the assist gas (AG) is not particularly limited, but it is preferable to use an incombustible gas, and nitrogen, argon, or the like can be used.

2 is a top view showing a state in which the glass laminate is cut. The glass laminate 10 is transported in the direction of arrow A together with the XY stage 21. [ The portion (laser light irradiation region 15) contacted by the laser light LB irradiated from the nozzle 22 in Fig. 1 moves along the line to be cut 14 (virtual line) on the glass laminate 10, The glass laminate 10 is cut. Here, the position of the laser beam irradiation area 15 is displaced by transporting the glass laminate 10, but instead, the glass laminate 10 may be fixed and the nozzle 22 may be moved. Further, the line along which the object is intended to be cut 14 is not limited to a straight line but may adopt any line such as a curve, an arc, and a broken line. In addition, the shape of the glass laminate 10 is not limited to a rectangle.

3 (a) and 3 (b) show one embodiment of the glass laminate according to the present invention. The composite 10a has a resin layer 12 including a polyimide resin or the like having a predetermined structure formed on a glass plate 11. [ The surface 12b of the resin layer 12 is in contact with the first main surface 11a of the glass plate 11 and the other surface of the resin layer 12 is not in contact with the other surface. The composite 10a is laminated on the glass plate 11 so that the front surface 12a of the resin layer 12 and the supporting glass 13 are in direct contact with each other as shown in Figure 3 (c) Or a member forming process for producing a member for an electronic device such as a liquid crystal display panel.

In the glass laminate 10, a member for an electronic device such as a TFT (Thin Film Transistor) is formed on the second main surface 11b of the glass plate 11 in a member forming process described later. Thereafter, the glass laminate 10 on which the member for an electronic device is formed is separated into the supporting glass 13 and the composite 10a. The separated support glass 13 may be reused by stacking a new composite, or may be reused in another application (such as used for manufacturing a large-size liquid crystal TV).

The resin layer 12 is fixed on the glass plate 11. The composite 10a is peelably laminated on the support glass 13 so that the resin layer 12 directly contacts the support glass 13 Both are in close contact. In the present invention, " fixed " and " peelable " means " peeling strength " (i.e., stress required for peeling), and " fixed " That is, the peel strength of the interface between the resin layer 12 and the glass plate 11 becomes larger than the peel strength of the interface between the resin layer 12 and the support glass 13.

More specifically, the interface between the glass plate 11 and the resin layer 12 has a peel strength x and a stress in the peeling direction exceeding the peel strength x is applied to the interface between the glass plate 11 and the resin layer 12 The interface between the glass plate 11 and the resin layer 12 is peeled off. The interface between the resin layer 12 and the supporting glass 13 has a peeling strength y and the stress in the peeling direction exceeding the peeling strength y is applied to the interface between the resin layer 12 and the supporting glass 13 The interface between the ground resin layer 12 and the supporting glass 13 is peeled off.

The peel strength x is higher than the peel strength y in the glass laminate 10 (also referred to as a laminate with an electronic device member described later). The glass laminate 10 is peeled off from the interface between the resin layer 12 and the supporting glass 13 when stress is applied to the glass laminate 10 in the direction in which the supporting glass 13 and the glass plate 11 are separated from each other, And is separated into the composite body 10a and the support glass 13.

In order to increase the adhesion of the resin layer 12 to the glass plate 11, for example, a method of forming the resin layer 12 on the glass plate 11 (preferably, Is cured on a glass plate 11 to form a predetermined resin layer 12) is carried out. The resin layer 12 bonded to the glass plate 11 with high bonding force can be formed by the adhesive force at the time of curing.

On the other hand, the bonding force of the resin layer 12 after curing with respect to the support glass 13 is generally lower than the bonding force generated at the time of curing. Therefore, by forming the resin layer 12 on the glass plate 11 and thereafter superposing the support glass 13 on the surface of the resin layer 12, the peel strengths (x) and (y) satisfy the desired relationship The glass laminate 10 can be produced.

Next, each layer (supporting glass 13, glass plate 11, and resin layer 12) constituting the composite 10a and the glass laminate 10 will be described in detail.

[Supported glass]

Although the composition of the support glass 13 is not particularly limited, for example, glass having various compositions such as glass containing alkali metal oxide (soda lime glass or the like) or alkali-free glass can be used. Among them, alkali-free glass is preferable in that the heat shrinkage rate is small. More specifically, it is preferable that the composition of the support glass 13 is in the following range as a glass transition temperature in terms of percentage of mass based on oxide in view of better effect of the present invention.

SiO ₂ : 50 to 73%

Al ₂ O ₃ : 10.5 to 24%

B ₂ O ₃ : 0 to 5%

MgO: 0 to 10%

CaO: 0 to 14.5%

SrO: 0 to 24%

BaO: 0 to 13.5%

MgO + CaO + SrO + BaO: 8 to 29.5%

Further, from the viewpoint of more excellent effects of the present invention, it is more preferable to be in the following range.

SiO ₂ : 53 to 70%

Al ₂ O ₃ : 15 to 22%

B ₂ O ₃ : 0.1 to 3%

MgO: 1 to 7%

CaO: 3 to 10%

SrO: 0 to 12%

BaO: 0 to 12%

MgO + CaO + SrO + BaO: 10 to 25%

Although the thickness of the support glass 13 is not particularly limited, it is preferable that the thickness of the glass laminate 10 is such that it can be processed in a production line of an existing electronic device panel. For example, the thickness of a glass plate used in current liquid crystal display panels is usually in the range of 0.4 to 1.2 mm, particularly 0.7 mm or 0.5 mm. The thickness of the glass laminate 10 is preferably as large as the thickness of the glass plate used in the current process because it can easily flow into the current production line.

For example, a current manufacturing line is designed to process a substrate having a thickness of 0.5 mm, and when the thickness of the composite body 10a is 0.1 mm, the thickness of the supporting glass 13 may be set to about 0.4 mm. If the current production line is designed to treat a glass plate having a thickness of 0.7 mm, the thickness of the supporting glass 13 may be set to about 0.5 mm if the composite 10a has a thickness of 0.2 mm.

The use of the composite body 10a in the present invention is not limited to the organic EL display panel or the liquid crystal display panel, but may be a solar power generation panel or the like. Therefore, the thickness of the supporting glass 13 is not limited, but is preferably 0.1 to 1.1 mm. It is preferable that the thickness of the supporting glass 13 is larger than that of the composite 10a in order to secure the rigidity of the composite 10a. The thickness of the supporting glass 13 is preferably 0.3 mm or more, more preferably 0.3 to 0.8 mm, and further preferably 0.4 to 0.7 mm.

The surface of the support glass 13 may be a polished surface subjected to mechanical polishing or chemical polishing, or a non-etched surface (non-polished surface) not subjected to polishing treatment. It is preferable that the non-etching surface (base surface) is in terms of productivity and cost.

The support glass 13 has a first major surface and a second major surface, and the shape thereof is not limited, but is preferably rectangular. The rectangle is a substantially rectangular shape and may have a corner cut. The size of the support glass 13 is not limited, but is preferably 100 to 2,000 mm x 100 to 2,000 mm, and more preferably 500 to 1,000 mm x 500 to 1,000 mm.

[Glass plate]

The first main surface 11a of the glass plate 11 is in contact with the resin layer 12 and the electronic device member is formed in the second main surface 11b on the opposite side. That is, the glass plate 11 is a substrate used for forming an electronic device to be described later.

The type of the glass plate 11 may be a common one, and examples thereof include glass plates for display devices such as LCDs and OLEDs. The glass plate 11 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. The coefficient of thermal expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio.

If the coefficient of linear expansion of the glass plate 11 is large, the member forming process often involves heat treatment, so that various problems are likely to occur. For example, in the case of forming the TFT on the glass plate 11, if the glass plate 11 on which the TFT is formed under heating is cooled, the positional deviation of the TFT due to the heat shrinkage of the glass plate 11 may be a problem.

The glass plate 11 is obtained by melting a glass raw material and shaping the molten glass into a plate. For example, a float method, a fusion method, a slot down draw method, a pull-call method, a rubber method, or the like is used. In particular, the glass plate 11 having a small thickness can be obtained by heating the glass molded into a plate shape at one time and heating the glass plate at a temperature capable of being formed, and stretching it by means of drawing or the like (thinning method).

The kind of the glass of the glass plate 11 is not particularly limited, but it is preferable to use an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, glass having a silicon oxide content of 40 to 90 mass% in terms of an oxide is preferable. The composition of the glass plate 11 may be the same as that of the support glass 13.

A glass suitable for the kind of the electronic device member and the manufacturing process thereof is adopted as the glass plate 11. For example, a glass plate for a liquid crystal panel includes a glass (alkali-free glass) substantially free from an alkali metal component in that the elution of the alkali metal component tends to affect the liquid crystal (note that the alkali- . Thus, the glass of the glass plate 11 is appropriately selected based on the kind of the applied device and the manufacturing process thereof.

The thickness of the glass plate 11 is preferably not more than 0.3 mm, more preferably not more than 0.15 mm, and further preferably not more than 0.10 mm from the viewpoint of reducing the thickness and / or weight of the glass plate 11. [ When it is 0.3 mm or less, it is possible to give good flexibility to the glass plate 11. If it is 0.15 mm or less, the glass plate 11 can be rolled up. However, it is preferable that the thickness of the glass plate 11 is 0.03 mm or more because of easy production of the glass plate 11, easy handling of the glass plate 11, and the like.

The glass plate 11 may be composed of two or more layers, and in this case, the materials forming the respective layers may be the same or different materials. For example, a transparent conductive film such as ITO may be formed on the surface of the glass plate 11. In this case, the "thickness of the glass plate 11" means the total thickness of all the layers.

[Resin Layer]

The resin layer 12 has a function of bringing the glass plate 11 and the supporting glass 13 into close contact with each other until they are separated from each other. The surface 12a of the resin layer 12 in contact with the supporting glass 13 is peelably laminated (tightly contacted) on the first main surface of the supporting glass 13. [ The resin layer 12 is bonded to the first main surface of the support glass 13 with a weak bonding force and the peel strength y of the interface is the peel strength of the interface between the resin layer 12 and the glass plate 11 x).

That is, when the glass plate 11 and the supporting glass 13 are separated from each other, the first main surface of the supporting glass 13 is peeled off from the interface between the glass substrate 11 and the resin layer 12, It is difficult to peel off. In the present invention, the property of easily peeling the support glass 13 from the resin layer 12 is called " peelability ". On the other hand, the first main surface of the glass plate 11 and the resin layer 12 are bonded with a bonding force that is relatively difficult to peel off. The bonding strength of the interface between the resin layer 12 and the supporting glass 13 is adjusted before and after the formation of the electronic device member on the surface (second main surface 12b) of the glass plate 11 of the glass laminate 10 (I.e., the peel strength (x) or the peel strength (y) may be changed). However, even after forming the member for electronic devices, the peel strength (y) is lower than the peel strength (x).

It is considered that the resin layer 12 and the supporting glass 13 are bonded with a bonding force due to a weak adhesive force or a van der Waals force. In the case where the supporting glass 13 is laminated on the surface of the resin layer 12 after the resin layer 12 is formed, if the polyimide resin in the resin layer 12 is sufficiently imidated so as not to exhibit the adhesive force, It is believed that they are joined by the bonding force resulting.

However, the polyimide resin in the resin layer 12 often has a weak adhesive strength to some extent. The polyimide in the resin layer 12 may be adhered to the support glass 13 by a heating operation or the like when the electronic device member is formed thereon after the production of the glass laminate 10, It is considered that the bonding force between the layer 12 and the layer of the supporting glass 13 is increased. In some cases, the surface of the resin layer 12 before lamination or the first main surface of the supporting glass 13 before lamination may be laminated by performing a treatment for weakening the bonding force therebetween. The peeling strength y can be weakened by weakening the bonding force between the interface between the resin layer 12 and the support glass 13 by performing non-adhesive treatment or the like on the surface to be laminated and then laminating it.

The resin layer 12 is bonded to the surface of the glass plate 11 by a strong bonding force such as an adhesive force or an adhesive force. For example, the resin layer 12 is formed on the glass plate 11 as described above (preferably, the curable resin to be a polyimide resin containing a repeating unit represented by the formula (1) is thermally cured to form a glass plate 11), it is possible to obtain a high bonding force by bonding the layer of the thermosetting polyimide resin to the surface of the glass plate 11. The bonding strength between the surface of the glass plate 11 and the resin layer 12 is determined by performing a treatment (for example, a treatment using a coupling agent) that generates a strong bonding force between the surface of the glass plate 11 and the resin layer 12 .

The thickness of the resin layer 12 is not particularly limited, but is preferably 0.1 to 100 占 퐉, more preferably 0.5 to 50 占 퐉, and further preferably 1 to 30 占 퐉. When the thickness of the resin layer 12 is within this range, it is possible to suppress the occurrence of deformation defects of the glass plate 11 even when bubbles or foreign matter intervene between the resin layer 12 and the supporting glass 13. [ In addition, if the thickness of the resin layer 12 is too thick, it takes time and material to form it, which is not economical and the heat resistance may be lowered. If the thickness of the resin layer 12 is too small, the adhesion between the resin layer 12 and the supporting glass 13 may be deteriorated. The resin layer 12 may include two or more layers. In this case, the " thickness of the resin layer 12 " means the total thickness of all the layers.

The surface roughness Ra of the surface of the resin layer 12 on the side of the supporting glass 13 is preferably 0 to 2.0 nm, more preferably 0 to 1.0 nm, and still more preferably 0.05 to 0.5 nm. When the surface roughness Ra is within the above range, the adhesion of the composite 10a to the support glass 13 is excellent, and the displacement of the composite 10a is difficult to occur. Generally, a method of forming a polyimide resin into a layer is a method of extruding a thermoplastic polyimide resin followed by extrusion molding, or a method of applying a solution containing a curable resin, which becomes a polyimide resin, by thermosetting onto a substrate, There is a method of curing. The latter method is preferable because a resin layer 12 having a surface roughness Ra within the above range is easily obtained.

Here, the surface roughness Ra is measured by an atomic force microscope (manufactured by Pacific Nanotechnology, Nano Scope IIIa; Scan Rate 1.0 Hz, Sample Lines 256, Off-line Modified Flatten order-2, Planefit order-2) Measurement of Surface Roughness of Fine Ceramics Thin Films by Force Microscope (JIS R 1683: 2007 Guideline)

The polyimide resin of the resin layer 12 includes a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the following formula (1). The polyimide resin contains the repeating unit represented by the formula (1) as a main component (preferably 95 mol% or more based on the total repeating units), but other repeating units other than the repeating units (for example, -1) or (2-2)). Further, the residue (X) of the tetracarboxylic acid is intended to mean a tetracarboxylic acid residue excluding a carboxy group from a tetracarboxylic acid, and a residue (A) of a diamine is intended to be a diamine residue excluding an amino group from a diamine.

[Chemical Formula 1]

In the formula (1), X represents a tetracarboxylic acid residue excluding a carboxy group from tetracarboxylic acids, and at least 50 mol% of the total number of X is a group consisting of the groups represented by the following formulas (X1) to (X4) And at least one group selected. Of these, 80 to 100 mol% of the total number of X is preferably replaced by the following formulas (X1) to (X4) because the peelability of the composite 10a and the supporting glass 13 or the heat resistance of the resin layer 12 is more excellent (100 mol%) of the total number of X is selected from the group consisting of the groups represented by the following formulas (X1) to (X4), and at least one group selected from the group consisting of And more preferably at least one kind of group selected from the group consisting of When less than 50 mol% of the total number of X contains at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4) At least one of peelability and heat resistance of the resin layer 12 is deteriorated.

Represents at least one kind of group selected from the group consisting of the groups represented by (A1) to (A7), wherein 50 mol% or more of the total number of "A" represents a diamine residue other than the amino group from the diamines . 80 to 100% by mole of the total number of "A" satisfy the following formulas (A1) to (A7) in view of better peelability of the composite 10a and the support glass 13 or heat resistance of the resin layer 12, (100 mol%) of the total number of A is at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A7) More preferably at least one group selected from the group consisting of When less than 50 mol% of the total number of A contains at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A7) At least one of peelability and heat resistance of the resin layer 12 is deteriorated.

It is preferable that 80 to 100 mol% of the total number of X is represented by the following formulas (X1) to (X4) because the peelability of the composite 10a and the supporting glass 13 or the heat resistance of the resin layer 12 is more excellent And at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A7) in an amount of 80 to 100 mol% of the total number of "A" (100 mol%) of the total number of X includes at least one kind of group selected from the group consisting of the following groups represented by the following formulas (X1) to (X4), and the group represented by A It is more preferable that substantially total number (100 mol%) of the total number includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A7).

(2)

Among these, "X" is preferably a group represented by the formula (X1) and a group represented by the formula (X2) because the peelability of the composite 10a and the supporting glass 13 is better or the heat resistance of the resin layer 12 is better , And a group represented by the formula (X1) is more preferable.

The "A" is selected from the group consisting of the groups represented by the formulas (A1) to (A4) in that the peelability of the composite 10a and the supporting glass 13 is better or the heat resistance of the resin layer 12 is better Group is preferable and a group selected from the group consisting of the groups represented by the formulas (A1) to (A3) is more preferable.

As the polyimide resin containing the group represented by the formulas (X1) to (X4) and the preferable combination of the groups represented by the formulas (A1) to (A7), it is preferable that the "X" is a group represented by the formula (X1) X2), and "A" is a group selected from the group consisting of the groups represented by the formulas (A1) to (A5), among which X is a group selected from the group consisting of Wherein X is a group represented by the formula (X1), A is a group represented by the formula (A1), and X is a group represented by the formula (X2) Polyimide resin 2 is preferably used. Polyimide resin 1 and polyimide resin 2 are preferable in view of long-term heat resistance under an environment of 450 占 폚, and polyimide resin 1 is more preferable in view of long-term heat resistance under an environment of 500 占 폚.

When X is a group represented by the formula (X4), and A is a combination of groups represented by the formulas (A6) and (A7), it is preferable from the viewpoint of transparency.

The repeating number (n) of the repeating unit represented by the formula (1) in the polyimide resin is not particularly limited, but is preferably an integer of 2 or more, and preferably 10 More preferably from 10 to 10,000, and even more preferably from 15 to 1,000. The molecular weight of the polyimide resin is preferably 500 to 100,000 from the viewpoint of coating workability and heat resistance.

The polyimide resin may be one or more selected from the group consisting of the following groups in which the proportion of less than 50 mol% of the total number of the residues (X) of the tetracarboxylic acids is within a range that does not impair the heat resistance. In addition, two or more of the groups illustrated below may be included.

(3)

In addition, the polyimide resin may be one or more selected from the group consisting of the groups exemplified below in which less than 50 mol% of the total number of the residues (A) of the diamines is within a range that does not impair the heat resistance. In addition, two or more of the groups illustrated below may be included.

[Chemical Formula 4]

The polyimide resin may have an alkoxysilyl group at the molecular end.

As a method for introducing an alkoxysilyl group at a molecular terminal, there is a method of reacting a carboxyl group or an amino group of a polyamic acid described later with an epoxy group-containing alkoxysilane or a partial condensate thereof. The epoxy group-containing alkoxysilane can be obtained, for example, by reacting an epoxy compound having a hydroxyl group in a molecule with an alkoxysilane or a partial condensate thereof. The epoxy compound having a hydroxyl group preferably has 15 or less carbon atoms, and examples thereof include glycidol. Examples of the alkoxysilane include tetraalkoxysilane having 4 or less carbon atoms or trialkoxysilane having an alkoxy group having 4 or less carbon atoms and an alkyl group having 8 or less carbon atoms. Specific examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and trialkoxysilanes such as methyltrimethoxysilane. The reaction between the epoxy compound having a hydroxyl group in the molecule and the alkoxysilyl group is preferably carried out in the range of hydroxyl equivalent / alkoxysilyl equivalent of the epoxy compound = 0.001 / 1 to 0.5 / 1.

The silica structure may be a structure obtained by subjecting an alkoxysilyl group at the molecular end of the polyimide resin to a sol-gel reaction or a de-alcohol condensation reaction by heat treatment or hydrolysis. The alkoxysilane may be added during the reaction. As the alkoxysilane, the above-mentioned compounds can be used.

When the molecular end is made into a silica structure, the heat resistance can be improved. Further, the coefficient of linear expansion of the polyimide resin can be lowered, so that even when the thickness of the supporting substrate is thin, the warpage of the supporting substrate with the resin layer can be reduced.

The content of the polyimide resin in the resin layer 12 is not particularly limited but from the viewpoint of the peelability of the composite 10a and the support glass 13 or the heat resistance of the resin layer 12, By mass, more preferably from 75 to 100% by mass, and still more preferably from 90 to 100% by mass.

The resin layer 12 may contain components other than the polyimide resin (for example, a filler that does not hinder heat resistance) if necessary.

Examples of the filler that does not impair the heat resistance include fibrous fillers such as fibrous, platy, scaly, granular, irregular, and crushed. Specific examples thereof include carbon fibers such as PAN or pitch carbon fibers, A metal fiber such as aluminum fiber or brass fiber, a gypsum fiber, a ceramic fiber, an asbestos fiber, a zirconia fiber, an alumina fiber, a silica fiber, a titanium oxide fiber, a silicon carbide fiber, a rock surface, a potassium titanate whisker, Calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, olustonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, calcium carbonate, graphite, Metal powder, metal flake, metal ribbon, metal oxide, carbon powder, graphite, carbon flake, scaly carbon, Carbon nanotubes, and the like. Specific examples of the metal species of the metal powder, the metal flake and the metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chrome and tin.

The resin layer 12 contains a repeating unit having a residue (X) of a tetracarboxylic acid represented by the formula (1) and a residue (A) of a diamine formed on the glass plate 11 by thermosetting A first heat treatment for heating a layer obtained by applying a layer of a curable resin to be a polyimide resin or a composition comprising the polyimide resin and a solvent at a temperature of 60 ° C or higher and lower than 250 ° C, And a second heat treatment in this order.

The manufacturing method of the resin layer 12 will be described in detail in the production method of the glass laminate at the downstream end.

[Production method of glass laminate]

As a first form of the method for producing the glass laminate 10 according to the present invention, a resin layer 12 is formed on a glass plate 11 by using a curable resin to be described later, and then a resin layer 12 is formed on the resin layer 12 The glass laminate 10 is produced.

It is considered that when the curable resin is cured on the surface of the glass plate 11, the peeling strength between the resin layer 12 and the surface of the glass plate 11 increases due to the interaction with the surface of the glass plate 11 during the curing reaction. Therefore, even if the glass plate 11 and the supporting glass 13 include the same material, the peel strength between the resin layer 12 and the both can be made different.

(Resin layer forming step)

The resin layer 12 is formed of a polyimide resin (polyimide resin) which is formed on a glass plate and contains a repeating unit having a residue (X) of a tetracarboxylic acid represented by the formula (1) And a second heat treatment for heating at a temperature of 250 DEG C or higher and 500 DEG C or lower are performed in this order on the surface of the cured resin layer. Further, it is preferable that at least 50 mol% of the total number of the residues (X) of the tetracarboxylic acids contains at least one group selected from the group consisting of the groups represented by the above formulas (X1) to (X4) A) contains at least one kind of group selected from the group consisting of the groups represented by the above formulas (A1) to (A7).

In the resin layer forming step, a layer of the curable resin which becomes a polyimide resin containing a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) In the order of 60 ° C or more and less than 250 ° C and a second heat treatment in which the temperature is 250 ° C or more and 500 ° C or less in this order to obtain a resin layer. As shown in Fig. 3A, the resin layer 12 is formed on at least one surface of the glass plate 11 in the process.

Hereinafter, the resin layer forming step will be described by dividing it into the following three steps.

Step (1): A step of applying a curable resin to form a polyimide resin represented by the above formula (1) by thermosetting on a glass plate 11 to obtain a coated film

Step (2): Step of heating the coating film at a temperature of 60 ° C or more and less than 250 ° C

Step (3): A step of forming a resin layer by further heating the coating film at a temperature of not less than 250 ° C and not more than 500 ° C

(Coating film forming step)

In this step, a curable resin to be a polyimide resin having a repeating unit represented by the above formula (1) is applied on a glass plate 11 by thermal curing to obtain a coated film. The curable resin preferably contains a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, and at least a part of the tetracarboxylic dianhydride is a compound represented by the following formulas (Y1) to (Y4) At least one diamine selected from the group consisting of compounds represented by the following formulas (B1) to (B7), at least one kind of diamine selected from the group consisting of And the like.

[Chemical Formula 5]

[Chemical Formula 6]

The polyamic acid is usually represented by a structural formula containing a repeating unit represented by the following formula (2-1) and / or formula (2-2). The definitions of X and A in the formulas (2-1) and (2-2) are as described above.

(7)

The reaction conditions of the tetracarboxylic acid dianhydride and the diamine are not particularly limited, and it is preferable to carry out the reaction at -30 to 70 占 폚 (preferably -20 to 40 占 폚) in order to efficiently synthesize the polyamic acid Do. The mixing ratio of the tetracarboxylic dianhydride to the diamine is not particularly limited, but it is preferably 0.66 to 1.5 moles, more preferably 0.9 to 1.1 moles, and still more preferably 0.9 to 1.5 moles, based on 1 mole of the diamine, of the tetracarboxylic dianhydride , The reaction is carried out at 0.97 to 1.03 mole.

When the tetracarboxylic dianhydride and the diamine are reacted, an organic solvent may be used if necessary. The kind of the organic solvent to be used is not particularly limited, and examples thereof include N, N-dimethylacetamide, N, But are not limited to, N, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethylsulfoxide, m-cresol, phenol, Diglyme, triglyme, tetraglyme, dioxane, gamma -butyrolactone, dioxolane, cyclohexanone, cyclopentanone, and the like may be used, and two or more of them may be used in combination.

In the above reaction, other tetracarboxylic acid dianhydrides other than the tetracarboxylic dianhydride selected from the group consisting of the compounds represented by the above-mentioned formulas (Y1) to (Y4) may be used together if necessary.

In the above reaction, diamines other than the diamines selected from the group consisting of the compounds represented by the above-mentioned formulas (B1) to (B7) may be used together if necessary.

The curable resin used in the present step may be a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine, or a tetracarboxylic acid dianhydride or a diamine, which is capable of reacting with a polyamic acid, do. A tetracarboxylic acid dianhydride or a diamine in addition to the polyamic acid may be added to the tetracarboxylic acid dianhydride or the tetracarboxylic acid dianhydride, Can be bonded via diamines.

When the polyamide acid has an amino group at the terminal thereof, a tetracarboxylic acid dianhydride may be added, or may be added so that the carboxyl group is 0.9 to 1.1 mols per mole of the polyamic acid. When a carboxyl group is present at the terminal of the polyamic acid, a diamine may be added, and the amino group may be added in an amount of 0.9 to 1.1 moles per mole of the polyamic acid. When the polyamide acid has a carboxyl group at the terminal thereof, the acid terminal may be obtained by ring opening the terminal acid anhydride group by adding water or an arbitrary alcohol.

The tetracarboxylic acid dianhydride to be added later is more preferably a compound represented by the formula (Y1) to (Y4). The diamines to be added later are preferably diamines having aromatic rings, more preferably compounds represented by the formulas (B1) to (B7).

When the tetracarboxylic acid dianhydrides or diamines are added later, the polymerization degree (n) of the polyamic acid having the repeating unit represented by the formula (2-1) or (2-2) is preferably 1 to 20 . When the polymerization degree (n) is within this range, the curable resin solution can be made to have a low viscosity even if the polyamic acid concentration in the curable resin solution is 30 mass% or more.

In the present step, components other than the curable resin may be used.

For example, a solvent may be used. More specifically, the curable resin may be dissolved in a solvent to be used as a solution (curable resin solution) of the curable resin. As the solvent, an organic solvent is particularly preferable from the viewpoint of the solubility of the polyamic acid. As the organic solvent to be used, an organic solvent used in the above-mentioned reaction may be mentioned.

In addition, as a suitable form of the solvent, it is preferable to use a solvent having a boiling point (under atmospheric pressure) of less than 250 ° C. When the solvent is used, the solvent tends to be volatilized in the first heat treatment step, and as a result, the appearance of the film is more excellent. The lower limit of the boiling point is not particularly limited, but is preferably 60 deg. C or more from the viewpoint of handling property.

When the organic solvent is contained in the curable resin solution, the content of the organic solvent is not particularly limited as long as the thickness of the coating film can be adjusted and the coating property can be improved. However, Preferably 99 mass%, more preferably 20 mass% to 90 mass%.

If necessary, a dehydrating agent or a dehydrating ring-closing catalyst may be used together to promote dehydration ring closure of the polyamic acid. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used.

The method of applying the curable resin (or the curable resin solution) on the surface of the glass plate 11 is not particularly limited and a known method can be used. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method and a gravure coating method.

The thickness of the coating film obtained by the above treatment is not particularly limited and is appropriately adjusted so that the resin layer 12 having the above-described desired thickness can be obtained.

(Process (2): first heat treatment process)

Step (2) is a step of heating the coated film at a temperature of 60 ° C or more and less than 250 ° C. By carrying out this step, it is possible to remove the solvent while avoiding the rubbing of the solvent, and it is difficult to form foams or orange peel-like film defects.

The method of the heat treatment is not particularly limited, and a known method (for example, a method in which a glass plate with a coated film is heated in a heating oven and heated) is suitably used.

The heating temperature is preferably 60 占 폚 to 250 占 폚, more preferably 600 to 150 占 폚, and more preferably 60 to 120 占 폚 in that foaming of the resin layer is further suppressed. It is particularly preferable to heat at a temperature lower than the boiling point of the solvent in the range of the heating temperature.

The heating time is not particularly limited and is appropriately selected in accordance with the structure of the curable resin to be used, but is preferably 5 to 60 minutes, more preferably 10 to 30 minutes in order to further prevent depolymerization of polyamic acid Do.

The atmosphere of heating is not particularly limited, and is carried out, for example, in air, under vacuum, or under an inert gas. If it is carried out under vacuum, it is possible to remove volatile components in a shorter time even if heated at a low temperature, and furthermore depolymerization of polyamic acid can be controlled more favorably.

The first heat treatment step may be performed stepwise (two or more steps) by changing the heating temperature and the heating time.

(Process (3): second heat treatment process)

The step (3) is a step of forming a resin layer by heating the coated film subjected to the heat treatment in the step (2) at 250 캜 or higher and 500 캜 or lower. By carrying out this step, the ring-opening reaction of the polyamic acid contained in the curable resin proceeds to form a desired resin layer.

The method of the heat treatment is not particularly limited, and a known method (for example, a method in which a glass plate with a coated film is heated in a heating oven and heated) is suitably used.

The heating temperature is 250 ° C or more and 500 ° C or less and the residual solvent ratio is lowered and the imidization rate is further increased and the peeling property of the composite 10a and the supporting glass 13 or the heat resistance of the resin layer 12 is more excellent And more preferably 350 to 500 ° C.

The heating time is not particularly limited and the optimal time is appropriately selected depending on the structure of the curable resin to be used. However, the residual solvent ratio is lowered and the imidization rate is further increased, and the temperature of the composite 10a and the support glass 13 Is preferably from 15 to 120 minutes, more preferably from 30 to 60 minutes, in view of better peelability or heat resistance of the resin layer (12).

The atmosphere of heating is not particularly limited, and is carried out, for example, in air, under vacuum, or under an inert gas.

The resin layer containing the polyimide resin is formed by the above-mentioned step (3).

The imidization ratio of the polyimide resin is not particularly limited, but is preferably not less than 99.0%, more preferably not less than 99.5%, from the viewpoint of the peelability of the composite 10a and the support glass 13 or the heat resistance of the resin layer 12 More preferable.

A method of measuring the imidization ratio is a method in which a cured resin is heated to 350 ° C for 2 hours under a nitrogen atmosphere to have an imidization ratio of 100% and a peak intensity before and after the second heat treatment in the IR spectrum of the curable resin (Peak originating from the benzene ring: about 1,500 cm ^-1 ), and the peak intensity derived from the imidecarbonyl group: peak intensity of about 1,780 cm ^-1 .

(Lamination step)

In the laminating step, the supporting glass 13 is laminated on the surface of the resin layer 12 obtained in the resin layer forming step, and the supporting glass 13, the resin layer 12 and the glass plate 11 are provided in this order To obtain the glass laminate 10.

The method of laminating the supporting glass 13 on the resin layer 12 is not particularly limited, and a known method can be adopted. For example, a method of superposing the supporting glass 13 on the surface of the resin layer 12 under an atmospheric pressure environment. If necessary, the supporting glass 13 may be placed on the surface of the resin layer 12, and then the supporting glass 13 may be pressed onto the resin layer 12 using a roll or press. The bubbles mixed in between the resin layer 12 and the layer of the support glass 13 are relatively easily removed by pressing by roll or press.

The vacuum lamination method or the vacuum press method is more preferable because it suppresses the incorporation of bubbles and secures good adhesion. Even when minute bubbles remain, the bubbles do not grow due to heating, and there is an advantage that it is difficult to lead to deformation defects of the supporting glass 13. Further, bubbles are less likely to remain by compression bonding under vacuum heating. When the support glass 13 is laminated, it is preferable to sufficiently clean the surface of the support glass 13 that contacts the resin layer 12 and to laminate it in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the support glass 13 is.

Further, after the support glass 13 is laminated, a pre-annealing treatment (heat treatment) may be performed if necessary. The adhesion of the laminated support glass 13 to the resin layer 12 is improved and the peel strength (y) can be made appropriate. By performing the pre-annealing process, So that the productivity of the electronic device is improved.

The conditions of the pre-annealing treatment are appropriately selected in accordance with the kind of the resin layer 12 to be used but the point of making the peel strength (y) between the support glass 13 and the resin layer 12 more appropriate It is preferable to carry out the heat treatment at 200 占 폚 or higher (preferably 200 to 400 占 폚) for 5 minutes or longer (preferably 5 to 30 minutes).

(Glass laminate)

The glass laminate 10 of the present invention can be used for various purposes, for example, a display panel, a solar cell, a thin-film secondary battery, a semiconductor wafer on which a circuit is formed on a surface, And the like. Further, in the intended use, the glass laminate 10 is often exposed (for example, 1 hour or more) under high temperature conditions (for example, 400 DEG C or more).

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

In the above description, the form in which the cured resin is used to produce the supporting substrate with the resin layer has been described in detail. However, the composite obtained by applying the composition containing the polyimide resin and the solvent may be used to produce the composite. More specifically, a layer (coating film) obtained by applying a composition containing the polyimide resin and a solvent onto a glass plate is formed, and a first heat treatment is performed at a temperature of 60 ° C or more and less than 250 ° C, And a second heating treatment for heating the mixture in this order.

The kind of the polyimide resin used is as described above. The type of the solvent to be used is not particularly limited, and examples thereof include the solvents contained in the above-mentioned curable resin solution.

(Cutting method of glass laminate)

A constitutional example of the above-described method of cutting a glass laminate will be described.

Here, the supporting glass 13 is referred to as a first glass plate, and the glass plate 11 is referred to as a second glass plate. That is, a laminate obtained by laminating a first glass plate and a second glass plate thinner than the first glass plate with a resin layer interposed therebetween can be used as the glass laminate described hitherto.

The method of cutting the glass laminate according to the present embodiment may have a step of irradiating the glass laminate with laser light as described with reference to Fig.

The pulsed fluorescence F [J / mm ² ] and the overlap ratio [%] L of the laser light preferably satisfy the following formulas (A) and (B).

F? 3 ... The formula (A)

F > -0.09 L + 11.8 ... The formula (B)

(Mm), v is the cutting speed (mm / s), and f is the oscillation frequency (Hz) of the laser light, where L = .

According to this cutting method of the glass laminate, the remaining amount of cutting the resin layer can be reduced as compared with the conventional method.

[Example]

4 is a flow chart showing an example of a series of steps from preparation of a polyamic acid solution to cutting of a laminate.

≪ Preparation of polyamic acid solution >

Para-phenylenediamine (10.8 g, 0.1 mol) was dissolved in N, N-dimethylacetamide (198.6 g) and stirred at room temperature. BPDA (29.4 g, 0.1 mmol) was added thereto for 1 minute, and the mixture was stirred at room temperature for 2 hours to contain a polyamic acid having a repeating unit represented by the formula (2-1) and / or the formula (2-2) To obtain a polyamic acid solution (P1) having a solid content concentration of 20 mass% (step S1).

The viscosity of this solution was measured and found to be 5,000 centipoise at 20 ° C. The viscosity was measured using a DVL-BII digital viscometer (B-type viscometer) manufactured by Toray McCarthy Co., Ltd. at 20 ° C. X in the repeating unit represented by the formula (2-1) and / or the formula (2-2) contained in the polyamic acid is a group represented by (X1) and A is a group represented by the formula (A1).

≪ Preparation of glass laminate &

First, a glass plate having a plate thickness of 0.1 mm was cleaned by pure water, followed by UV cleaning (step S2).

Subsequently, the polyamide acid solution (P1) was coated on the first main surface of the glass plate with a spin coater (rotation speed: 2,000 rpm, 15 seconds) (step S3), and a coating film containing polyamic acid was provided on the glass plate Construction amount 2 g / m ² ). The polyamic acid is a resin obtained by reacting a compound represented by the formula (Y1) with a compound represented by the formula (B1).

Subsequently, the coating film was heated in air at 60 占 폚 for 15 minutes and then at 120 占 폚 for 15 minutes, and then the coating film was heated at 350 占 폚 for 15 minutes to form a resin layer (step S4). A polyimide resin having a repeating unit represented by the following formula (3) (wherein X represents a group represented by (X1) and A includes a group represented by the formula (A1)) Was included.

[Chemical Formula 8]

The imidization rate was 99.7%. The surface roughness Ra of the formed resin layer surface was 0.2 nm. The measurement method of the imidization ratio and the measurement method of the surface roughness Ra were carried out by the above-mentioned method.

Thereafter, the support glass 13 and the resin layer 12 of the composite body 10a were joined together by a vacuum press at room temperature to obtain a glass laminate 10 (step S5).

In the obtained glass laminate 10, the supporting glass 13 and the glass plate 11 were in close contact with the resin layer 12 without generating air bubbles, had no deformed defects, and had good smoothness. The peel strength x of the interface between the glass plate 11 and the resin layer 12 in the glass laminate 10 was higher than the peel strength y of the interface between the resin layer 12 and the support glass 13 .

Subsequently, the glass laminate 10 was subjected to heat treatment at 450 캜 for 60 minutes under atmospheric conditions, and the glass laminate 10 was cooled to room temperature (step S6). As a result, the composite 10a in the glass laminate 10 was separated from the support glass 13 And appearance changes such as foaming and whitening of the resin layer 12 were not observed.

Thereafter, the glass laminate after the heating was cut using a carbon dioxide gas laser (step S7).

(Example 1)

Hereinafter, examples and comparative examples obtained by changing the cutting conditions will be described.

The laser light LB was incident vertically from above the glass laminate 10 directly from the support glass 13 side. At this time, the pulse-fluorescence was 14.1 J / mm ² and the coverage was 25%. Here, the pulse fluorescence is obtained by dividing the pulse average energy of the laser light LB by the pulse area. The overlap ratio L is represented by the following equation (4), and as shown schematically in Fig.

D0 is the condensing diameter (mm) of the pulse of the laser beam LB, v is the cutting speed (mm / s), and f is the oscillation frequency (Hz) of the laser beam LB. After the spot SP1 of the pulse is formed, the next spot SP2 is formed at the position moved from the SP1 by the moving distance v / f [mm].

L = (D0-v / f) / D0 * 100 ... Equation (4)

Tables 1 and 2 show examples, and Tables 3 and 4 show comparative examples.

The symbol in each table means the following.

◎: Easy to break operation and small in surface roughness

○: Breaking operation was necessary but broken

X: Not cut

(Cycle) Here, "breaking operation" means an operation of applying a load to a glass laminate after laser irradiation with a human hand to separate the glass laminate from the laser light irradiating portion.

A glass plate (length 200 mm, width 200 mm, plate thickness 0.1 mm, coefficient of linear expansion 38 x 10 ^-7 / 占 폚, manufactured by Asahi Glass Co., Ltd., trade name "AN100") containing no alkali borosilicate glass Respectively. A glass plate having the same composition as that of the glass plate 11 was used as the supporting glass 13, but a glass plate having a size and a plate thickness different from each other (240 mm in length, 240 mm in width and 0.5 mm in plate thickness) was used.

Other conditions are as follows. The glass laminate 10 after cutting shows a circular shape with a diameter of 160 mm. The thickness of the supporting glass 13 constituting the glass laminate 10 after cutting is 0.5 mm and the thickness of the glass plate 11 is 0.1 mm. The type of assisting gas (AG) is N ₂ . The flow rate of the assist gas (AG) is 50 l / min. The condensing diameter D0 of the laser beam LB is 0.3 mm. The thickness of the resin layer 12 is 23 mu m.

As a result, under the conditions of Example 1, there is a sufficient energy density, and by selecting a suitable lap rate, fusion bonding by glass or the like melted by the laser light irradiation portion does not occur and the glass laminate can be cut there was.

(Examples 2 to 4)

In Examples 2 to 4, the pulse-fluorescence and the overlap ratio in Example 1 were changed to the values shown in the table, and the other conditions were the same as those in Example 1.

(Comparative Examples 1 to 8)

In Comparative Examples 1 to 8, the pulse-fluorescence and the overlap ratio in Example 1 were changed to the values shown in the table, and the other conditions were the same as those in Example 1. All had insufficient energy density, and laser light did not penetrate through the glass laminate in the beginning, and the glass laminate did not break.

As described above, it can be seen that whether or not the glass laminate is cut has a large influence on the selection of the lap width of the laser beam and the value of the pulse fluorescence.

Fig. 6 shows the relationship between the pulse-fluence and the overlap ratio in the examples of Tables 1 and 2 and the comparative example of Tables 3 and 4. Fig. As shown in the figure, the results of? And? Are concentrated in the substantially upper region, and X is concentrated in the lower region. From this, it is possible to separate the area in which x is distributed and the area in which? And? Are distributed into one straight line. (5-1) and (5-2) shown below are used for the cutting of the glass laminate, and the pulse-fluorescence F [J / mm ² ] It was found desirable to satisfy.

F? 3 ... Equation (5-1)

F > -0.09 L + 11.8 ... Equation (5-2)

Although the embodiments and examples of the present invention have been described above, the present invention is not limited thereto. Various modifications and substitutions can be made to the embodiments and examples without departing from the scope of the present invention.

INDUSTRIAL APPLICABILITY As described above, the present invention can easily cut a conventional glass-laminated body including a glass plate and a resin layer, which is difficult to cut. Therefore, the present invention can be applied to the manufacture of various display device panels.

10: Glass laminate
10a: Complex
11: Glass plate
12: Resin layer
13: Support glass
14: Line to be cut
15: laser light irradiation area
20: Cutting device
21: XY stage
22: Nozzle
22a: tube
23: transmission optical system
24: laser oscillator
FS: Focus
AG: assist gas
LB: laser light

Claims (6)

A method for cutting a glass laminate in which a first glass plate and a second glass plate thinner than the first glass plate are laminated via a resin layer,
And a step of irradiating the glass laminate with laser light,
And the pulse-fluorescence F [J / mm ² ] and the overlap ratio [%] L of the laser light satisfy the following formulas (A) and (B).
F? 3 ... The formula (A)
F > -0.09 L + 11.8 ... The formula (B)
(Mm), v is the cutting speed (mm / s), and f is the oscillation frequency (Hz) of the laser light, where L = . The method of cutting a glass laminate according to claim 1, wherein the resin layer is a layer containing polyimide. The method according to claim 1 or 2, wherein the laser light is laser light by a CO ₂ laser. The method of cutting a glass laminate according to any one of claims 1 to 3, wherein the thickness of the first glass plate is 0.1 mm or more and 1.1 mm or less. The method for cutting a glass laminate according to any one of claims 1 to 4, wherein the thickness of the second glass plate is 0.03 mm or more and 0.3 mm or less. The method for cutting a glass laminate according to any one of claims 1 to 5, wherein the resin layer has a thickness of 0.1 占 퐉 or more and 100 占 퐉 or less.

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