JP6350163B2 - Glass laminate - Google Patents

Description

  The present invention relates to a glass laminate having a breakage preventing function capable of remarkably preventing the progress and breakage of cracks in a glass film.

  In recent years, electronic devices (electronic components) such as organic EL panels, solar cells, and thin film secondary batteries have been made thinner and lighter, and glass substrates used in these electronic devices have been made thinner. . However, when the strength of the glass substrate is reduced due to the thinning, there is a problem that the handling property of the glass substrate is deteriorated. Also, from the viewpoint of handling properties, a resin substrate can be used instead of the glass substrate, but the resin substrate has problems in chemical resistance, moisture resistance, heat resistance, and the like.

  Therefore, recently, a glass laminate excellent in visible light transmittance in which a transparent resin is laminated on a thin plate glass to improve handling properties has been proposed.

Examples of the glass laminate having improved handling properties include the following disclosure.
Patent Document 1 discloses a substrate in which a transparent resin having a thickness thinner than that of a glass sheet having a thickness of 100 μm or less is laminated. Polyurethane is disclosed as the transparent resin, and it is described that it is used as a substrate for poly LED elements and electrochromic elements.
In Patent Document 2, a glass layer in which a polymer layer of 200 μm or less is directly attached to at least one of a glass film having a thickness of 500 μm or less, and at least one side of the surface thereof has low undulation and low roughness— A plastic composite film is disclosed and described for use in electronic device substrates.
Patent Document 3 discloses a transparent substrate having a specific elastic modulus and fracture toughness value and having a transparent resin layer having a high glass transition temperature on one side or both sides of the glass. Is a specific value with respect to the glass film thickness, and that a thermoplastic resin is preferred.
Patent Document 4 discloses a transparent substrate having a transparent resin layer having a glass shrinkage stress of 5 MPa or more and showing a high glass transition temperature on one side or both sides of glass, and the resin used is thermoplastic. It is stated that resins are preferred.
Patent Document 5 discloses a method for producing a laminate in which a polyimide film having a specific structure is bonded to glass, and a difference in average linear expansion coefficient between glass and a resin layer is constant. It is described that warpage and peeling during heating and cooling can be suppressed.

JP 2002-521234 Gazette Special Table 2002-542971 JP 2010-132526 A JP 2011-088789 A International Publication 2011/030716 Publication Pamphlet

However, Patent Document 1 does not suggest any mechanical strength of the resin layer, and is insufficient for providing a glass laminate having excellent handling properties.
In addition, the resin used in Examples in Patent Document 2 has a problem in heat resistance when the laminate is used as an electronic device substrate.
Furthermore, the transparent resins disclosed in Patent Documents 3 and 4 still have a problem with heat resistance when the laminate is used as a substrate for an electronic device. In addition, since the resin layer is thicker than the glass thickness, when used as an electronic device substrate, a large amount of outgas is released, which may cause defects in the electronic device.
Although a polyimide is mentioned as a heat resistant resin, since the polyimide excellent in heat resistance generally contains an aromatic ring and / or a heterocyclic ring in the principal chain, it is known to be colored.
Known Document 5 discloses a method of laminating a polyimide film on glass. However, since the polyimide film requires a certain thickness to handle as a single body, the laminate does not have visible light transmittance. It was.

  On the other hand, a thin glass laminate having improved handling properties by being laminated with a resin layer can be rolled by reducing the thickness of the thin glass, which is advantageous in production. In general, a roll-shaped laminate is unwound from a roll, cut into a desired size, and used as a substrate for a device or the like. However, even in the case of a glass laminate having improved handling properties, cracks may propagate from the cut portion during cutting. The present invention solves such a problem.

As a result of intensive studies in view of the above-mentioned problems, the present inventors laminated a resin layer made of a polyimide resin composition having a specific mechanical property on a glass film at a specific thickness ratio, thereby developing cracks, It was also found that a glass laminate having a breakage preventing function capable of remarkably preventing breakage can be obtained. In addition, a glass laminate that can be suitably used as a substrate for an electronic device that has high heat resistance by using a polyimide resin composition and that is excellent in visible light transmittance due to a thin resin layer made of the polyimide resin composition. Led to the development.
That is, the present invention is as follows.

[1] A glass laminate in which a resin layer made of a polyimide resin composition is laminated on at least one side of a glass film having a thickness of 10 μm or more and 200 μm or less,
The polyimide resin composition has a tensile elongation at break of 10% or more and 500% or less, and a ratio of the total thickness of the resin layer to the thickness of the glass film (total thickness of the resin layer / thickness of the glass film) is 0.01. Above, the glass laminated body which is 0.4 or less.
[2] The glass laminate according to [1], wherein the resin layer made of the polyimide resin composition has a thickness of 1 μm or more and 25 μm or less.
[3] The glass laminate according to [1] or [2], wherein the glass film has a thickness of 20 μm or more and 100 μm or less.
[4] The glass laminate according to any one of [1] to [3], wherein the heat resistant temperature of the resin layer is 400 ° C. or higher.
[5] The glass laminate according to any one of [1] to [4], wherein a resin layer made of a polyimide resin composition is laminated on both surfaces of a glass film.
[6] The glass laminate according to [5], wherein at least one average surface roughness Sa of the laminate surface is 10 nm or less.
[7] The method for producing a glass laminate according to any one of [1] to [6], comprising at least the following steps (1) to (3).
(1) The process of forming the layer containing a polyimide precursor on a support film (2) The process of transferring the layer containing the polyimide precursor formed at the previous process to the glass film surface, and peeling the support film (3) The previous process Baking the layer containing the polyimide precursor transferred in step to form a resin layer comprising the polyimide resin composition

  According to the present invention, it is possible to provide a glass laminate having a breakage prevention function capable of remarkably preventing the progress and breakage of cracks as compared with conventional methods, and having high heat resistance and excellent transparency. Therefore, a glass laminate suitable as an electronic device substrate is provided.

  Hereinafter, the glass laminates according to the present invention and the materials constituting them will be described in detail. However, the description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention. It is not limited to these contents.

<Glass laminate>
The glass laminate of the present invention is formed by laminating a resin layer on one side or both sides of a glass film. The thickness of the glass laminate is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less from the viewpoint of flexibility. Moreover, it is 10 micrometers or more normally, it is preferable that it is 30 micrometers or more, and it is more preferable that it is 50 micrometers or more.

The glass laminate according to this embodiment preferably has an average surface roughness (arithmetic average roughness Sa) of at least one surface of 10 nm or less. If the average surface roughness (arithmetic average roughness Sa) of at least one surface is 10 nm or less, in the step of forming a circuit on the substrate surface using the glass laminate according to this embodiment as a substrate, for example, Since a conductive layer having a small thickness (several tens of nm) and a low surface resistance can be formed, the glass laminate according to this embodiment can be suitably used as a substrate of an electronic device.
The average surface roughness (arithmetic average roughness Sa) is more preferably 5 nm or less, and further preferably 3 nm or less. On the other hand, the lower limit is not limited, but is usually 0.1 nm or more.
In general, since the average surface roughness Sa of the glass surface tends to be a small numerical value, the average surface roughness Sa of the resin layer surface preferably satisfies the above value. In particular, in the case of a glass laminate in which resin layers are laminated on both surfaces of a glass film, it is preferable that the average surface roughness Sa on the surface of at least one resin layer satisfies the above value.

The average surface roughness Sa is measured as follows.
Surface observation (observation field of view: 93.97 μm × 71.30 μm) of the glass laminate was carried out using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.). The surface roughness (arithmetic average roughness Sa) is calculated.

As a method of adjusting the average surface roughness of the glass laminate surface, it is sufficient to prepare a resin layer made of a glass film or a polyimide resin composition having an average surface roughness in the above range, and the average surface roughness is determined by a known method. You may adjust and you may purchase the commercial item of the said range.
In addition, by forming a layer containing a polyimide precursor on a support film having a small average surface roughness, transferring the layer containing the polyimide precursor onto a glass film, and baking, a polyimide resin having a small average surface roughness. A resin layer made of the composition can be obtained.

As for the glass laminated body which concerns on this embodiment, ratio (total thickness of a resin layer / thickness of a glass film) of the total thickness of a resin layer and the thickness of a glass film is 0.01 or more and 0.4 or less. If it is 0.01 or more, the resin layer containing a polyimide resin can alleviate the impact applied to the glass laminate and improve the handleability of the laminate. If it is 0.4 or less, the visible light permeability of the laminate can be maintained high, and when the laminate is applied to a vacuum process, the amount of outgas composed of moisture and low molecular weight components can be suppressed. . Preferably it is 0.05 or more, More preferably, it is 0.1 or more, Preferably it is 0.3 or less, More preferably, it is 0.2 or less.

As described above, the glass laminate according to the present embodiment is excellent in transparency even though the polyimide resin is used because the thickness of the resin layer is small compared to the thickness of the glass film. It is a glass laminate.
Specifically, the spectral transmittance of visible light having a wavelength of 500 nm is usually 70% or more, preferably 75% or more, more preferably 78% or more, and further preferably 80% or more. preferable.

<Resin layer>
In this embodiment, a resin layer consists of a polyimide resin composition containing a polyimide resin. When the resin layer contains a polyimide resin, a glass laminate having high heat resistance is obtained. The thickness of the resin layer is usually 1 μm or more and 25 μm or less, preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 10 μm or less.
If thickness is the said range, the visible light transmittance of a glass laminated body can be maintained highly.

  In the present embodiment, the polyimide resin composition forming the resin layer has a tensile breaking elongation at 25 ° C. of 10% or more and 500% or less. Preferably they are 15% or more and 400% or less, More preferably, they are 20% or more and 300% or less, More preferably, they are 20% or more and 100% or less.

  When the tensile breaking elongation of the polyimide resin composition satisfies the above range, propagation of cracks from the cut portion can be suppressed when the glass laminate is cut. In addition, even when the glass film is broken inside the laminated body, the resin layer is not broken and the shape of the glass laminated body is maintained, so that the glass can be prevented from scattering. Moreover, since the shape of a glass laminated body is maintained, the contamination of the apparatus in the manufacturing process of an electronic device can be prevented, and a yield can be improved.

The tensile elongation at break of the polyimide resin composition is adjusted by a method of appropriately adjusting the polyamic acid used as a raw material for the polyimide resin, a method of appropriately adjusting the curing temperature and the curing time when the layer containing the polyimide precursor is cured, and the like. can do.
The polyamic acid is cured by heat or the like to obtain a polyimide resin, and is exemplified as a specific example of a polyimide precursor.
In this embodiment, in order to make the tensile elongation at break within the above range, for example, the curing temperature may be increased stepwise from a low temperature at which no polymerization reaction occurs. There are also commercially available products that satisfy the above range, and they can be obtained as appropriate.

The tensile elongation at break of the polyimide resin composition can be measured by the following method.
A strip-shaped resin sample having a thickness of 10 μm, a width of 10 mm, and a length of 60 mm was prepared, and the tensile breaking elongation of the strip-shaped resin sample was measured using a tensile tester (manufactured by Shimadzu Corporation, universal material testing machine AGS-X). . The test conditions are a distance between chucks of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

In this embodiment, the heat resistant temperature of the polyimide resin composition is preferably 400 ° C. or higher. If the heat-resistant temperature of the polyimide resin composition is 400 ° C. or higher, the amount of outgas generated from the resin layer can be suppressed in the step of forming a circuit in the glass laminate, and the performance degradation of the circuit due to outgas can be prevented. .
The heat resistant temperature of the polyimide resin composition is more preferably 500 ° C. or higher, and further preferably 550 ° C. or higher. Although an upper limit is not limited, Usually, it is 700 degrees C or less.

The heat resistant temperature of the polyimide resin composition is measured as follows.
Using RIGAKU Thermo plus TG8120, nitrogen 50 mL / mi
Under n atmosphere, the heat loss at a heating rate of 20 ° C./min is measured, and the temperature at which the heat loss is 5% is defined as the heat resistant temperature.

The heat-resistant temperature of the polyimide resin composition can be within the above range by increasing the proportion of the polyimide resin in the entire polyimide resin composition, for example, 80 wt% or more, preferably 90 wt%. Further, the heat-resistant temperature can be adjusted by a method of appropriately adjusting the polyamic acid used as a raw material for the polyimide resin, a method of increasing the imidization rate by performing sufficient firing, and the like.
In this embodiment, in order to increase the heat-resistant temperature of the polyimide resin composition, for example, p-phenylenediamine, m-phenyldiamine, 3,4'-diaminodiphenyl ether, and 4,4 'as diamine constituting the polyamic acid. -It may be selected from diaminodiphenyl ether. Further, as the tetracarboxylic dianhydride constituting the polyamic acid, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3', 4,4 ' -Diphenylsulfone tetracarboxylic dianhydride may be selected. There are also commercially available products that satisfy the above range, and they can be obtained as appropriate.

  The material constituting the polyimide resin composition is not limited as long as it includes a polyimide resin, and may include other resins and additives. However, the proportion of the polyimide resin in the entire polyimide resin composition is usually 70 wt% or more, preferably 80 wt% or more, more preferably 90 wt% or more, still more preferably 95 wt% or more, and particularly preferably 98 wt% or more. It is also preferable that it is 100 wt%.

The polyimide resin can be obtained by imidizing the following polyamic acid. The imidization reaction of polyamic acid is usually performed by heating.
A polyamic acid can be obtained by reaction of diamine and tetracarboxylic dianhydride.

Examples of the diamine include p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 3,3'-dimethyl-4,4. '-Diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis (anilino) ethane, diaminodiphenylsulfone, diaminobenzanilide, diaminobenzoate, diaminodiphenyl sulfide, 2, 2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 1,5-diaminonaphthalene, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p-amino) Phenoxy) benzene, , 4'-bis (p-aminophenoxy) biphenyl, diaminoanthraquinone, 4,4'-bis (3-aminophenoxyphenyl) diphenyl sulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis ( Anilino) octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane and the like can be used alone or as a mixture.
Among these, it is preferable to use p-phenylenediamine, m-phenyldiamine, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether from the viewpoint of obtaining a highly heat-resistant polyimide resin.

Examples of the tetracarboxylic dianhydride include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4'-diphenylsulfone tetracarboxylic acid, acid, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, 2,3,3', 4'-benzophenone tetracarboxylic acid, 2,3,6,7- Naphthalenetetracarboxylic acid, 1,4,5,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-diphenylmethanetetracarboxylic acid, 2,2- Bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,4,9,10-tetracarboxy Dianhydrides such as rylene, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, and 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane A thing etc. can be used individually or as a mixture. Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- from the viewpoint of obtaining a highly heat-resistant polyimide resin. It is preferred to use diphenylsulfone tetracarboxylic dianhydride.

<Glass film>
The glass film which comprises the glass laminated body which concerns on this embodiment will not be specifically limited if the flexibility of a laminated body is not inhibited. Specifically, soda lime glass, borosilicate glass, non-alkali glass and the like can be exemplified.

  For the purpose of improving the adhesion between the glass film and the resin layer, the surface of the glass film is treated with a coupling agent treatment such as a silane coupling agent or a titanium coupling agent, acid treatment, alkali treatment, ozone treatment, ion treatment, etc. Various surfaces such as chemical treatment, plasma treatment, glow discharge treatment, arc discharge treatment, corona treatment and other discharge treatments, ultraviolet treatment, X-ray treatment, gamma ray treatment, laser treatment and other electromagnetic wave irradiation treatments, and other surface treatments such as flame treatment Processing may be performed.

  From the viewpoint of flexibility, the thickness of the glass film is usually 10 μm or more and 200 μm or less, preferably 15 μm or more and 150 μm or less, and more preferably 20 μm or more and 100 μm or less.

As the glass film, a commercially available product can be used. Specifically, for example, a trade name “Spool” manufactured by Asahi Glass Co., Ltd., a trade name “Will Glass” manufactured by Corning,
A trade name “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. can be mentioned. Furthermore, commercially available glass having a thickness of 200 μm or more may be polished, or melted with hydrogen fluoride to form a thin film.

<Method for producing glass laminate>
Although the manufacturing method of the glass laminated body which concerns on this embodiment will not be specifically limited if the glass laminated body which laminated | stacked the resin layer on the at least single side | surface of a glass film can be manufactured, as an example, it is a resin composition directly on a glass film by the direct coating method. And a method of using a transfer film.
In the direct coating method, specifically, a coating composition containing at least a resin and a solvent is prepared, and the composition is applied by die coating, bar coating, spin coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, This is a technique of applying to a glass film by a method such as offset printing, flexographic printing, screen printing, dip coating or the like.
As the solvent, an organic solvent is usually used, and is appropriately selected depending on the type of resin contained in the resin layer.
In addition, after application | coating, you may include the process of removing a solvent as needed.
In the case of the direct application method, the application speed, the discharge amount, etc. are not particularly limited, and can be appropriately adjusted from the composition and thickness of the resin contained in the resin layer.

When using a transfer film, it is preferable to include the following steps (1) to (3).
(1) forming a layer containing a polyimide precursor on a support film and producing a transfer film;
(2) a step of transferring the layer containing the polyimide precursor formed in the previous step to the glass film surface, and peeling the support film after transfer,
(3) firing the layer containing the polyimide precursor transferred in the previous step, and forming a resin layer on the glass film;

The support film used in the step (1) is not limited as long as it can support the layer containing the polyimide precursor. Specific examples include polyester resins, polyolefin resins, and polycarbonate resins. Among these resins, polyester resins are preferable from the viewpoints of heat resistance and coatability.
Further, the surface of the support film to be laminated with the layer containing the polyimide precursor preferably has a small average surface roughness Sa, preferably 20 nm or less, and preferably 10 nm or less. When the average surface roughness of the support film surface is small, the average surface roughness of the resin layer surface in the glass laminate can be reduced.

Although the thickness of a support film is not specifically limited, Usually, it is 20 micrometers or more and 150 micrometers or less, and it is preferable that they are 30 micrometers or more and 130 micrometers or less.
Moreover, it does not specifically limit about the manufacturing method of a transfer film, What is necessary is just to manufacture using a known method.

In the step (2), the layer containing the polyimide precursor and the glass film in the transfer film produced in the step (1) are laminated to face each other, and the layer containing the polyimide precursor is transferred to the glass film. After the transfer, the support film of the transfer film is peeled from the laminate.
The transfer film may have an adhesive layer on the layer containing the polyimide precursor in order to improve the adhesion with the glass film.

As a method for transferring the layer containing the polyimide precursor to the glass film, a known method can be used, for example, thermal lamination.
In the case of thermal lamination, a known apparatus may be used. For example, a coating apparatus for coating a layer containing a polyimide precursor on a support film and a composition after coating are dried on a part of the thermal lamination apparatus. A heat laminating apparatus incorporating a drying apparatus may be used, and production of a transfer film and transfer to a glass film may be performed continuously.
The surface of the layer containing the polyimide precursor of the transfer film may be subjected to a surface treatment such as plasma treatment, corona treatment, or silane coupling treatment in order to improve adhesion before thermal lamination.

  In thermal lamination, the glass film may be used in the state of a single wafer cut into a size that is easy to handle, or may be used after being unwound from a roll state.

Thermal lamination is usually performed by passing a laminated body in which a transfer film is laminated on at least one side of a glass film between nip rolls heated to a predetermined temperature. The heating temperature is preferably not less than the glass transition temperature of the polyimide precursor and not more than + 50 ° C. from the viewpoint of satisfactory transfer.
The nip roll pressure is usually 0.1 MPa · cm or more and 5 MPa · cm or less from the viewpoint of adhesion between the glass film and the layer containing the polyimide precursor, while preventing breakage of the glass film.

In the step (3), the polyimide precursor layer of the laminate obtained by transferring in the step (2) is baked to cause a curing reaction, thereby obtaining the glass laminate according to the present embodiment.

The baking temperature for curing the polyimide precursor is not particularly limited as long as the temperature is sufficient to cure the polyimide precursor. Specifically, the glass transition temperature of the cured polyimide resin is not lower than + 100 ° C. and preferably not lower than + 20 ° C. and not higher than + 80 ° C., for example, the glass transition temperature of the polyimide resin + 50 ° C. It may be. When the glass transition temperature (Tg) of the polyimide resin is not clear, it may be the use temperature of the laminate + 50 ° C.
The heating time is not particularly limited as long as it is sufficient to cure the polyimide precursor, and is usually 10 minutes to 2 hours, preferably 20 minutes to 1.5 hours, more preferably 30 minutes to 1 hour. It is as follows.
The heating atmosphere is not particularly limited, but it is preferably performed in an inert gas atmosphere such as nitrogen or argon.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the specific modes described in the following examples.
In addition, the measuring methods, such as a physical property measured in the Example, are as follows.

(Tensile rupture elongation of polyimide resin composition)
For the polyimide resin composition constituting the resin layer, a strip-shaped resin sample having a thickness of 10 μm, a width of 10 mm, and a length of 60 mm is prepared, and the strip is prepared using a tensile tester (manufactured by Shimadzu Corporation, universal material testing machine AGS-X). The tensile elongation at break of each resin sample was measured. The test conditions were a distance between chucks of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

(Crack propagation of glass laminate)
The glass laminate was cut 5 cm with scissors (“Hasa 151B” manufactured by KOKUYO S & T) from the end face, and the condition of cracks propagating from the cutting direction was evaluated according to the following criteria.
○: Propagation of crack from cutting direction is less than 5 mm Δ: Propagation of crack from cutting direction is from 5 mm to less than 10 mm ×: Propagation of crack from cutting direction is 10 mm or more

(Average surface roughness (arithmetic average roughness Sa))
Surface observation (observation field of view: 93.97 μm × 71.30 μm) of the glass laminate using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.) Average surface roughness (arithmetic average roughness Sa) was calculated.

(Spectral transmittance)
Using a spectrophotometer “UV-4000” manufactured by Hitachi High-Tech, the spectral transmittance of the glass laminate at a wavelength of 500 nm was measured.

(Heat-resistant temperature of polyimide resin composition)
Using RIGAKU Thermo plus TG8120, nitrogen 50 mL / mi
Under n atmosphere, the heat loss at a heating rate of 20 ° C./min was measured, and the temperature at which the heat loss was 5% was defined as the heat resistant temperature.

<Example 1>
Unitika's “U imide varnish AR”, which is a polyamic acid solution with a solid content of 18%, is applied to a smooth surface of a support film (polyethylene terephthalate biaxially stretched film (product name “A4100”, thickness 50 μm, manufactured by Toyobo Co., Ltd.) with a bar coater. The transfer film which has the polyimide precursor layer adjusted so that the thickness after baking was set to 3 micrometers by drying at 100 degreeC for 5 minutes was obtained.
A glass film (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 40 μm) is prepared, and a transfer film is laminated on both sides of the glass film so that the glass film and the polyimide precursor layer face each other. Using a laminator having a metal roll and a rubber roll having a diameter of 200 mm, thermal lamination was performed at a linear pressure of 0.4 MPa · cm and a heating temperature of 150 ° C.
After thermal lamination, the support film is peeled off from the laminate, and the polyimide precursor is allowed to advance by imidation reaction of the polyimide precursor by firing at 250 ° C. for 30 minutes and at 450 ° C. for 30 minutes in a nitrogen atmosphere. A glass laminate 1 having a resin layer was prepared.

<Example 2>
A transfer film was obtained in the same manner as in Example 1 except that “Uimide varnish CR” manufactured by Unitika, which is a polyamic acid solution having a solid concentration of 18%, was applied to the support film.
In the same manner as in Example 1, the support film was peeled off from the laminate after heat lamination, and the polyimide precursor was allowed to proceed to imidation by firing in a nitrogen atmosphere at 250 ° C. for 30 minutes and 350 ° C. for 30 minutes. A glass laminate 2 having a resin layer made of a polyimide resin composition was prepared.

<Example 3>
A glass laminate 3 was prepared in the same manner as in Example 2 except that a transfer film was laminated only on one side of a glass film (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 40 μm) and heat laminated.

<Comparative Example 1>
Thermosetting epoxy resin with solid content of 100% (made by ADEKA, trade name “KRX-950-1”)
After coating with a wire bar coater so that the thickness after curing is 3 μm on both sides of the glass film, the solvent is dried, removed, and further cured by heat treatment, from the epoxy resin composition A glass laminate 4 having a resin layer was obtained.

<Comparative example 2>
“Uimide varnish AR” manufactured by Unitika, which is a polyamic acid solution having a solid concentration of 18%, was applied to one side of a glass film (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm) with a spin coater at 100 ° C. Drying for 5 minutes, and further baking at 250 ° C. for 30 minutes and 450 ° C. for 30 minutes in a nitrogen atmosphere creates a glass laminate 5 having a resin layer thickness of 0.1 μm made of the polyimide resin composition. did.

<Comparative Example 3>
After producing a transfer film having a polyimide precursor layer adjusted to have a thickness after firing of 30 μm by drying at 100 ° C. for 15 minutes during the production of the transfer film, a glass film (Nippon Electric Glass Co., Ltd.) The glass laminate 6 was prepared in the same manner as in Example 1 except that the transfer film was thermally laminated so that the glass film and the polyimide precursor layer face each other on one side of “OA-10G” (product thickness: 50 μm). Tried to create.
However, after firing, the sample warped and the glass film was damaged.
Moreover, the surface of the resin layer made of the polyimide resin composition was foamed by the evaporation of the solvent or moisture contained during firing.

<Comparative example 4>
A glass film (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 40 μm) was used without laminating the resin layer.

According to the present invention, the progress and breakage of cracks can be remarkably prevented as compared with the prior art. That is, when a roll-shaped glass laminate is cut into a desired size, it is possible to provide a glass laminate that is less prone to crack propagation.
In addition, a glass laminate having high heat resistance and good visible light transmittance can be provided.
Therefore, a glass laminate suitable as an electronic device substrate is provided.

Claims (6)

A method for producing a glass laminate comprising at least the following steps (1) to (3):
Said glass laminate has a thickness of 10μm or more, on at least one surface of the following glass film 200 [mu] m, Ri glass laminate der obtained by laminating a resin layer made of a polyimide resin composition,
The polyimide resin composition has a tensile elongation at break of 10% or more and 500% or less, and a ratio of the total thickness of the resin layer to the thickness of the glass film (total thickness of the resin layer / thickness of the glass film) is 0.01. Above, the manufacturing method of the glass laminated body which is 0.4 or less.
(1) The process of forming the layer containing a polyimide precursor on a support film
(2) Step of transferring the layer containing the polyimide precursor formed in the previous step to the glass film surface and peeling the support film
(3) A step of firing the layer containing the polyimide precursor transferred in the previous step to form a resin layer made of the polyimide resin composition The manufacturing method of the glass laminated body of Claim 1 whose thickness of the resin layer which consists of the said polyimide resin composition is 1 micrometer or more and 25 micrometers or less. The manufacturing method of the glass laminated body of Claim 1 or 2 whose thickness of the said glass film is 20 micrometers or more and 100 micrometers or less. The heat resistance temperature of the said polyimide resin composition is 400 degreeC or more, The manufacturing method of the glass laminated body of any one of Claims 1-3. The manufacturing method of the glass laminated body of any one of Claims 1-4 which laminated | stacked the resin layer which consists of a polyimide resin composition on both surfaces of a glass film. The method for producing a glass laminate according to claim 5, wherein the average surface roughness Sa of at least one of the laminate surfaces is 10 nm or less.