Laminated body, supporting base material with silicone resin layer, resin substrate with silicone resin layer, and method for producing electronic device

Abstract

The present invention relates to a laminate, a support substrate with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for producing an electronic device. The present invention provides a laminate having excellent foaming resistance, comprising, in this order, a support substrate, a silicone resin layer, and a substrate, wherein the silicone resin layer contains at least one metal element selected from the group consisting of zirconium, aluminum, and tin.

Description

[0001] This application is a divisional application of the invention patent application with application number 201711435286.6, application date December 26, 2017, and invention name "Laminate, supporting substrate with silicone resin layer, resin substrate with silicone resin layer, and method for manufacturing electronic device". Technical Field

[0002] The present invention relates to a laminate, a supporting base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for producing an electronic device. Background Art

[0003] In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), organic electroluminescent panels (OLED), and sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible light, and infrared rays have become increasingly thinner and lighter. Consequently, the substrates used in these devices, typically glass substrates, have become increasingly thinner. If this thinning reduces the strength of the substrate, this can reduce the substrate's handling during the device manufacturing process.

[0004] Recently, to address the above-mentioned problem, a method has been proposed: preparing a glass laminate comprising a glass substrate and a reinforcing plate, forming a component for an electronic device such as a display device on the glass substrate of the glass laminate, and then separating the reinforcing plate from the glass substrate (for example, Patent Document 1). The reinforcing plate comprises a support plate and a silicone resin layer fixed to the support plate, the silicone resin layer being releasably adhered to the glass substrate.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2007 / 018028 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] As a material used for thin film transistors and the like, for example, low temperature polysilicon (LTPS) formed at 600° C. or lower is known.

[0010] When LTPS is used as (a part of) an electronic device member, the glass laminate is subjected to a heat treatment at a high temperature of 500 to 600° C. in an inert gas atmosphere, for example.

[0011] Furthermore, in semiconductor manufacturing processes, high-temperature CVD film formation is performed for annealing (sintering) of metal wiring and forming a highly reliable insulating film, requiring high-temperature resistance of 400° C. or higher.

[0012] The present inventors prepared the glass laminate described in Patent Document 1 and subjected it to a heat treatment under the above-mentioned conditions. As a result, they found that bubbles were sometimes generated in the silicone resin layer in the glass laminate.

[0013] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a laminate having excellent foaming resistance.

[0014] Another object of the present invention is to provide a supporting base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for producing an electronic device that can be applied to the above-mentioned laminate.

[0015] Solutions for solving problems

[0016] The inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by the following configuration.

[0017] [1] A laminate comprising, in this order, a supporting base material, a silicone resin layer, and a substrate, wherein the silicone resin layer contains at least one metal element selected from the group consisting of zirconium, aluminum, and tin.

[0018] [2] The laminate according to [1] above, wherein the silicone resin layer contains at least one metal element selected from the group consisting of zirconium and tin.

[0019] [3] The laminate according to [1] or [2] above, wherein the silicone resin layer contains a zirconium element.

[0020] [4] The laminate according to any one of [1] to [3] above, wherein the content of each of the metal elements in the silicone resin layer is 0.02 to 1.5% by mass.

[0021] [5] The laminate according to any one of [1] to [4] above, wherein a plurality of the substrates are laminated on the supporting base material with the silicone resin layer interposed therebetween.

[0022] [6] The laminate according to any one of [1] to [5] above, wherein the substrate is a glass substrate.

[0023] [7] The laminate according to any one of [1] to [5] above, wherein the substrate is a resin substrate.

[0024] [8] The laminate according to [7] above, wherein the resin substrate is a polyimide resin substrate.

[0025] [9] The laminate according to any one of [1] to [5] above, wherein the substrate is a substrate containing a semiconductor material.

[0026]

[10] The stacked body according to [9] above, wherein the semiconductor material is Si, SiC, GaN, gallium oxide or diamond.

[0027]

[11] A support substrate with a silicone resin layer, comprising a support substrate and a silicone resin layer in this order, wherein the silicone resin layer contains at least one metal element selected from the group consisting of zirconium, aluminum, and tin.

[0028]

[12] A method for manufacturing an electronic device, comprising:

[0029] a member forming step of forming an electronic device member on the surface of the substrate of the laminated body described in any one of [1] to

[10] to obtain a laminated body with an electronic device member; and

[0030] The separation step is to remove the support substrate with the silicone resin layer, which includes the support substrate and the silicone resin layer, from the laminate with the electronic device member to obtain an electronic device having the substrate and the electronic device member.

[0031]

[13] A resin substrate with a silicone resin layer, comprising a resin substrate and a silicone resin layer in this order, wherein the silicone resin layer contains at least one metal element selected from the group consisting of zirconium, aluminum, and tin.

[0032]

[14] A method for manufacturing an electronic device, comprising:

[0033] a step of forming a laminate, comprising forming the laminate using the resin substrate with the silicone resin layer described in

[13] and a supporting substrate;

[0034] a member forming step of forming an electronic device member on the surface of the resin substrate of the laminate to obtain a laminate with an electronic device member; and

[0035] The separation step is to remove the supporting base material and the silicone resin layer from the laminate with the electronic device member to obtain an electronic device having the resin substrate and the electronic device member.

[0036] Effects of the Invention

[0037] According to the present invention, a laminate having excellent foaming resistance can be provided.

[0038] According to the present invention, there can also be provided a supporting base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for producing an electronic device that can be applied to the above-mentioned laminate. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1This is a schematic cross-sectional view of one embodiment of the glass laminate of the present invention.

[0040] Figure 2 (A) and Figure 2 (B) is a schematic cross-sectional view showing one embodiment of the method for manufacturing an electronic device of the present invention in order of steps.

[0041] Description of Reference Numerals

[0042] 10 Glass laminate

[0043] 12 Support substrate

[0044] 14 Silicone resin layer

[0045] 14a Surface of silicone resin layer

[0046] 16 Glass substrate

[0047] 16a First main surface of the glass substrate

[0048] 16b Second main surface of the glass substrate

[0049] 18 Support substrate with silicone resin layer

[0050] 20 Components for electronic devices

[0051] 22 Laminated body with components for electronic devices

[0052] 24 Substrate with components (electronic devices) DETAILED DESCRIPTION

[0053] Hereinafter, the embodiment for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiment, and various modifications and substitutions may be made to the following embodiment without departing from the scope of the present invention.

[0054] Figure 1 This is a schematic cross-sectional view of one embodiment of a glass laminate as one aspect of the laminate of the present invention.

[0055] like Figure 1 As shown, the glass laminate 10 is a laminate comprising a support base 12, a glass substrate 16, and a silicone resin layer 14 disposed therebetween. One surface of the silicone resin layer 14 contacts the support base 12, and the other surface contacts the first main surface 16a of the glass substrate 16.

[0056] In the glass laminate 10, the peel strength between the silicone resin layer 14 and the glass substrate 16 is lower than the peel strength between the silicone resin layer 14 and the supporting substrate 12. Therefore, the silicone resin layer 14 and the glass substrate 16 are peeled off and separated into a laminate of the silicone resin layer 14 and the supporting substrate 12 and the glass substrate 16. In other words, the silicone resin layer 14 is fixed to the supporting substrate 12, and the glass substrate 16 is laminated on the silicone resin layer 14 in a releasable manner.

[0057] The two-layer portion including the support base 12 and the silicone resin layer 14 has the function of reinforcing the glass substrate 16. The two-layer portion including the support base 12 and the silicone resin layer 14 produced in advance for manufacturing the glass laminate 10 is referred to as the support base 18 with a silicone resin layer.

[0058] The glass laminate 10 is separated into the glass substrate 16 and the supporting base material 18 with a silicone resin layer by the steps described below. The supporting base material 18 with a silicone resin layer can be laminated with a new glass substrate 16 and reused as a new glass laminate 10.

[0059] The peel strength between the support substrate 12 and the silicone resin layer 14 is the peel strength (x). When a stress in the peeling direction exceeding the peel strength (x) is applied between the support substrate 12 and the silicone resin layer 14, the support substrate 12 and the silicone resin layer 14 peel. The peel strength between the silicone resin layer 14 and the glass substrate 16 is the peel strength (y). When a stress in the peeling direction exceeding the peel strength (y) is applied between the silicone resin layer 14 and the glass substrate 16, the silicone resin layer 14 and the glass substrate 16 peel.

[0060] In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, when stress is applied to the glass laminate 10 in a direction that causes the support base 12 and the glass substrate 16 to separate, the glass laminate 10 peels between the silicone resin layer 14 and the glass substrate 16, separating into the glass substrate 16 and the support base 18 with the silicone resin layer.

[0061] The peel strength (x) is preferably sufficiently higher than the peel strength (y).

[0062] To improve the adhesion of the silicone resin layer 14 to the support substrate 12, the curable silicone described below is preferably cured on the support substrate 12 to form the silicone resin layer 14. The adhesive force during curing allows the silicone resin layer 14 to be bonded to the support substrate 12 with high strength.

[0063] On the other hand, the bonding strength of the cured silicone resin to the glass substrate 16 is generally lower than the bonding strength generated during the curing process. Therefore, the glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the supporting base 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14.

[0064] Hereinafter, first, each layer constituting the glass laminate 10 (the supporting base material 12 , the glass substrate 16 , and the silicone resin layer 14 ) will be described in detail, and then a method for producing the glass laminate will be described in detail.

[0065] <Supporting Base Material>

[0066] The support base 12 is a member that supports and reinforces the glass substrate 16 .

[0067] As the support base 12, for example, a glass plate, a plastic plate, a metal plate (e.g., a SUS plate), etc. can be used. Generally, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16, and more preferably formed of the same material as the glass substrate 16. It is particularly preferred that the support base 12 is a glass plate formed of the same glass material as the glass substrate 16.

[0068] The thickness of the support base material 12 may be thicker or thinner than the glass substrate 16. From the viewpoint of the handleability of the glass laminate 10, the thickness of the support base material 12 is preferably thicker than the glass substrate 16.

[0069] When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.03 mm or more for reasons of ease of handling and resistance to breakage. The thickness of the glass plate is preferably 1.0 mm or less for reasons of rigidity to allow moderate bending without breakage when the glass substrate is peeled off.

[0070] The difference in average linear expansion coefficient between the support base 12 and the glass substrate 16 at 25 to 300° C. is preferably 10×10 -7 / ℃ or less, more preferably 3×10 -7 / ℃ or less, more preferably 1×10 -7 / ℃ below.

[0071] <Glass Substrate>

[0072] The type of glass used for the glass substrate 16 is not particularly limited, but preferably includes alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high-silica glass, and other oxide-based glasses containing silicon oxide as a main component. Oxide-based glasses preferably have a silicon oxide content of 40 to 90% by mass, calculated as oxide.

[0073] As the glass substrate 16, more specifically, as a glass substrate for display devices such as LCD and OLED, and a glass substrate for a receiving sensor panel for electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc., a glass plate formed of alkali-free borosilicate glass (trade name "AN100" manufactured by Asahi Glass Co., Ltd.) can be listed.

[0074] The thickness of the glass substrate 16 is preferably 0.5 mm or less, more preferably 0.4 mm or less, further preferably 0.2 mm or less, and particularly preferably 0.10 mm or less from the perspective of thinning and / or weight reduction. A thickness of 0.5 mm or less provides good flexibility to the glass substrate 16. A thickness of 0.2 mm or less allows the glass substrate 16 to be wound into a roll.

[0075] From the viewpoint of easy handling of the glass substrate 16 , the thickness of the glass substrate 16 is preferably 0.03 mm or more.

[0076] Furthermore, the area of ​​the glass substrate 16 (the area of ​​the main surface) is not particularly limited, but is preferably 300 cm 2 above.

[0077] The glass substrate 16 may include two or more layers. In this case, the materials forming each layer may be the same material or different materials. In this case, the "thickness of the glass substrate 16" refers to the total thickness of all layers.

[0078] The method for producing the glass substrate 16 is not particularly limited, and can generally be obtained by melting glass raw materials and forming the molten glass into a plate. Such forming methods may be common methods, such as float glass, fusion glass, and slot-draw glass.

[0079] <Silicone Resin Layer>

[0080] The silicone resin layer 14 prevents the glass substrate 16 from being displaced and from being damaged during separation. A surface 14 a of the silicone resin layer 14 that contacts the glass substrate 16 is in close contact with a first main surface 16 a of the glass substrate 16 .

[0081] It is considered that the silicone resin layer 14 and the glass substrate 16 are bonded together by a weak adhesive force or a bonding force due to van der Waals force.

[0082] The silicone resin layer 14 is bonded to the surface of the support substrate 12 through a strong bonding force. Known methods can be used to improve the adhesion between the two. For example, as described later, by forming the silicone resin layer 14 on the surface of the support substrate 12 (more specifically, by curing a curable silicone (organopolysiloxane) capable of forming a predetermined silicone resin on the support substrate 12), the silicone resin in the silicone resin layer 14 adheres to the surface of the support substrate 12, thereby achieving a high bonding force. Treatment to generate a strong bonding force between the surface of the support substrate 12 and the silicone resin layer 14 (e.g., treatment with a coupling agent) can also improve the bonding force between the surface of the support substrate 12 and the silicone resin layer 14.

[0083] The thickness of the silicone resin layer 14 is not particularly limited, but is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 10 μm or less. There is no particular lower limit, but it is often 0.001 μm or greater. When the thickness of the silicone resin layer 14 falls within this range, cracks are less likely to form in the silicone resin layer 14, and even if bubbles or foreign matter become trapped between the silicone resin layer 14 and the glass substrate 16, deformation defects in the glass substrate 16 can be suppressed.

[0084] The thickness mentioned above means an average thickness, which is a value obtained by measuring the thickness of the silicone resin layer 14 at five or more arbitrary positions using a contact-type film thickness measuring device and taking the arithmetic average of the measured values.

[0085] The surface roughness Ra of the surface of the silicone resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably 0.1 to 20 nm, more preferably 0.1 to 10 nm, from the viewpoint of better lamination and peeling properties of the glass substrate 16 .

[0086] The surface roughness Ra is measured according to JIS B 0601-2001, and the value obtained by taking the arithmetic average of Ra measured at five or more arbitrary locations corresponds to the surface roughness Ra.

[0087] (Specific elements)

[0088] The silicone resin layer contains at least one metal element selected from the group consisting of zirconium (Zr), aluminum (Al), and tin (Sn) (hereinafter, these elements are also collectively referred to as "specific elements").

[0089] By including these specific elements in the silicone resin layer, the generation of bubbles in the silicone resin layer during high-temperature heat treatment (eg, 500 to 600° C.) in an inert gas atmosphere can be suppressed, thereby achieving excellent foaming resistance.

[0090] The reason (mechanism) for achieving the above effect is not clear, but it is considered that the specific element undergoes a polymerization reaction in the silicone resin layer, or that the specific element crosslinks with the decomposed portion in the silicone resin layer.

[0091] Among the above-mentioned specific elements, the silicone resin layer preferably contains at least one metal element selected from the group consisting of zirconium (Zr) and tin (Sn), and more preferably contains zirconium (Zr) because of its superior foaming resistance.

[0092] The silicone resin layer preferably contains Zr and Sn because the glass substrate can be easily separated from the silicone resin layer after the heat treatment.

[0093] The content of each of the specific elements in the silicone resin layer is preferably 0.02 to 1.5 mass %, more preferably 0.03 to 1.0 mass %, further preferably 0.04 to 0.3 mass %, and particularly preferably 0.06 to 0.3 mass %, because of better foaming resistance.

[0094] This content is a ratio (unit: mass %) of the specific element when the mass of the silicone resin layer is taken as 100 mass %.

[0095] The content means the “content of each individual element” rather than the “total content” of the specific elements.

[0096] The silicone resin layer may contain other metal elements (hereinafter also simply referred to as "other metal elements") in addition to the above-mentioned specific elements.

[0097] The specific element and the other metal element in the silicone resin layer may be in the form of a metal, an ion, a compound, or a complex.

[0098] The method for measuring the specific elements and the aforementioned other metal elements in the silicone resin layer is not particularly limited, and known methods may be employed, such as ICP atomic emission spectroscopy (ICP-AES) or ICP mass spectrometry (ICP-MS). Examples of apparatus used in these methods include the inductively coupled plasma atomic emission spectrometer PS3520UVDDII (Hitachi High-Technologies Corporation) and the inductively coupled plasma (triple quadrupole) mass spectrometer Agilent 8800 (Agilent Technologies).

[0099] As an example of a specific step based on the above method, first, the mass of the silicone resin layer is measured. Then, the silicone resin layer is oxidized and converted to silicon dioxide using an oxygen burner or the like. Then, in order to remove the SiO2 component from the oxidized silicone resin layer, the oxidized silicone resin layer is cleaned with hydrofluoric acid. The resulting residue is dissolved in hydrochloric acid, and the specified specific elements and / or other metal elements are quantified using the above-mentioned ICP atomic emission spectrometry (ICP-AES) or ICP mass spectrometry (ICP-MS). Then, the content of the specific elements or other metal elements relative to the pre-measured mass of the silicone resin layer is calculated.

[0100] The method for forming the silicone resin layer containing the specific element is not particularly limited. For example, a method of forming the silicone resin layer using a curable composition containing a curable silicone and a metal compound containing the specific element described below is mentioned.

[0101] As a method for introducing other metal elements into the silicone resin layer, for example, a method of forming the silicone resin layer using the above-mentioned curable composition containing the curable silicone described below, a metal compound containing the specific element, and a metal compound containing other metal elements, as in the case of the above-mentioned specific element, can be cited.

[0102] The details are described in detail in the following paragraphs.

[0103] (Silicone resin)

[0104] The silicone resin layer 14 is mainly formed of silicone resin.

[0105] Generally, organosiloxy units include monofunctional organosiloxy units referred to as M units, bifunctional organosiloxy units referred to as D units, trifunctional organosiloxy units referred to as T units, and tetrafunctional organosiloxy units referred to as Q units. Q units are units that do not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but are considered organosiloxy units (silicon-containing bond units) in the present invention. Monomers that form M units, D units, T units, and Q units are also referred to as M monomers, D monomers, T monomers, and Q monomers, respectively.

[0106] The total organosiloxy unit means the total of M units, D units, T units and Q units. The ratio of the number (molar amount) of M units, D units, T units and Q units can be calculated based on 29 The calculation was based on the peak area ratio obtained by Si-NMR.

[0107] In the organosiloxy unit, the siloxane bond is a bond formed by two silicon atoms being bonded via one oxygen atom. Therefore, the oxygen atom per silicon atom in the siloxane bond is considered to be 1 / 2, which is represented by O in the formula. 1 / 2 More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit, so that the formula is -O 1 / 2 -(R)2Si-O 1 / 2 -(R represents a hydrogen atom or an organic group). Because there are 2 O 1 / 2 , so the D unit is usually represented as (R)2SiO 2 / 2 (In other words, (R)2SiO).

[0108] In the following description, oxygen atoms O bonded to other silicon atoms are ＊ The oxygen atom that binds two silicon atoms refers to the oxygen atom in the bond represented by Si-O-Si. Therefore, there is one oxygen atom between the silicon atoms of the two organosiloxy units. ＊ .

[0109] M unit means (R)3SiO 1 / 2 Here, R represents a hydrogen atom or an organic group. The number after (R) (here 3) means that three hydrogen atoms or organic groups are bonded to the silicon atom. That is, the M unit has one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom. ＊ More specifically, the M unit has: three hydrogen atoms or organic groups bonded to one silicon atom, and an oxygen atom O bonded to one silicon atom. ＊ .

[0110] D unit means (R)2SiO 2 / 2 (R represents a hydrogen atom or an organic group). That is, the D unit is an organosiloxy unit having one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and two oxygen atoms O bonded to other silicon atoms. ＊ unit.

[0111] T unit means RSiO 3 / 2 (R represents a hydrogen atom or an organic group). That is, the T unit is an organosiloxy unit having one silicon atom, one hydrogen atom or organic group bonded to the silicon atom, and three oxygen atoms bonded to other silicon atoms. ＊ unit.

[0112] The Q unit means an organosiloxy unit represented by SiO2. That is, the Q unit has one silicon atom and four oxygen atoms O bonded to other silicon atoms. ＊ unit.

[0113] Examples of the organic group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogen-substituted monovalent hydrocarbon groups such as halogenated alkyl groups (e.g., chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc.). The organic group is preferably an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms (preferably about 1 to 10 carbon atoms).

[0114] The structure of the silicone resin constituting the silicone resin layer 14 is not particularly limited, but it is preferably selected from the group consisting of (R)3SiO 1 / 2 The organosiloxy unit (M unit) and (R)SiO 3 / 2 At least one specific organosiloxy unit among the group consisting of the organosiloxy units (T units) shown above.

[0115] The ratio of the specific organosiloxy units is preferably 60 mol% or more, more preferably 80 mol% or more, relative to the total organosiloxy units. The upper limit is not particularly limited, but is often 100 mol% or less.

[0116] The ratio of the number (molar amount) of M units and T units can be determined based on 29 The calculation was based on the peak area ratio obtained by Si-NMR.

[0117] (Curing silicone)

[0118] Silicone resins are generally obtained by curing (crosslinking) curable silicone that forms the silicone resin through a curing treatment. In other words, silicone resins correspond to cured products of curable silicone.

[0119] Curable silicones are classified into condensation reaction type silicones, addition reaction type silicones, UV curing type silicones, and electron beam curing type silicones according to their curing mechanisms, and all of them can be used.

[0120] As condensation-reaction organosilicon, a hydrolyzable organosilane compound or a mixture thereof (monomer mixture) as a monomer, or a partially hydrolyzed condensate (organopolysiloxane) obtained by subjecting a monomer or monomer mixture to a partial hydrolysis-condensation reaction, can be suitably used. A mixture of a partially hydrolyzed condensate and a monomer is also possible. The monomers may be used alone or in combination of two or more.

[0121] By using this condensation-reaction type silicone to carry out a hydrolysis-condensation reaction (sol-gel reaction), a silicone resin can be formed.

[0122] The above monomer (hydrolyzable organosilane compound) is usually composed of (R'-) a Si(-Z) 4-a Indicated by . Wherein, a represents an integer from 0 to 3, R' represents a hydrogen atom or an organic group, and Z represents a hydroxyl group or a hydrolyzable group. In this chemical formula, the compound with a=3 is the M monomer, the compound with a=2 is the D monomer, the compound with a=1 is the T monomer, and the compound with a=0 is the Q monomer. In the monomer, the Z group is usually a hydrolyzable group. When there are 2 or 3 R's (when a is 2 or 3), the multiple R's may be different.

[0123] The curable silicone as a partially hydrolyzed condensate can be converted into oxygen atoms O by converting part of the Z group of the monomer ＊ When the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by hydrolysis reaction, and then the two hydroxyl groups bonded to other silicon atoms undergo dehydration condensation reaction, and the two silicon atoms are connected by oxygen atoms O. ＊ Hydroxyl groups (or unhydrolyzed Z groups) remain in the curable silicone. During the curing of the curable silicone, these hydroxyl groups and Z groups react in the same manner as described above, resulting in the curing. The cured product of the curable silicone generally forms a three-dimensionally crosslinked polymer (silicone resin).

[0124] When the Z group of the monomer is a hydrolyzable group, examples of the Z group include an alkoxy group, a halogen atom (e.g., a chlorine atom), an acyloxy group, and an isocyanate group. In many cases, a monomer in which the Z group is an alkoxy group is used as the monomer, and such a monomer is also called an alkoxysilane.

[0125] Alkoxy groups are hydrolyzable groups with lower reactivity than other hydrolyzable groups such as chlorine atoms. In curable silicones obtained using monomers (alkoxysilanes) in which the Z group is an alkoxy group, unreacted alkoxy groups often exist as Z groups together with hydroxyl groups.

[0126] As the condensation reaction type organosilicon, from the perspective of reaction control and processing, a partially hydrolyzed condensate (organopolysiloxane) obtained from a hydrolyzable organosilane compound is preferred. The partially hydrolyzed condensate is obtained by subjecting the hydrolyzable organosilane compound to partial hydrolysis and condensation. There are no particular restrictions on the method of partial hydrolysis and condensation. It is generally produced by reacting the hydrolyzable organosilane compound in a solvent in the presence of a catalyst. Examples of catalysts include acid catalysts and base catalysts. Water is generally preferably used in the hydrolysis reaction. The partially hydrolyzed condensate is preferably produced by reacting the hydrolyzable organosilane compound in a solvent in the presence of an acid or alkaline aqueous solution.

[0127] As mentioned above, a suitable form of the hydrolyzable organosilane compound to be used includes alkoxysilane. That is, as one suitable form of the curable silicone, a curable silicone obtained by the hydrolysis reaction and condensation reaction of alkoxysilane can be mentioned.

[0128] When alkoxysilane is used, the degree of polymerization of the partially hydrolyzed condensate tends to be high, and the effect of the present invention is more excellent.

[0129] As addition reaction type silicone, a curable composition comprising a main agent and a crosslinking agent, which is cured in the presence of a catalyst such as a platinum catalyst, can be appropriately used. The curing of the addition reaction type silicone can be accelerated by heat treatment. The main agent in the addition reaction type silicone is preferably an organopolysiloxane (i.e., an organoalkenylpolysiloxane. Preferably linear) having an alkenyl group (vinyl group, etc.) bonded to a silicon atom, and the alkenyl group, etc. serves as a crosslinking point. The crosslinking agent in the addition reaction type silicone is preferably an organopolysiloxane (i.e., an organohydrogenpolysiloxane. Preferably linear) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom, and the hydrosilyl group, etc. serves as a crosslinking point.

[0130] Addition-reaction silicones cure through an addition reaction between the main agent and the crosslinking points of the crosslinking agent. To achieve superior heat resistance derived from the crosslinked structure, the molar ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane to alkenyl groups in the organoalkenylpolysiloxane is preferably 0.5 to 2.

[0131] The weight average molecular weight (Mw) of the curable silicones, such as the condensation-reaction silicones and addition-reaction silicones, is not particularly limited, but is preferably 5,000 to 60,000, more preferably 5,000 to 30,000. An Mw of 5,000 or greater provides excellent coating properties, while an Mw of 60,000 or less provides good solubility in solvents and coating properties.

[0132] (Curable composition)

[0133] The method for producing the silicone resin layer 14 is not particularly limited, and a known method may be employed. However, in terms of excellent productivity of the silicone resin layer 14, a preferred method for producing the silicone resin layer 14 is to coat a curable composition containing a curable silicone forming the silicone resin and a metal compound containing a specific element onto the support substrate 12, remove the solvent as needed to form a coating film, and cure the curable silicone in the coating film to produce the silicone resin layer 14.

[0134] As described above, curable silicones may be hydrolyzable organosilane compounds as monomers and / or partially hydrolyzed condensates (organopolysiloxanes) obtained by subjecting monomers to partial hydrolysis and condensation reactions. Curable silicones may also be mixtures of organoalkenylpolysiloxanes and organohydrogenpolysiloxanes.

[0135] The metal compound containing a specific element contained in the curable composition is not particularly limited in structure as long as it contains the predetermined specific element, and examples thereof include known metal compounds. In this specification, the complex compound is included in the above-mentioned metal compound.

[0136] The metal compound containing the specific element is preferably a complex containing the specific element. A complex is an aggregate formed by bonding ligands (atoms, atomic groups, molecules, or ions) to an atom or ion of a metal element as a center.

[0137] The type of the ligand contained in the complex is not particularly limited, and examples thereof include ligands selected from the group consisting of β-diketones, carboxylic acids, alkoxides, and alcohols.

[0138] Examples of the β-diketone include acetylacetone, methyl acetoacetate, ethyl acetoacetate, and benzoylacetone.

[0139] Examples of the carboxylic acid include acetic acid, 2-ethylhexanoic acid, cyclohexanecarboxylic acid, and neodecanoic acid.

[0140] Examples of the alkoxide include methoxide, ethoxide, n-propoxide, isopropoxide, and n-butoxide.

[0141] Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0142] Specific examples of the metal compound containing a specific element include zirconium compounds such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, and zirconium tetra-n-butoxide; aluminum compounds such as aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, and aluminum acetylacetonate; tin compounds such as tin bis(2-ethylhexanoate), tin bis(neodecanoate), dibutyltin bis(acetylacetonate), and dibutyltin dilaurate; and the like, but are not limited to these.

[0143] The content of the metal compound containing the specific element in the curable composition is not particularly limited, but is preferably adjusted so that the content of the specific element in the silicone resin layer falls within an appropriate range.

[0144] As described above, the curable composition may contain a metal compound containing other metal elements.

[0145] The metal compound containing another metal element is preferably a complex containing another metal element. The definition of the complex is as described above, and the appropriate range of ligands that can be contained in the complex is the same as that of the complex containing a specific metal.

[0146] When an addition reaction type silicone is used as the curable silicone, the curable composition may contain a platinum catalyst as a metal compound containing other metal elements, if necessary.

[0147] The platinum catalyst is a catalyst for advancing or accelerating the hydrosilylation reaction between the alkenyl groups in the organoalkenylpolysiloxane and the hydrogen atoms in the organohydrogenpolysiloxane.

[0148] The curable composition may contain a solvent. In this case, the thickness of the coating film can be controlled by adjusting the concentration of the solvent. In view of excellent handling properties and easier control of the thickness of the silicone resin layer 14, the content of curable silicone in the curable composition containing curable silicone is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, relative to the total mass of the composition.

[0149] The solvent is not particularly limited as long as it can easily dissolve the curable silicone under the working environment and can be easily volatilized and removed. Specific examples include butyl acetate, 2-heptanone, and 1-methoxy-2-propanol acetate.

[0150] In addition, the curable composition may contain various additives. For example, a leveling agent may be included. Examples of the leveling agent include fluorine-based leveling agents such as Megafac F558, Megafac F560, and Megafac F561 (all manufactured by DIC Corporation).

[0151] <Glass laminate and its manufacturing method>

[0152] As described above, the glass laminate 10 is a laminate including the supporting base material 12 and the glass substrate 16 , and the silicone resin layer 14 disposed therebetween.

[0153] The method for producing the glass laminate 10 is not particularly limited. However, in order to obtain a laminate having a peel strength (x) higher than a peel strength (y), a method of forming a silicone resin layer 14 on the surface of a supporting substrate 12 is preferred. Among these methods, a method of coating the surface of the supporting substrate 12 with a curable composition containing a curable silicone and a metal compound containing a specific element, curing the resulting coating film to obtain the silicone resin layer 14, and then laminating a glass substrate 16 on the surface of the silicone resin layer 14 to produce the glass laminate 10 is preferred.

[0154] It is believed that when the curable silicone is cured on the surface of the support substrate 12, the silicone resin adheres to the surface of the support substrate 12 through interaction with the surface during the curing reaction, thereby increasing the peel strength between the silicone resin and the surface of the support substrate 12. Therefore, even if the glass substrate 16 and the support substrate 12 are formed of the same material, it is possible to design a difference in the peel strength between the silicone resin layer 14 and the two.

[0155] Hereinafter, the process of forming a layer of curable silicone on the surface of the supporting substrate 12 and forming the silicone resin layer 14 on the surface of the supporting substrate 12 will be referred to as resin layer forming process 1, and the process of laminating the glass substrate 16 on the surface of the silicone resin layer 14 to form the glass laminate 10 will be referred to as laminating process 1. The steps of each process will be described in detail.

[0156] (Resin Layer Forming Step 1)

[0157] In the resin layer forming step 1 , a layer of curable silicone is formed on the surface of the support base 12 , thereby forming the silicone resin layer 14 on the surface of the support base 12 .

[0158] First, in order to form a curable silicone layer on the support substrate 12, the curable composition is applied to the support substrate 12. Next, the curable silicone layer is preferably cured to form a cured layer.

[0159] The method for coating the curable composition on the surface of the support substrate 12 is not particularly limited, and known methods can be used. For example, spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, gravure coating, etc. can be used.

[0160] Next, the curable silicone on the supporting substrate 12 is cured to form a cured layer.

[0161] There are no particular restrictions on the curing method, and an optimal treatment can be appropriately performed depending on the type of curable silicone used. For example, when using condensation-reaction silicone or addition-reaction silicone, heat curing is preferred as the curing treatment.

[0162] The temperature conditions for thermal curing are preferably 150 to 550° C., more preferably 200 to 450° C. The heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 minutes. The heating conditions can be varied and carried out in stages.

[0163] In the heat curing treatment, it is preferable to perform post-curing (main curing) after performing pre-curing (preliminary curing). By performing pre-curing, the silicone resin layer 14 having excellent heat resistance is obtained.

[0164] (Lamination process 1)

[0165] The lamination step 1 is a step of laminating the glass substrate 16 on the surface of the silicone resin layer 14 obtained in the resin layer forming step to obtain a glass laminate 10 including the supporting base 12 , the silicone resin layer 14 , and the glass substrate 16 in this order.

[0166] The method of laminating the glass substrate 16 on the silicone resin layer 14 is not particularly limited, and a known method may be used.

[0167] For example, a method of laminating the glass substrate 16 on the surface of the silicone resin layer 14 under normal pressure can be mentioned. If necessary, after laminating the glass substrate 16 on the surface of the silicone resin layer 14, the glass substrate 16 can be pressed against the silicone resin layer 14 using a roller or a press. Pressing with a roller or a press is preferred because bubbles trapped between the silicone resin layer 14 and the glass substrate 16 can be more easily removed.

[0168] Compression bonding by vacuum lamination or vacuum pressing is preferred because it can suppress the incorporation of bubbles and achieve good adhesion. Compression bonding under vacuum also has the advantage that even if tiny bubbles remain, they will not grow due to heating, making it less likely to cause deformation defects in the glass substrate 16.

[0169] When laminating the glass substrate 16, it is preferred to thoroughly clean the surface of the glass substrate 16 that contacts the silicone resin layer 14 and perform lamination in a clean environment. A higher cleanliness is preferred because the flatness of the glass substrate 16 improves.

[0170] After laminating the glass substrates 16, a pre-annealing treatment (heating treatment) may be performed as needed. This pre-annealing treatment improves the adhesion of the laminated glass substrates 16 to the silicone resin layer 14, and enables appropriate peel strength (y) to be achieved.

[0171] In the above, the case where a glass substrate is used as the substrate has been described in detail, but the type of the substrate is not particularly limited.

[0172] For example, examples of substrates include metal substrates, semiconductor substrates, resin substrates, and glass substrates. A substrate may be composed of multiple materials of the same type, such as a metal plate composed of two different metals. Furthermore, a substrate may be a composite substrate of different materials (e.g., two or more materials selected from metal, semiconductor, resin, and glass), such as a substrate composed of resin and glass.

[0173] The thickness of a substrate such as a metal plate or semiconductor substrate is not particularly limited. However, from the perspective of thinning and / or weight reduction, it is preferably 0.5 mm or less, more preferably 0.4 mm or less, further preferably 0.2 mm or less, and particularly preferably 0.10 mm or less. The lower limit of the thickness is not particularly limited, but is preferably 0.005 mm or more.

[0174] The area of ​​the substrate (the area of ​​the main surface) is not particularly limited, but is preferably 300 cm 2 above.

[0175] The shape of the substrate is not particularly limited and may be rectangular or circular. The substrate may be formed with an orientation flat (a flat portion formed on the periphery of the substrate) or a notch (one or more V-shaped notches formed on the periphery of the substrate).

[0176] <Resin Substrate and Method for Manufacturing a Laminated Body Using the Same>

[0177] As the resin substrate, it is preferable to use a resin substrate having excellent heat resistance that can withstand heat treatment in the device manufacturing process.

[0178] Examples of the resin constituting the resin substrate include polybenzimidazole resin (PBI), polyimide resin (PI), polyetheretherketone resin (PEEK), polyamide resin (PA), fluororesin, epoxy resin, and polyphenylene sulfide resin (PPS). In particular, a polyimide resin substrate formed of a polyimide resin is preferred from the viewpoints of excellent heat resistance, excellent chemical resistance, low thermal expansion coefficient, and high mechanical properties.

[0179] In order to form high-definition wiring of electronic devices on a resin substrate, the surface of the resin substrate is preferably smooth. Specifically, the surface roughness Ra of the resin substrate is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 10 nm or less.

[0180] The thickness of the resin substrate is preferably 1 μm or more, more preferably 10 μm or more, from the viewpoint of handleability in the production process, and is preferably 1 mm or less, more preferably 0.2 mm or less, from the viewpoint of flexibility.

[0181] The thermal expansion coefficient of the resin substrate is preferably smaller than that of the electronic device or the supporting substrate because it can suppress the warping of the laminate after heating or cooling. Specifically, the difference in thermal expansion coefficient between the resin substrate and the supporting substrate is preferably 0 to 90×10 -6 / °C, more preferably 0 to 30×10 -6 / ℃.

[0182] There are no particular limitations on the method for producing a laminate using a resin substrate as the substrate. For example, the laminate can be produced using the same method as described above for the case of using a glass substrate. Specifically, the laminate can be produced by forming a silicone resin layer on a supporting base material and then laminating the resin substrate on the silicone resin layer.

[0183] Hereinafter, a laminate including a supporting base material, a silicone resin layer, and a resin substrate in this order is also referred to as a resin laminate.

[0184] As another method for producing a resin laminate, a method of forming a silicone resin layer on the surface of a resin substrate to produce the resin laminate is also preferred.

[0185] Silicone resin layers generally tend to have low adhesion to resin substrates. Therefore, when a resin laminate is obtained by forming a silicone resin layer on the surface of a resin substrate and laminating the resulting silicone resin layer-carrying resin substrate with a support substrate, the peel strength (x) between the support substrate and the silicone resin layer tends to be higher than the peel strength (y') between the silicone resin layer and the resin substrate. This tendency is particularly pronounced when a glass plate is used as the support substrate.

[0186] That is, the resin laminate can be separated into the resin substrate and the supporting base material with the silicone resin layer, similarly to the case of the glass laminate.

[0187] Other methods for manufacturing the above-mentioned resin laminate mainly include: forming a layer of curable silicone on the surface of a resin substrate to form a silicone resin layer on the surface of the resin substrate (resin layer forming step 2); and laminating a supporting substrate on the surface of the silicone resin layer to form a resin laminate (laminating step 2).

[0188] Hereinafter, the steps of each of the above processes will be described in detail.

[0189] (Resin Layer Formation Step 2)

[0190] The resin layer forming step 2 is a step of forming a layer of curable silicone on the surface of the resin substrate, thereby forming a silicone resin layer on the surface of the resin substrate. This step can provide a resin substrate with a silicone resin layer, which sequentially comprises a resin substrate and a silicone resin layer.

[0191] In this step, the curable composition is applied to the resin substrate to form a curable silicone layer on the resin substrate. The curable silicone layer is then preferably cured to form a cured layer.

[0192] The method for applying the curable composition to the surface of the resin substrate is not particularly limited, and known methods may be used, for example, spray coating, die coating, spin coating, dip coating, roll coating, rod coating, screen printing, gravure coating, etc.

[0193] Next, the curable silicone on the resin substrate is cured to form a cured layer (silicone resin layer).

[0194] There are no particular restrictions on the curing method, and an optimal treatment can be appropriately performed depending on the type of curable silicone used. For example, when using condensation-reaction silicone or addition-reaction silicone, heat curing is preferred as the curing treatment.

[0195] The heat curing treatment is carried out under conditions within the heat resistance range of the resin substrate. For example, the heat curing temperature is preferably 50 to 400° C., more preferably 100 to 300° C. The heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 minutes.

[0196] The method for forming the silicone resin layer is as described above.

[0197] (Lamination process 2)

[0198] The lamination step 2 is a step of laminating a support substrate on the surface of the silicone resin layer to form a resin laminate. In other words, this step is a step of forming a resin laminate using a resin substrate with a silicone resin layer and a support substrate.

[0199] The method for laminating the supporting substrate on the silicone resin layer is not particularly limited, and a known method may be used, including the method mentioned in the description of the lamination step 1 in the production of the glass laminate.

[0200] After laminating the support substrate, a heat treatment may be performed as needed. The heat treatment improves the adhesion of the laminated support substrate to the silicone resin layer, thereby achieving an appropriate peel strength (x).

[0201] The temperature conditions for the heat treatment are preferably 50 to 400° C., more preferably 100 to 300° C. The heating time is usually preferably 1 to 120 minutes, more preferably 5 to 60 minutes. The heating may be performed in stages by changing the temperature conditions.

[0202] When the resin laminate is heated in the step of forming an electronic device member described later, the heating treatment may be omitted.

[0203] From the viewpoint of improving the peel strength (x) and adjusting the balance between the peel strength (x) and the peel strength (y'), it is preferred to perform a surface treatment on at least one of the support substrate and the silicone resin layer before laminating the support substrate on the silicone resin layer, and it is more preferred to perform a surface treatment on the silicone resin layer.

[0204] Examples of the surface treatment method include corona treatment, plasma treatment, and UV ozone treatment. Among these, corona treatment is preferred.

[0205] The resin substrate with a silicone resin layer can be produced by a so-called roll-to-roll method in which a silicone resin layer is formed on the surface of a resin substrate wound into a roll and then the roll is rewound, thereby achieving excellent production efficiency.

[0206] When a silicone resin layer is formed on a supporting substrate and a curable composition is applied to the supporting substrate, the thickness of the silicone resin layer at the periphery tends to be thicker than the thickness at the center due to the so-called coffee ring phenomenon. In this case, the peripheral portion of the supporting substrate where the silicone resin layer is disposed must be cut and removed. This requires significant effort and cost when the supporting substrate is a glass plate.

[0207] On the other hand, when a silicone resin layer is formed on a resin substrate, the resin substrate generally has excellent handleability and cost. Therefore, even if the above-mentioned problem occurs, it is relatively easy to remove the outer peripheral portion of the resin substrate where the silicone resin layer is disposed.

[0208] <Method for Manufacturing a Semiconductor Substrate and a Laminated Body Using the Semiconductor Substrate>

[0209] The semiconductor substrate is preferably a substrate made of a semiconductor material. Examples of semiconductor materials include Si, SiC, GaN, gallium oxide, and diamond. A Si substrate is also referred to as a Si wafer.

[0210] In order to form high-definition wiring of electronic devices on a semiconductor substrate, the surface of the semiconductor substrate is preferably smooth. Specifically, the surface roughness Ra of the semiconductor substrate is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.

[0211] The thickness of the semiconductor substrate is preferably 1 μm or more, more preferably 10 μm or more, from the viewpoint of handleability in the manufacturing process, and is preferably 1 mm or less, more preferably 0.2 mm or less, from the viewpoint of miniaturization of electronic devices.

[0212] The difference in thermal expansion coefficient between the semiconductor substrate and the electronic device or the supporting substrate is preferably small because it can suppress the warping of the laminate after heating or cooling. Specifically, the difference in thermal expansion coefficient between the semiconductor substrate and the supporting substrate is preferably 0 to 90×10 -6 / °C, more preferably 0 to 30×10 -6 / ℃.

[0213] There are no particular limitations on the method for producing a laminate using a semiconductor substrate as the substrate. For example, the laminate can be produced using the same method as described above for the case of using a glass substrate. Specifically, the laminate can be produced by forming a silicone resin layer on a supporting base material and then laminating the semiconductor substrate on the silicone resin layer.

[0214] Hereinafter, a stacked body including a supporting base material, a silicone resin layer, and a semiconductor substrate in this order is also referred to as a semiconductor stacked body.

[0215] It should be noted that Figure 1 , a configuration is shown in which a single substrate (glass substrate, resin substrate, or semiconductor substrate) is laminated on a supporting base material with a silicone resin layer sandwiched therebetween. However, the laminate of the present invention is not limited to this configuration. For example, a configuration in which multiple substrates are laminated on a supporting base material with a silicone resin layer sandwiched therebetween (hereinafter also referred to as a "multi-sided lamination configuration").

[0216] More specifically, the multi-sided lamination method is a method in which multiple substrates are in contact with the support base with the silicone resin layer interposed therebetween. In other words, it is not a method in which multiple substrates are stacked (only one of the multiple substrates is in contact with the support base with the silicone resin layer interposed therebetween).

[0217] In a multi-sided bonding approach, for example, multiple silicone resin layers can be provided on each substrate, and multiple substrates and silicone resin layers can be placed on a single supporting substrate. However, this is not limiting. For example, each substrate can be placed on a single silicone resin layer (e.g., the same size as the supporting substrate) formed on a single supporting substrate.

[0218] <Application of Laminated Body>

[0219] The laminate of the present invention (e.g., the glass laminate 10 described above) can be used in various applications, including the manufacture of electronic components such as display panels, photovoltaic (PV), thin-film secondary batteries, semiconductor wafers with circuits formed on their surfaces, and sensor panels. It should be noted that in some of these applications, the laminate may be exposed to high temperatures (e.g., 450°C or higher) in an atmospheric atmosphere for a period of time (e.g., for 20 minutes or longer).

[0220] Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, micro LED display panel, MEMS (Micro Electro Mechanical Systems) shutter panel, etc.

[0221] Here, the receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet light receiving sensor panel, a visible light receiving sensor panel, an infrared light receiving sensor panel, etc. The substrate used in these receiving sensor panels may be reinforced with a reinforcing sheet such as resin.

[0222] <Electronic device and manufacturing method thereof>

[0223] In the present invention, the above-mentioned laminate is used to produce an electronic device including a substrate and a member for an electronic device (hereinafter also referred to as a "substrate with a member" as appropriate).

[0224] Hereinafter, a method for manufacturing an electronic device using the above-mentioned glass laminate 10 will be described in detail.

[0225] There are no particular restrictions on the method for manufacturing electronic devices. From the perspective of excellent productivity of electronic devices, the following method is preferred: forming components for electronic devices on the glass substrate in the above-mentioned glass laminate to manufacture a laminate with components for electronic devices, and using the glass substrate side interface of the silicone resin layer as a peeling surface from the obtained laminate with components for electronic devices to separate the electronic device (substrate with components) and the supporting substrate with the silicone resin layer.

[0226] Hereinafter, the process of forming a component for an electronic device on the glass substrate in the above-mentioned glass laminate to manufacture a laminate with a component for an electronic device is referred to as a component forming process; and the process of separating the laminate with a component for an electronic device into a substrate with a component and a supporting base material with a silicone resin layer using the glass substrate side interface of the silicone resin layer as a peeling surface is referred to as a separation process.

[0227] The materials and procedures used in each process are described in detail below.

[0228] (Member Forming Process)

[0229] The component forming step is a step of forming a component for an electronic device on the glass substrate 16 in the glass laminate 10. More specifically, Figure 2 As shown in FIG. 1 (A), the electronic device member 20 is formed on the second main surface 16 b (exposed surface) of the glass substrate 16 to obtain a laminate 22 with an electronic device member.

[0230] First, the electronic device member 20 used in this process will be described in detail, and then the process steps will be described in detail.

[0231] (Components for electronic devices (functional elements))

[0232] The electronic device member 20 is a member formed on the glass substrate 16 in the glass laminate 10 and constituting at least a portion of an electronic device. More specifically, the electronic device member 20 includes members used in electronic components such as display panels, solar cells, thin-film secondary batteries, or semiconductor wafers having circuits formed on their surfaces, and receiving sensor panels (for example, display devices such as LTPS, solar cell components, thin-film secondary battery components, electronic component circuits, and receiving sensor components).

[0233] For example, as components for solar cells, for the silicon type, transparent electrodes such as tin oxide for the positive electrode, silicon layers represented by p-layer / i-layer / n-layer, and metals for the negative electrode can be listed. In addition, various components corresponding to the compound type, dye-sensitized type, quantum dot type, etc. can be listed.

[0234] As components for thin film secondary batteries, for lithium ion types, transparent electrodes such as metals or metal oxides for the positive and negative electrodes, lithium compounds for the electrolyte layer, metals for the collector layer, resins as sealing layers, etc. can be listed. In addition, various components corresponding to nickel-hydrogen types, polymer types, ceramic electrolyte types, etc. can be listed.

[0235] As circuits for electronic components, in CCDs and CMOSs, metals for conductive parts and silicon oxides and silicon nitrides for insulating parts can be listed. In addition, various components corresponding to various sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, flexible printed circuit boards, and rigid-flexible printed circuit boards can be listed.

[0236] (Steps of the process)

[0237] There is no particular limitation on the method for manufacturing the laminate 22 with the electronic device component. The electronic device component 20 is formed on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a conventionally known method according to the type of components constituting the electronic device component.

[0238] The electronic device member 20 may not be the entire member (hereinafter referred to as the "entire member") ultimately formed on the second main surface 16b of the glass substrate 16, but may be a portion of the entire member (hereinafter referred to as the "partial member"). The substrate with the partial member peeled off from the silicone resin layer 14 may be used as a substrate with the entire member (equivalent to the electronic device described later) in a subsequent step.

[0239] Other electronic device components can be formed on the peeled surface (first main surface 16a) of the substrate with all components peeled from the silicone resin layer 14. Furthermore, two laminates with all components can be assembled, and then the two supporting substrates with silicone resin layers can be peeled from the laminate with all components to produce a substrate with components having two glass substrates.

[0240] For example, in the case of manufacturing an OLED, in order to form an organic EL structure on the surface of the glass substrate 16 of the glass laminate 10 opposite to the silicone resin layer 14 (corresponding to the second main surface 16b of the glass substrate 16), various layer formation and processing can be performed, such as forming a transparent electrode, then vapor-depositing a hole injection layer / hole transport layer / light-emitting layer / electron transport layer on the surface formed with the transparent electrode, forming a back electrode, and sealing with a sealing plate. Specific examples of these layer formation and processing include film formation, vapor deposition, and bonding of a sealing plate.

[0241] For example, in the case of manufacturing a TFT-LCD, there are various processes including the following: a TFT forming process in which a thin film transistor (TFT) is formed on the second main surface 16b of the glass substrate 16 of the glass laminate 10 using a material such as LTPS; a CF forming process in which a color filter (CF) is formed on the second main surface 16b of the glass substrate 16 of another glass laminate 10 using an anti-etching liquid for pattern formation; and a bonding process in which the laminate with TFT obtained in the TFT forming process and the laminate with CF obtained in the CF forming process are stacked.

[0242] For example, when manufacturing a micro-LED display, the process includes: a TFT formation step, in which thin-film transistors (TFTs) are formed using a material such as LTPS on at least the second main surface 16b of the glass substrate 16 of the glass laminate 10; and an LED mounting step, in which LED chips are mounted on the TFTs formed in the above step. Additionally, planarization, wiring formation, and sealing steps may be performed.

[0243] In the TFT forming step and the CF forming step, TFTs and CFs are formed on the second main surface 16b of the glass substrate 16 using well-known photolithography technology, etching technology, etc. At this time, a resist solution can be used as a coating liquid for pattern formation.

[0244] Before forming TFTs and CFs, the second main surface 16b of the glass substrate 16 may be cleaned as needed. As a cleaning method, well-known dry cleaning or wet cleaning can be used.

[0245] In the lamination process, the thin-film transistor-forming surface of the stack with TFTs and the color filter-forming surface of the stack with CFs are placed opposite each other and bonded together using a sealant (e.g., a UV-curable sealant for cell formation). Then, a liquid crystal material is injected into the cell formed by the stack with TFTs and the stack with CFs. Examples of methods for injecting the liquid crystal material include reduced-pressure injection and dropwise injection.

[0246] When manufacturing the electronic device member 20 , for example, heating in an inert gas atmosphere at 500 to 600° C. can be included. In the case of the laminate of the present invention, excellent foaming resistance is also achieved under the above conditions.

[0247] (Separation process)

[0248] Separation process such as Figure 2 (B) shows the following process: the laminated body 22 with components for electronic devices obtained from the above-mentioned component forming process is separated into a glass substrate 16 (substrate with components) on which the components 20 for electronic devices are laminated, and a supporting base material 18 with a silicone resin layer, using the interface between the silicone resin layer 14 and the glass substrate 16 as a peeling surface, thereby obtaining a substrate with components (electronic device) 24 including the components 20 for electronic devices and the glass substrate 16.

[0249] When the electronic device member 20 on the glass substrate 16 during the peeling is a part of the formation of all necessary constituent members, the remaining constituent members may be formed on the glass substrate 16 after separation.

[0250] There is no particular restriction on the method of peeling off the glass substrate 16 and the silicone resin layer 14. For example, a sharp knife-like object can be inserted into the interface between the glass substrate 16 and the silicone resin layer 14, and after providing a peeling starting point, a mixed fluid of water and compressed air is blown to perform peeling. Preferably, the support substrate 12 of the stacked body 22 with the electronic device component is arranged on a flat plate in a manner that the support substrate 12 is on the upper side and the electronic device component 20 side is on the lower side, so that the electronic device component 20 side is vacuum-adsorbed on the flat plate, and in this state, the knife is first intruded into the glass substrate 16-silicone resin layer 14 interface. Moreover, thereafter, the support substrate 12 side is adsorbed by multiple vacuum adsorption pads, and the vacuum adsorption pads are sequentially raised from the vicinity of the position where the knife is inserted. Thus, an air layer is formed at the interface between the silicone resin layer 14 and the glass substrate 16 and the cohesive failure surface of the silicone resin layer 14, and the air layer spreads over the entire surface of the interface and the cohesive failure surface, so that the support substrate 18 with the silicone resin layer can be easily peeled off.

[0251] The supporting base material 18 with the silicone resin layer can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

[0252] When separating the substrate 24 with the member from the laminate 22 with the electronic device member, by controlling the blowing and humidity by the ionizer, it is possible to further suppress electrostatic adsorption of the remaining pieces of the silicone resin layer 14 to the substrate 24 with the member.

[0253] The above-described method for manufacturing a substrate 24 with a component is suitable for manufacturing small display devices used in mobile terminals such as mobile phones and PDAs. Display devices are mainly LCDs or OLEDs. LCDs include TN, STN, FE, TFT, MIM, IPS, and VA types. It is applicable to any display device, whether passive or active.

[0254] Examples of the substrate 24 with a component manufactured by the above method include display panels comprising a glass substrate and display components, solar cells comprising a glass substrate and solar cell components, thin-film secondary batteries comprising a glass substrate and thin-film secondary battery components, receiving sensor panels comprising a glass substrate and receiving sensor components, and electronic components comprising a glass substrate and electronic device components. Examples of display panels include liquid crystal panels, organic EL panels, plasma display panels, and field emission panels. Examples of receiving sensor panels include electromagnetic wave receiving sensor panels, X-ray receiving sensor panels, ultraviolet light receiving sensor panels, visible light receiving sensor panels, and infrared light receiving sensor panels.

[0255] In the above description, the method for manufacturing an electronic device using the glass laminate 10 has been described in detail. However, when the above-mentioned resin laminate is used, the electronic device can also be manufactured through the same steps.

[0256] More specifically, as other methods of manufacturing electronic devices, there can be listed a scheme comprising the following steps: a step of forming a resin laminate using a resin substrate having a silicone resin layer and a supporting substrate; a component forming step of forming a component for an electronic device on the surface of the resin substrate of the resin laminate to obtain a laminate with a component for an electronic device; and a separation step of removing the supporting substrate and the silicone resin layer from the laminate with a component for an electronic device to obtain an electronic device having a resin substrate and a component for an electronic device.

[0257] The step of forming the resin laminate may include a step including the above-mentioned resin layer forming step 2 and laminating step 2.

[0258] As the procedures of the member forming step and the separation step when the resin laminate is used, the same procedures as those of the member forming step and the separation step when the glass laminate is used can be cited.

[0259] As described above, since the adhesion between the resin substrate and the silicone resin layer is relatively weak, the resin substrate and the silicone resin layer are more easily separated during the separation process than the silicone resin layer and the supporting substrate. This tendency is particularly pronounced when a glass plate is used as the supporting substrate.

[0260] In the above-described method for manufacturing an electronic device using the glass laminate 10 , an electronic device can also be manufactured by the same steps using a semiconductor laminate in which a semiconductor substrate is used instead of a glass substrate.

[0261] [Example]

[0262] Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these Examples.

[0263] In the following Examples 1 to 19, a glass plate (linear expansion coefficient 38×10 -7 / ℃, trade name "AN100" manufactured by Asahi Glass Co., Ltd.).

[0264] In the following Examples 20 to 26, a glass plate made of alkali-free borosilicate glass (linear expansion coefficient 38×10 -7 / °C, trade name "AN100" manufactured by Asahi Glass Co., Ltd.) was used as a supporting base material, and a polyimide film (manufactured by Toyobo Co., Ltd.) was used as a substrate.

[0265] Examples 1 to 13 are embodiments, Examples 14 to 16 are comparative examples, Examples 17 to 18 are embodiments, Example 19 is a comparative example, Examples 20 to 22 are embodiments, Examples 23 to 26 are comparative examples, Example 27 is an embodiment, and Example 28 is a comparative example.

[0266] <Example 1>

[0267] (Preparation of Curable Silicone 1)

[0268] Triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25°C for 20 minutes, then heated to 60°C and reacted for 12 hours. The resulting crude reaction solution was cooled to 25°C and washed three times with water (300 g).

[0269] Chlorotrimethylsilane (70 g) was added to the washed reaction crude liquid, and the mixture was stirred at 25°C for 20 minutes and then heated to 50°C for 12 hours. The obtained reaction crude liquid was cooled to 25°C and washed three times with water (300 g).

[0270] Toluene was removed from the washed crude reaction solution by vacuum distillation to form a slurry, which was then dried overnight in a vacuum dryer to obtain a white organopolysiloxane compound, namely, curable silicone 1. Curable silicone 1 had a molar ratio of 87:13 for the number of T units and 87:13 for the number of M units.

[0271] (Preparation of Curable Composition 1)

[0272] Curable silicone 1 (50 g), zirconium tetra-n-propoxide ("Orgatics ZA-45", manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 21.1%) (0.12 g) as a metal compound, and Isosorbide-5-Nitrae (manufactured by Tonen General Sekiyu KK) (75 g) as a solvent were mixed, and the resulting mixed liquid was filtered through a filter with a pore size of 0.45 μm to obtain a curable composition 1.

[0273] (Production of Glass Laminate)

[0274] The obtained curable composition 1 was applied to a 200×200 mm, 0.5 mm thick support substrate by spin coating and heated on a hot plate at 100°C for 10 minutes. The substrate was then heated in an oven at 250°C for 30 minutes in atmospheric air to form a 4 μm thick silicone resin layer.

[0275] Then, a glass substrate having a size of 200×200 mm and a thickness of 0.2 mm was placed on the silicone resin layer and bonded together using a bonding device to produce a glass laminate.

[0276] <Example 2>

[0277] A glass laminate was produced in the same manner as in Example 1 except that the amount of the metal compound added was 0.24 g.

[0278] <Example 3>

[0279] A glass laminate was produced in the same manner as in Example 1 except that the amount of the metal compound added was 0.71 g.

[0280] <Example 4>

[0281] A glass laminate was produced in the same manner as in Example 1, except that ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a solvent, aluminum (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd., metal content 8.3%) was used as a metal compound, and the amount of the metal compound added was set to 0.6 g.

[0282] <Example 5>

[0283] A glass laminate was produced in the same manner as in Example 1, except that ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a solvent, aluminum (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd., metal content 8.3%) was used as a metal compound, and the amount of the metal compound added was set to 1.8 g.

[0284] <Example 6>

[0285] A glass laminate was produced in the same manner as in Example 1 except that bis(2-ethylhexanoate)tin(II) ("Neostann U-28", manufactured by Nitto Kasei Co., Ltd., metal content 29%) was used as the metal compound and the amount of the metal compound added was changed to 0.17 g.

[0286] <Example 7>

[0287] A glass laminate was produced in the same manner as in Example 1 except that bis(2-ethylhexanoate)tin(II) ("Neostann U-28", manufactured by Nitto Kasei Co., Ltd., metal content 29%) was used as the metal compound and the amount of the metal compound added was 0.86 g.

[0288] <Example 8>

[0289] A glass laminate was produced in the same manner as in Example 1 except that a solution of zirconium tetra-n-propoxide ("Orgatics ZA-45", manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 21.1%) diluted 10-fold with Isper G (manufactured by Tonen General Sekiyu KK) was used as the metal compound and the amount added was changed to 0.24 g.

[0290] <Example 9>

[0291] A glass laminate was produced in the same manner as in Example 1 except that the amount of the metal compound added was 4.74 g.

[0292] <Example 10>

[0293] A glass laminate was prepared in the same manner as in Example 1, except that ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a solvent, a solution of aluminum acetylacetonate (III) (manufactured by Tokyo Chemical Industry Co., Ltd., metal content 8.3%) diluted 10 times with ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a metal compound, and the amount of addition was set to 0.6 g.

[0294] <Example 11>

[0295] A glass laminate was produced in the same manner as in Example 1, except that ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a solvent, aluminum (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd., metal content 8.3%) was used as a metal compound, and the amount of the metal compound added was set to 12.05 g.

[0296] <Example 12>

[0297] A glass laminate was produced in the same manner as in Example 1 except that a solution of bis(2-ethylhexanoate)tin(II) ("Neostann U-28", manufactured by Nitto Kasei Co., Ltd., metal content 29%) diluted 10-fold with Isper G (manufactured by Tonen General Sekiyu KK) was used as the metal compound and the amount added was changed to 0.17 g.

[0298] <Example 13>

[0299] A glass laminate was produced in the same manner as in Example 1 except that bis(2-ethylhexanoate)tin(II) ("Neostann U-28", manufactured by Nitto Kasei Co., Ltd., metal content 29%) was used as the metal compound and the amount of the metal compound added was 3.45 g.

[0300] <Example 14>

[0301] A glass laminate was produced in the same manner as in Example 1 except that tetra-n-butyl titanate ("Orgatics TA-21", manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 14.1%) was used as the metal compound and the amount of the metal compound added was 1.06 g.

[0302] <Example 15>

[0303] A glass laminate was produced in the same manner as in Example 1 except that ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a solvent, zinc (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd., metal content 24.8%) was used as a metal compound, and the amount of the metal compound added was set to 0.6 g.

[0304] <Example 16>

[0305] A glass laminate was produced in the same manner as in Example 1 except that bismuth (III) neodecanoate ("Bismuth neodecanoate 16%", manufactured by Nippon Chemical Industry Co., Ltd., metal content 16%) was used as the metal compound and the amount of the metal compound added was 0.94 g.

[0306] <Example 17>

[0307] A glass laminate was produced in the same manner as in Example 1 except that zirconium tetra-n-propoxide ("Orgatics ZA-45", manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 21.1%) (0.24 g) and tin(II) bis(2-ethylhexanoate) ("Neostann U-28", manufactured by Nitto Kasei Co., Ltd., metal content 29%) (0.52 g) were used as metal compounds.

[0308] The glass laminate of Example 17 was confirmed to be capable of separating the glass substrates by inserting a razor blade into the boundary between the silicone resin layer and the glass substrate after heating from room temperature to 550° C. and then cooling to room temperature.

[0309] <Example 18>

[0310] (Synthesis of Organohydrogensiloxane)

[0311] A mixture of 1,1,3,3-tetramethyldisiloxane (5.4 g), tetramethylcyclotetrasiloxane (96.2 g), and octamethylcyclotetrasiloxane (118.6 g) was cooled to 5°C. 11.0 g of concentrated sulfuric acid was slowly added to the mixture while stirring. Then, 3.3 g of water was added dropwise to the mixture over 1 hour. After stirring for 8 hours while maintaining the temperature of the mixture at 10-20°C, toluene was added to the mixture, and the mixture was washed with water and the waste acid was separated until the siloxane layer became neutral. The neutral siloxane layer was concentrated by heating under reduced pressure to remove low-boiling point fractions such as toluene, thereby obtaining an organohydrogensiloxane with k=40 and l=40 in the following formula (1).

[0312]

[0313] (Synthesis of alkenyl-containing siloxane)

[0314] Potassium hydroxide silicate was added to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (3.7 g), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (41.4 g), and octamethylcyclotetrasiloxane (355.9 g) at a Si / K ratio of 20,000 / 1. The mixture was then equilibrated at 150°C for 6 hours under a nitrogen atmosphere. 2 mol of 2-chloroethanol was then added relative to the potassium (potassium) content, and the mixture was neutralized at 120°C for 2 hours. The resulting mixture was then heated and bubbled at 160°C and 666 Pa for 6 hours to remove volatile components, yielding an alkenyl-containing siloxane with an alkenyl equivalent weight La of 0.9 per 100 g and an Mw of 26,000.

[0315] (Preparation of Curable Silicone 2)

[0316] Curable silicone 2 was obtained by mixing organohydrogensiloxane and alkenyl group-containing siloxane so that the molar ratio of all alkenyl groups to all hydrogen atoms bonded to silicon atoms (hydrogen atoms / alkenyl groups) was 0.9.

[0317] The curable silicone 2 (100 parts by mass) was mixed with a silicon compound having an acetylenically unsaturated group represented by the following formula (2) (1 part by mass), and a platinum catalyst was added so that the platinum element content became 100 ppm to obtain a mixture A.

[0318] HC≡CC(CH3)2-O-Si(CH3)3(2)

[0319] (Preparation of Curable Composition 2)

[0320] Mixture A (50 g), zirconium tetra-n-propoxide ("Orgatics ZA-45", manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 21.1%) (0.71 g) as a metal compound, and PMX-0244 (manufactured by Dow Corning Toray Co., Ltd.) (50 g) as a solvent were mixed, and the resulting mixed liquid was filtered with a filter having a pore size of 0.45 μm to obtain a curable composition 2.

[0321] (Production of Glass Laminate)

[0322] The obtained curable composition 2 was applied to a 200×200 mm, 0.5 mm thick support substrate by spin coating and heated on a hot plate at 140°C for 10 minutes. Thereafter, the substrate was heated in an oven at 220°C for 30 minutes in atmospheric air to form an 8 μm thick silicone resin layer.

[0323] Then, a glass substrate having a size of 200×200 mm and a thickness of 0.2 mm was placed on the silicone resin layer and bonded together using a bonding device to produce a glass laminate.

[0324] <Example 19>

[0325] A curable composition was prepared in the same manner as in Example 18, except that tetra-n-butyl titanate ("Orgatics TA-21", manufactured by Matsumoto Fine Chemical Co., Ltd., with a metal content of 14.1%) was used as the metal compound and the amount of the metal compound added was changed to 1.06 g. The resulting curable composition was applied to a 200×200 mm, 0.5 mm thick support substrate by spin coating and heated on a hot plate at 140°C for 10 minutes. Subsequently, the composition was heated in an oven at 220°C for 30 minutes in atmospheric air to form an 8 μm thick silicone resin layer.

[0326] Then, a glass substrate having a size of 200×200 mm and a thickness of 0.2 mm was placed on the silicone resin layer and bonded together using a bonding device to produce a glass laminate.

[0327] <Example 20>

[0328] A curable composition prepared by the same procedure as in Example 3 was spin-coated onto a 200×200 mm, 0.5 mm thick supporting substrate and heated on a hot plate at 100°C for 10 minutes. The composition was then heated in an oven at 250°C for 30 minutes in atmospheric air to form a 4 μm thick silicone resin layer.

[0329] Then, a polyimide film having a thickness of 0.038 mm (trade name: "XENOMAX" manufactured by Toyobo Co., Ltd.) was placed on the silicone resin layer and laminated using a laminating device to produce a resin laminate.

[0330] <Example 21>

[0331] A curable composition prepared by the same procedure as in Example 18 was spin-coated onto a 200×200 mm, 0.5 mm thick supporting substrate and heated on a hot plate at 140°C for 10 minutes. Subsequently, the composition was heated in an oven at 220°C for 30 minutes in atmospheric air to form an 8 μm thick silicone resin layer.

[0332] Then, a polyimide film having a thickness of 0.038 mm (trade name: "XENOMAX" manufactured by Toyobo Co., Ltd.) was placed on the silicone resin layer and laminated using a laminating device to produce a resin laminate.

[0333] <Example 22>

[0334] The curable composition prepared by the same procedure as in Example 18 was applied onto a 0.038 mm thick polyimide film (trade name "XENOMAX" manufactured by Toyobo Co., Ltd.) and heated at 140° C. for 10 minutes on a hot plate.

[0335] Next, a supporting substrate of 200×200 mm and 0.5 mm in thickness was placed on the silicone resin layer and laminated using a laminating device, and then heated in an oven at 220° C. for 30 minutes in atmospheric air to produce a resin laminate.

[0336] <Example 23>

[0337] A curable composition prepared by the same procedure as in Example 14 was spin-coated onto a 200×200 mm, 0.5 mm thick supporting substrate and heated on a hot plate at 100°C for 10 minutes. The composition was then heated in an oven at 250°C for 30 minutes in atmospheric air to form a 4 μm thick silicone resin layer.

[0338] Then, a polyimide film having a thickness of 0.038 mm (trade name: "XENOMAX" manufactured by Toyobo Co., Ltd.) was placed on the silicone resin layer and laminated using a laminating device to produce a resin laminate.

[0339] <Example 24>

[0340] A curable composition was prepared in the same manner as in Example 18, except that tetra-n-butyl titanate ("Orgatics TA-21", manufactured by Matsumoto Fine Chemical Co., Ltd., with a metal content of 14.1%) was used as the metal compound and the amount of the metal compound added was changed to 1.06 g. The prepared curable composition was applied to a 200×200 mm, 0.5 mm thick support substrate by spin coating and heated on a hot plate at 140°C for 10 minutes. Subsequently, the composition was heated in an oven at 220°C for 30 minutes in atmospheric air to form an 8 μm thick silicone resin layer.

[0341] Then, a polyimide film having a thickness of 0.038 mm (trade name: "XENOMAX" manufactured by Toyobo Co., Ltd.) was placed on the silicone resin layer and laminated using a laminating device to produce a resin laminate.

[0342] <Example 25>

[0343] The silicon compound having an acetylenically unsaturated group represented by the above formula (2) (1 part by mass) was mixed with curable silicone 2 (100 parts by mass), and a platinum catalyst was added so that the platinum element content became 100 ppm to obtain a mixture A.

[0344] Mixture A (50 g) and PMX-0244 (manufactured by Dow Corning Toray Co., Ltd.) (50 g) as a solvent were mixed, and the resulting mixed liquid was filtered through a filter having a pore size of 0.45 μm to obtain mixture B (curable composition).

[0345] Mixture B (curable composition) was spin-coated onto a 200×200 mm, 0.5 mm thick support substrate and heated on a hot plate at 140°C for 10 minutes. The substrate was then heated in an oven at 220°C for 30 minutes in atmospheric air to form an 8 μm thick silicone resin layer.

[0346] Then, a polyimide film having a thickness of 0.038 mm (trade name: "XENOMAX" manufactured by Toyobo Co., Ltd.) was placed on the silicone resin layer and laminated using a laminating device to produce a resin laminate.

[0347] <Example 26>

[0348] The mixture B (curable composition) was applied to a polyimide film having a thickness of 0.038 mm (manufactured by Toyobo Co., Ltd., trade name "XENOMAX") and heated at 140° C. for 10 minutes using a hot plate.

[0349] Next, a supporting substrate of 200×200 mm and 0.5 mm in thickness was placed on the silicone resin layer and laminated using a laminating device, and then heated in an oven at 220° C. for 30 minutes in the atmosphere to produce a resin laminate.

[0350] <Evaluation of Foaming Resistance>

[0351] The glass laminate and resin laminate obtained in each example were cut into 15×15 mm samples free of bubbles with a diameter of 1 mm or greater. Each sample was placed in an infrared heating furnace, and the furnace atmosphere was replaced with nitrogen. The temperature was then raised from room temperature to 600°C at a rate of 20°C / minute while observing the condition of the sample within the furnace. The temperature at which bubbles with a diameter of 5 mm or greater were observed during the heating period was defined as the "heat-resistant temperature" of the sample.

[0352] The foaming resistance of the sample was evaluated according to the following criteria based on the heat resistance temperature. "A" to "D" indicate excellent foaming resistance. · "A": Heat resistance temperature 600°C or higher · "B": Heat resistance temperature 550°C or higher and less than 600°C · "C": Heat resistance temperature 530°C or higher and less than 550°C · "D": Heat resistance temperature 500°C or higher and less than 530°C · "E": Heat resistance temperature less than 500°C

[0353] The above results are summarized and shown in Tables 1 to 4 below.

[0354] The following Tables 1 to 4 show the type of curable silicone used in each example (curable silicone 1 or 2).

[0355] Tables 1 to 4 below list the types and contents of the metal elements contained in the silicone resin layer for each example. In this case, if there is only one type, it is listed in "Metal Element 1," and "Metal Element 2" is listed as "-." If there are two types, they are listed in "Metal Element 1" and "Metal Element 2." The content represents the content (ratio) of each metal element in the silicone resin layer, expressed in "mass %," but is abbreviated as "%" in Tables 1 to 3 below.

[0356] Furthermore, the evaluation results of the heat-resistant temperature and the foaming resistance in each example are also described in Tables 1 to 4 below.

[0357] In Table 4 below, only the trade names of the substrates (coated substrates) coated with the curable compositions are shown.

[0358] [Table 1]

[0359]

[0360] [Table 2]

[0361]

[0362] [Table 3]

[0363]

[0364] [Table 4]

[0365]

[0366] As is clear from the results shown in Tables 1 to 4 above, the glass laminates of Examples 1 to 13 and Examples 17 to 18, in which the silicone resin layer contains at least one metal element (specific element) selected from the group consisting of zirconium (Zr), aluminum (Al), and tin (Sn), and the resin laminates of Examples 20 to 22 have excellent foaming resistance.

[0367] In contrast, the glass laminates of Examples 14 to 16, the glass laminate of Example 19, and the resin laminates of Examples 23 to 26, which did not contain the above-mentioned specific element, were inferior in foaming resistance.

[0368] Comparing Examples 2, 4, and 6, Example 2 in which the silicone resin layer contained Zr had better foaming resistance than Examples 4 and 6 in which the silicone resin layer contained Al or Sn.

[0369] <Example 27>

[0370] A laminate was prepared by laminating a Si wafer with a diameter of 150 mm and a thickness of 625 μm in place of the 200×200 mm, 0.2 mm thick glass substrate in Example 18. This laminate was evaluated for blister resistance under the same conditions as in Example 18, and the blister resistance was rated D. The semiconductor laminate of Example 27 exhibited excellent blister resistance.

[0371] <Example 28>

[0372] A laminate was prepared by laminating a Si wafer with a diameter of 150 mm and a thickness of 625 μm in place of the 200×200 mm, 0.2 mm thick glass substrate in Example 19. This laminate was evaluated for blister resistance under the same conditions as in Example 19, and the blister resistance was rated E. The semiconductor laminate of Example 28 had poor blister resistance.

[0373] This application is based on Japanese Patent Application No. 2016-255206 filed on December 28, 2016, Japanese Patent Application No. 2017-120689 filed on June 20, 2017, and Japanese Patent Application No. 2017-185777 filed on September 27, 2017, the contents of which are incorporated herein by reference.

Claims

1. A curable composition for laminating glass, The curable composition comprises curable silicone and aluminum as a metal component. The content of the metal component is 0.099 to 0.290 mass % relative to the total amount of the silicone resin layer formed from the curable composition.

2. The curable composition according to claim 1, wherein The metal component is contained in the form of a metal compound.

3. The curable composition according to claim 2, wherein The metal compound is a complex.

4. The curable composition according to claim 1, wherein The weight average molecular weight of the curable silicone is 5,000 to 60,000.

5. The curable composition according to any one of claims 1 to 4, wherein The curable composition is used for bonding a substrate containing a semiconductor material to glass.

6. A laminate comprising: a substrate containing a semiconductor material; and glass provided on the substrate with a silicone resin layer interposed therebetween. The organic silicone resin layer contains organic silicone resin and aluminum element as a metal component, The content of the metal component in the silicone resin layer is 0.099 to 0.290 mass %.

7. The laminate according to claim 6, wherein The thickness of the organic silicone resin layer is 0.001 to 50 μm.

8. The laminate according to claim 7, wherein The thickness of the silicone resin layer is 0.001 to 10 μm.

9. The laminate according to any one of claims 6 to 8, wherein The substrate includes an LED.

10. Glass with a silicone resin layer, comprising a silicone resin layer and glass. The organic silicone resin layer contains organic silicone resin and aluminum element as a metal component, The content of the metal component in the silicone resin layer is 0.099 to 0.290 mass %.

11. The glass with a silicone resin layer according to claim 10, wherein: The thickness of the organic silicone resin layer is 0.001 to 50 μm.

12. The glass with a silicone resin layer according to claim 11, wherein: The thickness of the silicone resin layer is 0.001 to 10 μm.

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