JP2017019133A - Laminate, substrate for electronic device, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate by laminating a resin layer on a brittle material layer such as a glass layer, capable of being cut by a laser scribe method even though handling ability is added to the brittle material layer, suppressing crack generation or breakage on a cut surface of the brittle material layer even after cutting and having suppressed modification of the resin layer.SOLUTION: There is provided a laminate obtained by preparing a laminate having at least a brittle material layer 1 with thickness of 10 to 200 μm and a resin layer 2, applying a laser along a cutting schedule line 7 of the laminate from the brittle material layer 1 side of the laminate, forming a scribe on a surface of the brittle material layer 1 and cutting them, where the resin layer 2 satisfies the formulae (i) and (ii) and surface roughness (arithmetic average roughness (Ra)) of the cut surface of the brittle material layer 1 is 500 nm or less. (i) 1.0×10≤x≤1.0×10, (ii) 0.8<log(x)/y<6.0, where x:elastic modulus of the resin layer (Pa) and y:thickness of the resin layer (μm).SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminate including a brittle material layer such as glass, an electronic device substrate, and an electronic device. Specifically, the present invention relates to a laminate in which a resin layer having specific physical properties is laminated on a brittle material layer such as glass that can be cleaved by laser scribing, an electronic device substrate using the laminate, and an electronic device .

In recent years, electronic devices (electronic components) in organic EL display devices, solar cells, thin film secondary batteries, etc. have been made thinner and lighter, and glass layers used in these electronic devices have been made thinner. Yes. However, when the strength of the glass layer is reduced due to thinning, the handling property of the glass layer is deteriorated, cracks are generated by a slight impact, and further, the crack propagates in the surface direction and the shape cannot be maintained. there were.
In addition, with the reduction in strength due to thinning, it has been difficult to apply the conventional mechanical scribing and breaking glass methods that require mechanical strength.
Furthermore, if there are minute cracks in the cut surface of the thinned glass layer, there is a problem that the crack propagates in the surface direction with a slight impact and the entire glass is broken.

  Therefore, when manufacturing an electronic device using a very thin glass (hereinafter, thin glass) as a substrate, for example, Patent Document 1 discloses a method of laminating a synthetic resin layer on a glass sheet in order to improve handling properties. Is disclosed.

  On the other hand, as a method for cleaving thin glass, for example, in Patent Document 2, a glass surface is heated by irradiating with a laser, and immediately after that, a large tensile stress is generated on the surface of the glass substrate to generate a scribe line. A method for forming and cleaving (hereinafter referred to as laser scribing method) has been disclosed, and has attracted attention as a glass cleaving method that can be cleaved in a non-contact manner and that can suppress the occurrence of cracks in the cleaved surface.

  Furthermore, Patent Document 3 discloses a method for cleaving a laminated body in which thin glass sheets are laminated and integrated on both sides of a resin plate, in which the laser beam is focused on the laminated body and the laminated body is subjected to laser fusing. It is disclosed.

JP 2002-521234 Gazette JP 2006-347783 A JP 2012-254627 A

However, when the laminated sheet obtained by laminating the glass sheet and the synthetic resin layer described in Patent Document 1 is to be cleaved by the laser scribing method, scribing does not occur in the heating / cooling process because of the flexibility of the synthetic resin material layer. Therefore, it was found that the synthetic resin layer cannot be cleaved simultaneously with the glass sheet depending on the type and thickness of the laminated synthetic resin layer.
Further, when trying to cleave the laminated body in which the thin glass and the resin layer are laminated by the cleaving method of Patent Document 3, in the glass near the fractured surface, cracks are generated due to stress caused by melting and cooling, and the laminated body. There was a concern that the impact resistance of the material would decrease. In addition, since the resin layer itself is melted, the resin layer may be burnt and deteriorated by heat, or there may be a portion of the thin glass that is not covered with the resin layer, and the thin glass may be easily damaged. It was.

  The present invention has been made in order to solve the above-described conventional problems. The purpose of the present invention is to provide a resin layer on a brittle material layer such as a glass layer, to provide handling properties, and to propagate cracks. Even if it is a laminated body in which cracking is suppressed, it can be cleaved by a laser scribing method, and even after cleaving, a laminated body in which crack generation and breakage in the brittle material layer split section is suppressed, and alteration of the resin layer is suppressed. Is to provide.

As a result of earnestly examining the above problems, the present inventors have a resin layer satisfying specific physical properties on one side of a brittle material layer such as a glass layer having a thickness of 10 to 200 μm, and can be cleaved by laser scribing. It has been found that a laminate having excellent handling properties, crack propagation suppression and impact resistance can be obtained even after cleaving.
That is, the present invention is as follows.

(1) Prepare a laminate having at least a brittle material layer having a thickness of 10 μm or more and 200 μm or less and a resin layer, and follow the planned cutting line of the laminate from the brittle material layer side of the laminate A laminated body obtained by irradiating a laser to form a scribe on the surface of the brittle material layer and cleaving,
The laminate, wherein the resin layer satisfies the following formulas (i) and (ii), and the surface roughness (arithmetic average roughness (Ra)) of the fractured surface of the brittle material layer is 500 nm or less.
(I) 1.0 × 10 ⁶ ≦ x ≦ 1.0 × 10 ¹⁰
(Ii) 0.8 <log (x) / y <6.0
x: Elastic modulus (Pa) of resin layer
y: thickness of resin layer (μm)
(2) The laminate according to (1), wherein a 5% weight reduction temperature of the resin layer is 250 ° C. or higher.
(3) An electronic device substrate using the laminate according to (1) or (2).
(4) An electronic device comprising the laminate according to (1) or (2).

  According to the present invention, it is possible to provide a brittle material layer laminate that can be cleaved by laser scribing and has excellent handling properties and impact resistance even after cleaving. The obtained brittle material layer laminate can be suitably used as an electronic device substrate.

Sectional drawing of a glass laminated body is shown. The schematic diagram which shows one Embodiment of the manufacturing method of a laminated body is shown.

  Hereinafter, a brittle material layer laminate (hereinafter, also simply referred to as a laminate) according to the present invention and a method for producing the laminate will be described in detail with reference to the drawings, but the laminate according to the present invention and the production of the laminate are described below. The method is not limited to these specific embodiments.

  FIG. 1 is a cross-sectional view of a glass laminate according to a specific embodiment of the present invention, and FIG. 2 is a schematic diagram showing an embodiment of a method for producing a laminate according to the present invention. In FIG. 1, a glass layer 1 is used as a brittle material layer, and a resin layer 2 is laminated on one side of the glass layer 1.

FIG. 2 schematically shows a process of cleaving the glass laminate shown in FIG. 1 by laser scribing. On the support 3 having a length shorter than the vertical direction (also referred to as the width direction) of the planned cutting line 7 of the glass laminate, the laminate is arranged so that the resin layer side faces the support 3. The initial crack 4 is created by a mechanical method at the start point which is one end of the planned cutting line. Then, on the surface of the glass layer 1, the laser irradiation (heating) part 6 and the cooling part 5 are moved from the initial crack 4 along the planned cutting line 7 toward the other end of the planned cutting line 7. A scribe is formed on the surface of layer 1. At this time, a predetermined physical stress 8 is applied from the glass layer 1 side toward the resin layer 2 (in the thickness direction of the laminate) on the lateral end of the laminate, whereby the glass layer 1 is Cleavage immediately after laser irradiation.
In the present invention, in order to provide a laminate that can be cleaved by laser scribing in this way, it is important to have a resin layer having specific properties.

  Next, although the material structure which concerns on this invention is demonstrated in detail, this invention is not limited to these embodiment.

<Brittle material layer>
Any appropriate material can be adopted as the brittle material layer in the present invention as long as the thickness is a plate-like material having a thickness of 10 μm or more and 200 μm or less. In the present invention, the “brittle material” is a material that has low ductility and toughness, and is ruptured and broken with a slight strain. For example, it refers to a material having a smaller tensile strength than a compressive strength. Specific examples of the brittle material include glass, ceramic, silicon, sapphire, and the like, and a glass layer is preferable because it can be suitably used as a substrate for various electronic devices.
As the material of the glass layer, for example, almost any glass composition such as soda lime glass, borosilicate glass, non-alkali glass, etc. can be applied, and those subjected to secondary processing such as tempering and surface treatment are also possible. It is properly used by.
For brittle material layer, for example, coupling agent treatment with silane coupling agent, titanium coupling agent, etc., chemical treatment such as acid treatment, alkali treatment, ozone treatment, ion treatment, plasma treatment, glow discharge treatment, arc discharge treatment Various surface treatments such as discharge treatment such as corona treatment, ultraviolet ray treatment, X-ray treatment, gamma ray treatment, electromagnetic wave irradiation treatment such as laser treatment, and other flame treatment may be applied. In particular, from the viewpoint of improving the adhesion with the resin layer, it is preferable that one surface is surface-treated with a silane coupling agent.

A known method can be adopted as a method for manufacturing the brittle material layer. For example, glass having a thickness of 10 μm or more and 200 μm or less stretches the glass melt in principle at a temperature above the temperature at which the glass melt solidifies. It is possible to make it. The glass thickness can be controlled by the glass composition, the glass melt thickness, the temperature, and the take-off speed.
The thickness of the brittle material layer is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more. On the other hand, it is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.
If thickness is 10 micrometers or more, mechanical strength can be ensured and the damage by the stress by the thermal expansion / contraction of the laminated resin layer can be suppressed. On the other hand, when the thickness is 200 μm or less, it is effective to laminate a resin layer for the purpose of improving handling properties and secondary workability.

The average surface roughness of the brittle material layer is preferably 5 nm or less, more preferably 2 nm or less, and particularly preferably 1 nm or less.
If the average surface roughness of the brittle material layer is 5 nm or less, when forming an electronic device on the brittle material layer surface, for example, a very thin (several tens of nm) conductive layer having a low surface resistance value can be formed. Therefore, the laminate can be suitably used as an electronic device substrate.
The average surface roughness is measured as follows.
The average surface roughness (arithmetic average roughness (Sa)) can be measured using an optical interference type non-contact surface shape measuring instrument. For example, using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.), the surface of the brittle material layer is observed (observation field: 93.97 μm × 71.
30 μm), and the average surface roughness (arithmetic average roughness Sa) is calculated for the surface of the brittle material layer.

<Resin layer>
The resin layer is composed of a resin composition, and the resin composition constituting the resin layer includes a resin and other additives as necessary.
The resin contained in the resin composition may be a thermoplastic resin or a resin obtained by curing a curable resin composition as long as it is within the thickness and elastic modulus ranges defined below. Good.
As the resin composition constituting the resin layer, a curable resin composition that cures at least by heat or active energy ray irradiation is preferable because the laminating process is easy and the film thickness can be adjusted. A curable resin composition that is cured by irradiation is more preferable.

  Specific examples of the thermoplastic resin contained in the resin layer include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide resins, polyether sulfone resins, polyether imide resins, and polyether ether ketones. Examples thereof include cyclic olefin resins such as resin, polyimide resin, acrylic resin, polycarbonate resin, cyclic olefin homopolymer, and cyclic olefin copolymer. Among the above thermoplastic resins, a resin having a melting point of 230 ° C. or higher is preferable from the viewpoint of heat resistance. For example, polyethylene terephthalate (melting point: about 260 ° C.), polyethylene naphthalate (melting point: about 270 ° C.), polyetherimide resin ( Resin such as polyphenylene sulfide resin (melting point approximately 280 ° C.), polyether sulfone resin, polyether ether ketone resin (melting point approximately 334 ° C.), polyimide resin (melting point approximately 350 ° C.), etc. It is preferable to include a polyimide resin or a polyether ether ketone resin. Moreover, these resin can be used 1 type or in combination of 2 or more types.

  Specific examples of the curable resin composition that is cured by heat include a curable resin composition containing, as a curing component, an acrylic resin, a urethane resin, an epoxy resin, a silicone resin, a polyimide precursor, and the like. A thermosetting resin composition containing a silicone-based resin and a polyimide precursor is preferable, and a thermosetting resin composition containing a polyimide precursor is more preferable from the viewpoint of little dimensional change during heating.

As a curable resin composition that is cured by irradiation with active energy rays, a curable resin composition containing an ultraviolet curable monomer and an oligomer as a curing component is preferable because it can be cured in a short time and relatively easily. Can be mentioned.
As the ultraviolet curable monomer and oligomer, a (meth) acrylic monomer and a (meth) acrylic oligomer are preferable from the viewpoints of mechanical properties, transparency and processability.
For example, monomers and oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are preferable examples.
Furthermore, some of these are exemplified by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipenta Examples thereof include monofunctional and polyfunctional acrylic monomers and methacrylic monomers having one or more carbon-carbon double bonds, such as erythritol hexamethacrylate, isoamyl acrylate, ethoxydiethylene glycol acrylate, and methoxydiethylene glycol acrylate.

As the (meth) acrylic monomer and the (meth) acrylic oligomer, a functional group equivalent, that is, a (meth) acrylic monomer and a (meth) acrylic oligomer having a molecular weight / functional group number in the range of 500 or more and 5000 or less are more preferable.
By using (meth) acrylic monomers and (meth) acrylic oligomers within the functional group equivalent range, the elastic modulus of the resin layer can be adjusted to an appropriate range and adhesion to the glass layer can be expressed. It becomes.
Further, it is more preferable to use urethane acrylate having a functional group equivalent in the range of 500 or more and 5000 or less. By using an acrylate having a urethane bond and having a functional group equivalent within this range, the toughness and impact resistance of the resin layer are improved, so that it is possible to particularly suppress the breakage and breakage of the glass layer.
In addition, these can be used 1 type or in combination of 2 or more types.

  When the ultraviolet curable monomer and oligomer are included in the curable resin composition that is cured by irradiation with active energy rays, a photopolymerization initiator is also included as necessary. The photopolymerization initiator is used for absorbing (activating) and activating (exciting) ultraviolet rays and initiating the reaction via a cleavage reaction or the like.

  Examples of the photopolymerization initiator include benzoin, acetophenone, thioxanthone, phosphine oxide, and peroxide. Specific examples include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-methyl-propan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methyl Thio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenyl Examples include phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, and the like. it can. These can be used alone or in combination of two or more.

  The concentration of the photopolymerization initiator in the curable resin composition that is cured by irradiation with active energy rays is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of reliably proceeding the curing reaction. More preferably, it is 1 mass% or more. On the other hand, from the viewpoint of preventing outgassing due to unreacted substances of the polymerization initiator, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The curable resin composition that is cured by irradiation with heat and active energy rays preferably contains a curable resin such as an acrylic resin, a urethane resin, an epoxy resin, or a silicone resin as a curing component from the viewpoint of optical properties and heat resistance. From the viewpoint of heat resistance, mechanical properties, workability, etc., it is more preferable to include an epoxy curable resin.
Examples of the epoxy curable resin include an epoxy resin having an alicyclic compound group, an epoxy resin having a glycidyl ether group, an epoxy resin having an aromatic group, and the like, specifically, bisphenol A type and bilphenol. An F-type epoxy curable resin is more preferable.
As a commercial item, the brand name "KRX-690-5" by ADEKA Co., Ltd. which is an ultraviolet-ray and a thermosetting epoxy resin is mentioned, for example.

The curable resin composition can be used by adding a solvent as necessary. That is, it can be used as a solution containing the curable resin composition.
Although it will not specifically limit if it is a solvent which dilutes the component contained in curable resin composition uniformly as said solvent, For example, methyl isobutyl ketone, butyl acetate, propylene glycol monomethyl ether etc. are mentioned. These can be used alone or in combination of two or more.

  The total concentration of the resin contained in the resin composition constituting the resin layer is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably, from the viewpoints of viscosity during processing and mechanical properties after processing. 80% by mass or more.

  The resin composition constituting the resin layer is a silane coupling agent, a sensitizer, a crosslinking agent, a UV absorber, a polymerization inhibitor, a surfactant, a filler, and a mold release agent as long as the object of the present invention is not impaired. Antioxidants, leveling agents, slip agents, dispersants and the like can be optionally added. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.

<Tensile elastic modulus of resin layer>
In the present invention, the resin layer satisfies the following formulas (i) and (ii).
(I) 1.0 × 10 ⁶ ≦ x ≦ 1.0 × 10 ¹⁰
(Ii) 0.8 <log (x) / y <6.0
x: Elastic modulus (Pa) of resin layer
y: thickness of resin layer (μm)
The elastic modulus (hereinafter also referred to as tensile elastic modulus) of the resin layer is preferably 1.0 × 10 ⁶ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more, and further preferably 1.0 ×. 10 ⁹ Pa or more, particularly preferably 2.0 × 10 ⁹ Pa or more. The upper limit of the tensile modulus is not particularly limited, but is preferably 1.0 × 10 ¹⁰ Pa or less, more preferably 5.0 × 10 ⁹ Pa or less, still more preferably 4.0 × 10 ⁹ Pa or less, particularly preferably 3 0.0 × 10 ⁹ Pa or less.
If the tensile elastic modulus of the resin layer is 1.0 × 10 ⁶ Pa or more, the resin layer does not deform excessively and tends to be easily cleaved when a laser scribing treatment is performed on the brittle material layer surface. . On the other hand, when the tensile modulus is 1.0 × 10 ¹⁰ Pa or less, the flexibility of the resin layer can be ensured, and therefore, the brittle material layer tends to be flexible by being laminated.

The tensile elastic modulus of the resin layer can be measured by the following method.
A strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm is prepared and stretched in the longitudinal direction of the strip-shaped resin sample using a universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation). The tensile elastic modulus is measured from the stress. The test conditions are a distance between chucks of 10 cm, a pulling speed of 10 mm / min, and measurement at 25 ° C.

  The tensile elastic modulus of the resin layer may be appropriately selected from thermoplastic resins or curable resins having the above properties, and the tensile elastic modulus is within the above range by using means such as stretching treatment, heat annealing treatment, and aging treatment. Can be adjusted.

<Thickness of resin layer>
The thickness of the resin layer is preferably adjusted so that the resin layer is in a range that satisfies the above formula (ii). At this time, if log (x) / y in the above formula (ii) is larger than 0.8, the resin is simultaneously formed with the brittle material layer by the tensile stress generated in the brittle material layer by the laser scribing treatment on the brittle material layer surface. The layer tends to be easily broken. On the other hand, if log (x) / y is less than 6.0, sufficient handling properties and impact resistance can be imparted to the brittle material layer, and crack propagation in the brittle material layer can be suppressed. it can.
More preferably, log (x) / y in formula (ii) is greater than 1.0 and less than 5.0, more preferably log (x) / y in formula (ii) is greater than 2.0, It is less than 5.0.

<Relationship between crack propagation of resin layer and laminate>
In order to suppress the crack propagation of the brittle material layer, the thickness of the resin layer and the tensile elastic modulus are important. If the thickness of the resin layer is too thin or the tensile elastic modulus is too high, the resin is used together with the brittle material layer. There is a tendency that cracks are easily propagated by cracking into layers.
As described above, if the resin layer has log (x) / y of formula (ii) less than 6.0, crack propagation in the brittle material layer tends to be suppressed.

<Heat resistance of resin layer>
The resin layer has heat resistance corresponding to the process and application such as the heating temperature during the formation process of the electronic device and the heat to which the electronic device such as organic EL lighting, organic EL display, and organic solar cell is practically exposed. Is desirable. Specifically, the 5% weight loss temperature is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 400 ° C. or higher.
The 5% weight reduction temperature of the resin layer can be determined by using a thermal analyzer (for example, Thermoplus TG8120 manufactured by RIGAKU) in a nitrogen atmosphere of 50 mL / min and a resin layer at a heating rate of 20 ° C./min. The temperature at which the heat loss is 5% is determined as the 5% weight loss temperature of the resin layer.
The heat resistance of the resin layer can be adjusted to the above range by adding transparent inorganic particles, organic particles with high heat resistance, fibrous substances such as glass and cellulose, crosslinking accelerators, etc. You may select suitably resin which has.

<Lamination structure of resin layer>
The resin layer may have a configuration in which a plurality of resin layers are stacked. In order to suppress outgas, a resin film in which an inorganic layer having low gas permeability is laminated may be laminated on the brittle material layer. As the material of these resin layers, the thermoplastic resin and the curable resin composition mentioned above can be combined, and as the material constituting the inorganic layer, silicon oxide, silicon nitride and silicon oxynitride Examples thereof include silicon compounds and carbon compositions. In addition, these laminated thickness shall be the above-mentioned thickness range as the whole laminated resin layer.

<Adhesiveness between brittle material layer and resin layer>
In the present invention, it is preferable that the laminate has a high peel strength between the brittle material layer and the resin layer because it can be easily cleaved when the surface of the brittle material layer is subjected to laser scribing treatment.
The peel strength between the brittle material layer and the resin layer is usually 50 N / 50 mm or more, preferably 100 N / 50 mm or more, and more preferably 200 N / 50 mm or more. By disposing an adhesive layer described later between the brittle material layer and the resin layer, the peel strength can be improved. In addition, the upper limit of peeling strength is not specifically limited.

<Other layers>
This laminated body may contain layers other than those described above as long as the effects of the present invention are not impaired.
Specifically, an adhesive layer can be provided between the brittle material layer and the resin layer. By providing the adhesive layer, the peel strength between the resin layer and the brittle material layer can be increased. The adhesive layer can be used without particular limitation as long as it has a bonding force.
When the laminate has an adhesive layer, the total thickness of the adhesive layer and the resin layer is set as the above-described resin layer thickness range, that is, the above y is expressed as “the thickness of the adhesive layer and the resin layer (μm)”. It is preferable to satisfy (ii).
Moreover, it can also have a support layer, such as an inorganic material, on the surface of the resin layer that does not face the brittle material layer. By further providing the support layer, the handling properties of the laminate can be further improved. As the support layer, a glass plate, a resin plate, a metal plate such as a SUS plate, or the like is used, and the thickness thereof is not particularly limited, and is usually 0.1 mm or more and 5 mm or less.

When this laminated body has a support layer, it is preferable that a support layer is provided with easy peelability with respect to a resin layer. The resin layer is bonded to the brittle material layer with a certain bonding force, and at the same time, when peeling from the brittle material layer after the device formation, without destroying the brittle material layer on which the electronic device is formed, It is preferable that they are bonded with a bonding force that can be easily peeled.
Note that if easy peelability is expressed by specific numerical values, it can also be expressed that the peel strength between the resin layer and the brittle material layer is 0.1 N / 50 mm or more and 5 N / 50 mm or less. However, this numerical range is an example, and it is not limited to the above numerical range as long as it satisfies the easily peelable property described above.

<Lamination method of laminate>
The manufacturing method of this laminated body will not be specifically limited if the resin layer is laminated | stacked on the single side | surface of a brittle material layer. In addition, the brittle material layer side of the laminate may be laminated with a light emitting element, a power generating element, an accompanying electrode, or an inorganic material in the manufacturing process, and this may interfere with laser scribing, particularly on the planned cutting line. If not, these electronic device members may be laminated.

Examples of the method for laminating the resin layer on the brittle material layer include a direct coating method, a transfer method using a transfer film, a laminating method by heating, and bonding of the resin layer through an adhesive layer.
In the direct coating method, specifically, a coating composition containing at least a resin for forming a resin layer, an additive, and a solvent is prepared, and the composition is applied to a die coater, a bar coater, a spin coater, a Mayer bar, an air knife. This is a technique of applying to a brittle material layer by a method such as coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, dip coating, spray 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, and the process of hardening a resin layer.
In the case of the direct coating method, the coating speed, the discharge amount, etc. are not particularly limited, and can be appropriately adjusted depending on the composition of the resin contained in the resin layer and the thickness of the laminated resin layer.

  The transfer method using a transfer film is a method in which a transfer film in which a resin layer is laminated on a support film is transferred with the resin layer side surface facing a brittle material layer, and then the support film is peeled off.

  The laminating method by heating is a method in which a resin molded into a film is heated with a heating roll or the like and brought into contact with the brittle material layer at a predetermined pressure to be laminated with the brittle material layer.

  The bonding of the resin layer through the adhesive layer is a method in which the resin layer formed into a film and the brittle material layer are bonded through the adhesive layer. If the adhesive layer contains a curable resin composition, the bonding is performed. After the alignment, a curing process is performed as necessary.

<Manufacturing method of laminate (cleaving method)>
In this invention, the laminated body which concerns on this invention can be manufactured by cleaving the said laminated body.
The cleaving method is particularly limited as long as it is a cleaving method (hereinafter also simply referred to as laser scribe) in which a laser beam is irradiated from the brittle material layer side of the laminate along the planned cutting line to form a scribe on the brittle material layer surface. Not. Hereinafter, the cutting method by laser scribing is described.

  One of the known methods for cleaving brittle materials typified by glass is a cleaving method using thermal stress. The principle is as follows. If a brittle material such as glass is heated to such an extent that it does not melt locally, the heated part will try to thermally expand, but due to the reaction from the surrounding glass, it cannot expand sufficiently, and the compressive stress is centered on the heated part. Will occur. Even in the peripheral non-heated region, the peripheral portion is further distorted by the expansion from the heating portion, and as a result, compressive stress is generated. Further cooling thereafter causes shrinkage of the cooling section, which causes a large tensile stress on the material. By continuously performing this heating and cooling in a linear shape, a scribe is formed in the material, and by applying a bending pressure to the portion, it becomes possible to break the glass along the scribe.

Regarding the cleaving due to the thermal stress, a method using continuous laser irradiation as a method for applying the thermal stress is referred to as laser scribe in the text. Specifically, laser scribing in a brittle material, such as glass, typically has the following steps: (a) Generates initial cracks on the glass end face for initiating scribing.
(B) The glass surface is heated by irradiating a laser along the planned cutting line from the glass end face.
(C) Cooling with a cooling fluid immediately after heating.
(D) Take out the glass and break.
In addition, the planned cutting line refers to a boundary line when separating the laminated body, and may have some mark or no mark.

In the present embodiment, since the thickness of the brittle material layer is 200 μm or less, the step (d) is performed by performing the steps (b) and (c) while applying the bending pressure along the planned cutting line. The glass can be cleaved without passing (refer to Patent Document 2).
That is, by simultaneously performing the step of forming a scribe on the surface of the brittle material layer and the step of cleaving the laminated body on which the scribe is formed, the time required for the cleaving can be eliminated. Production efficiency is improved.

  The advantage of the method of cleaving the brittle material layer by laser scribing is that, unlike the crushing process by the pulse laser, the micro-crack of the fractured surface does not occur and melting due to excessive generation of heat does not occur, so the brittle material layer cross section is very It is mentioned that it is smooth. In particular, when using a thin glass layer, microcracks existing in the cross section and stress generated by melting cause cracks in the laminate, so the brittle material layer must not be melted and the fractured section should be smooth Has an important role for the handling properties of the laminate obtained by cleaving. On the other hand, laser scribing has less energy to crush the brittle material layer than cleaving with a pulsed laser, and does not melt the laminated resin layer. Since it is possible to prevent the brittle material layer surface near the cross-section from being exposed, there is an advantage that the impact resistance of the brittle material layer is not lost.

Note that the type and output of the laser is not particularly limited as long as the laser used for laser scribing can apply heating to the brittle material layer so as not to melt locally. The amount of heating that does not melt locally in the brittle material layer can be determined according to the wavelength absorbed by the brittle material layer. Specifically, for example, a laser having a wavelength of 1 μm or more is applied to the glass layer, a laser having a wavelength of 2 μm or more is applied to the ceramic substrate, a laser having a wavelength of 3 μm or more is applied to the silicon substrate, and a laser having a wavelength of 2 μm or more is applied to the sapphire substrate. Can be used. In any of the above, a CO ₂ gas laser (wavelength: 10.6 μm) can be applied.

<Surface roughness of the brittle material split section>
The presence or absence of cracks that can cause breakage in the brittle material layer section can be evaluated by measuring the surface roughness (arithmetic average roughness (Ra)) of the brittle material layer section.
The surface roughness (arithmetic mean roughness (Ra)) of the fractured surface in the brittle material layer portion after cleaving is measured using a fine shape measuring device, for example, a fully automatic fine shape measuring machine ("Surfcorder ET 4000A" manufactured by Kosaka Laboratory) It can be measured according to JIS B0601: 2013.
The smaller the surface roughness (arithmetic mean roughness (Ra)) of the brittle material layer split section after cleaving is, the better, but in the present invention it is 500 nm or less, preferably 200 nm or less, and more preferably 100 nm or less. If it is 500 nm or less, the impact resistance and bending characteristics of the laminate are not impaired. Further, the lower limit of the surface roughness is not particularly limited, but is usually 0.1 nm.

  The surface roughness of the brittle material layer split section of the laminate after cleaving can be reduced by means such as dissolution of uneven portions by a solvent, smoothing by polishing, and resin coating.

The laminate thus produced can be suitably used as a substrate for an electronic device, and particularly suitably used as a substrate for producing an organic electronic device such as an organic electroluminescence element and an organic photoelectric conversion element. it can.
These electronic devices can be formed on the laminate by a known method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to description to a following example. Moreover, in various tests, the case where the glass layer is used as a brittle material layer is demonstrated.

<Clearance>
Regarding the cleaving of the laminated body, it is desirable that the laminated body is naturally cleaved after the laser scribing process or can be easily cleaved with a slight force. Therefore, the following criteria were evaluated as criteria for determining whether or not the examples and comparative examples were cleaved.
◯: After the laser scribing process, a laminate was obtained by naturally cleaving without applying a specific stress from the outside, or the laminate was externally horizontal to the laminate and perpendicular to the cutting line. It was possible to cleave with a stress of 5 N / cm or less per unit length in the cutting line direction of the laminate by applying a force in the direction.
X: After the laser scribing treatment, the glass laminate is not cleaved, and in order to cleave, the laminate is externally applied with a force in the direction horizontal to the laminate and perpendicular to the cutting line. More than 5 N / cm of stress was required per unit length in the cutting line direction.

<Surface roughness of the glass layer split section>
The surface roughness (arithmetic mean roughness (Ra)) of the fractured glass layer after cleaving is measured using a fully automatic fine shape measuring machine (“Surfcorder ET 4000A” manufactured by Kosaka Laboratory) in accordance with JIS B060.
Based on 1: 2013, the measurement weight was 100 μN and the measurement speed was 0.02 mm / sec.

<Exposure evaluation of resin layer split section>
Regarding the resin part of the laminate split section, even if some roughness occurs, it does not lead to damage of the laminate, but the resin melts, deteriorates or shrinks with the energy applied when the brittle material layer is cleaved, If the glass surface is exposed at the interface between the glass layer and the resin layer, the effect of improving the impact resistance by the resin layer coating is lost at that portion. Therefore, the following criteria were evaluated as judgment criteria.
○: In the brittle material layer, there is no portion exposed by 0.2 mm or more from the cutting line. Δ: In the brittle material layer, a portion exposed by 0.2 mm or more and less than 1.0 mm from the cutting line exists.
X: In the brittle material layer, there is a portion exposed 1.0 mm or more from the cutting line.
In addition, a judgment is made by using an optical microscope (trade name “Digital Microscope VHX-500” manufactured by Keyence Corporation) after cutting the laminate, and randomly cutting lines with respect to the plane direction of the brittle material layer at a magnification of 20 times. The upper five points were observed.

<Evaluation of crack propagation of laminates>
In order to confirm the effect of suppressing the crack propagation by the resin layer when a crack occurs in a part of the brittle material layer, the laminate before cleaving is cut from the end face by 5 cm with scissors ("Hasa 151B" manufactured by KOKUYO S & T). The distance by which the crack propagated 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

<Measurement of tensile modulus of resin layer>
A strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm is prepared, and using a tensile tester (manufactured by Shimadzu Corp., AGS-X), the tensile elastic modulus is calculated from the elongation and stress in the longitudinal direction of the strip-shaped resin sample. It was measured.
The test conditions were a distance between chucks of 10 cm, a tensile speed of 10 mm / min, and measurement at 25 ° C.

<Measurement of resin layer thickness>
The thickness of the resin layer is calculated by measuring the thickness of the brittle material layer in advance using a micrometer (Quick Micrometer MDQ-30 manufactured by Mitutoyo Corporation) and then taking the difference. did.

<Measurement of heat resistance of resin layer>
About the resin composition which comprises the resin layer obtained by the Example and the comparative example, 5% weight reduction | decrease temperature was measured as follows.
Using RIGAKU Thermo plus TG8120, nitrogen 50 mL / mi
In the n atmosphere, the heat loss was measured for the resin composition constituting the resin layer at a heating rate of 20 ° C./min. did.

[Example 1]
An ultraviolet curable resin composition (ultraviolet curable urethane acrylate monomer (Shin Nakamura Chemical Co., Ltd.) was formed as a resin layer on the entire surface of the glass layer (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm, size 10 cm square). Product name “UA-122P”) 97% by mass and 1-hydroxy-cyclohexyl-ketone (3% by mass, product name “IRGACURE184” manufactured by BASF) as a photopolymerization initiator) after curing A glass laminate was obtained by applying the film so as to have a thickness of 5 μm and further irradiating and curing it with a high pressure mercury lamp (160 W / cm).
The 5% weight reduction temperature of the resin layer was 287 ° C.
Crack propagation property evaluation was implemented about the obtained glass laminated body.
As a cleaving test, the obtained glass laminate was installed as shown in FIG. 2, and a laser scribe engine (LEMI-SE1002 manufactured by Remi Co., Ltd.) was used to make an initial crack on the glass layer surface, and then a speed of 400 mm / sec. Then, cleaving by laser scribing was performed under conditions of an output of 33W. About the broken glass laminated body, evaluation of the cut surface was implemented. The results are shown in Table 1.

[Example 2, Comparative Examples 1-3]
The same materials and methods as in Example 1 were used, and the glass laminate was prepared by changing the thickness after curing of the ultraviolet ray and curable resin composition as shown in Table 1, respectively. The cleaving test, the evaluation of the cut section and the crack propagation evaluation were carried out. The results are shown in Table 1.

[Examples 3-4, Comparative Examples 4-5]
Thermosetting which used the glass layer similar to Example 1, and mixed the thermosetting silicone resin (The product name "LSR-7060A" by Momentive company name and "LSR-7060B" in an equal amount as a resin layer on the whole surface on it. The resin composition was applied so that the thickness after curing was as shown in Table 1, and further cured by heating in an oven at 150 ° C. for 1 hour to obtain a glass laminate.
The 5% weight reduction temperature of the resin layer was 375 ° C.
About the obtained glass laminated body, crack propagation property evaluation, the cleaving test similar to Example 1, and evaluation of the fractured surface were implemented. The results are shown in Table 1.

[Examples 5-6, Comparative Examples 6-7]
Using a glass layer similar to that in Example 1, a polyamic acid solution having a solid content concentration of 18% (“U imide varnish AR” manufactured by Unitika Ltd.) containing a polyimide precursor on the entire surface thereof, the thickness after firing is It apply | coated so that it might become the predetermined | prescribed thickness of Table 1.
After coating, drying at 100 ° C. for 5 minutes, baking at 250 ° C. for 30 minutes, and 450 ° C. for 30 minutes in a nitrogen atmosphere to advance the imidization reaction of the polyimide precursor, and the resin layer containing the polyimide resin The glass laminated body which has was obtained.
The 5% weight reduction temperature of the resin layer was 600 ° C. or higher.
About the obtained glass laminated body, crack propagation property evaluation, the cleaving test similar to Example 1, and evaluation of the fractured surface were implemented. The results are shown in Table 1.

[Comparative Example 8]
After creating a glass laminate with the same materials and methods as in Comparative Example 3, evaluation of crack propagation was performed.
The obtained glass laminate was cleaved in the same manner as in Example 1 except that the laser scribing conditions were changed to a speed of 400 mm / sec and an output of 85 W. About the broken glass laminated body, evaluation of the cut surface was implemented. The results are shown in Table 1. At this time, the resin fractured surface was burnt black, and the glass fractured surface was partially melted and deformed.

[Comparative Example 9]
After forming a glass laminate with the same materials and methods as in Example 1, evaluation of crack propagation was performed.
Moreover, about the obtained glass laminated body, using a laser processing machine (Comnet Co., Ltd. "LaserPro VenusII V-12"), speed 5inch / sec, output 90% / 12W, irradiation frequency 1500 times / sec from the glass layer side. The cleaving process by pulse laser irradiation was performed. About the cut glass laminated body, fractured-section evaluation was performed. The results are shown in Table 1. At this time, the cracked surface of the resin was burnt black, and when the broken glass surface was observed, a part was melted and deformed.

[Comparative Example 10]
Using the same glass layer as in Example 1, a polyimide tape (Arakawa Chemical Industries, Ltd., model number 1030-02, thickness 55 μm, width 20 mm) was double-bonded on one side of the glass layer so that there were no bubbles, A glass laminate was obtained.
About the obtained glass laminated body, crack propagation property evaluation was performed.
Moreover, about the obtained glass laminated body, a laser processing machine (LaserPro Gia)
(60W)), the number of irradiations was 1500 times / inch output, and the cleaving treatment was performed by irradiating a pulse laser from the glass layer side along the center of the tape under the condition of 38%. About the broken glass laminated body, evaluation of the cut surface was performed. The results are shown in Table 1. At this time, the cracked surface of the resin was burnt black, and when the broken glass surface was observed, a part was melted and deformed.

[Comparative Example 11]
The glass laminate obtained in Comparative Example 10 was cleaved in the same manner as in Comparative Example 10 except that the laser output was changed to 10%.
As a result of lowering the output, the glass layer was cleaved, but the resin layer was not cleaved, and the whole glass laminate could not be cleaved. Moreover, surface roughness evaluation was implemented about the glass layer split cross section. The results are shown in Table 1.

<Discussion>
It can be seen that in the laminates described in the examples, the crack propagation of the brittle material layer can be suppressed by the resin layer, the fractured surface of the brittle material layer is smooth, and no large cracks are generated. In addition, the brittle material layer is not largely exposed in the split section of the laminate, suggesting that a laminate excellent in impact resistance is obtained.
In Comparative Examples 1, 5 and 6, although the resin layer and the brittle material layer could be cleaved at the same time, the thickness of the resin layer was small and the formula (ii) was not satisfied, and crack propagation in the brittle material layer was sufficiently suppressed. Not done.
On the other hand, in Comparative Examples 2 to 4 and Comparative Example 7, although the resin layer can suppress crack propagation of the brittle material layer, the thickness of the resin layer is large and does not satisfy the formula (ii), and laser scribing treatment After that, it was found that the glass laminate was not cleaved and required a large stress for cleaving. If stress is applied to force cleaving after the laser scribing process, the brittle material layer may be damaged.
Comparative Example 8 increases the output of the laser to irradiate in order to cleave a laminate having a large resin layer thickness. As a result, a large amount of heat is applied to the resin layer, the surface state deteriorates, and the resin melts and shrinks. As a result, the fractured surface of the brittle material layer was exposed.
In Comparative Examples 9 to 11, the type of laser is changed. In particular, Comparative Examples 10 to 11 are methods that follow the examples of Japanese Patent Application Laid-Open No. 2014-28755, but as in Comparative Example 8, a brittle material layer is used. The surface roughness of the fractured surface of the material was increased, and the fractured surface of the brittle material layer was exposed.
Thus, the laminate having the resin layer satisfying the formula (i) and the formula (ii) and the brittle material layer can suppress crack propagation in the brittle material layer and can be cleaved by laser scribing. Is a laminate that is very smooth, does not generate large cracks, and has excellent impact resistance.

DESCRIPTION OF SYMBOLS 1 Glass layer 2 Resin layer 3 Support body 4 Initial crack 5 Cooling part 6 Laser irradiation (heating) part 7 Plane line 8 Stress

Claims (4)

At least a laminated body having a brittle material layer having a thickness of 10 μm or more and 200 μm or less and a resin layer is prepared, and a laser is irradiated along the planned cutting line of the laminated body from the brittle material layer side of the laminated body. Irradiated to form a scribe on the brittle material layer surface, and a laminate obtained by cleaving,
The laminate, wherein the resin layer satisfies the following formulas (i) and (ii), and the surface roughness (arithmetic average roughness (Ra)) of the fractured surface of the brittle material layer is 500 nm or less.
(I) 1.0 × 10 ⁶ ≦ x ≦ 1.0 × 10 ¹⁰
(Ii) 0.8 <log (x) / y <6.0
x: Elastic modulus (Pa) of resin layer
y: thickness of resin layer (μm)   The laminate according to claim 1, wherein a 5% weight reduction temperature of the resin layer is 250 ° C. or more.   The board | substrate for electronic devices which uses the laminated body of Claim 1 or 2.   An electronic device comprising the laminate according to claim 1.

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