Laminate, support substrate with silicone resin layer, resin substrate with silicone resin layer, method for manufacturing electronic device

Abstract

This invention relates to a laminate, a support substrate with an organosilicon layer, a resin substrate with an organosilicon layer, and a method for manufacturing electronic devices. The invention provides a laminate that suppresses end deterioration of the organosilicon layer, comprising a support substrate, an organosilicon layer, and a substrate in sequence. The organosilicon layer contains at least one metal element selected from the group consisting of 3d transition metals, 4d transition metals, lanthanides, and bismuth.

Description

[0001] This application is a divisional application of the application filed on December 26, 2017, with application number 201711435275.8, entitled "Laminated body, support substrate with silicone resin layer, resin substrate with silicone resin layer, and method for manufacturing electronic device". Technical Field

[0002] This invention relates to a laminate, a support substrate with an organosilicone layer, a resin substrate with an organosilicone layer, and a method for manufacturing electronic devices. Background Technology

[0003] In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), organic OLED panels, and sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible light, and infrared light have been gradually becoming thinner and lighter. The substrates used in these devices, represented by glass substrates, are also becoming thinner. If the strength of the substrate is insufficient due to thinning, the substrate's processability will be reduced during the device manufacturing process.

[0004] Recently, in order to address the aforementioned problems, the following method has been proposed: preparing a glass laminate formed by stacking 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 has a support plate and an organosilicon resin layer fixed to the support plate, and in the glass laminate, the organosilicon resin layer is peelably bonded to the glass substrate.

[0005] Existing technical documents

[0006] Patent documents

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

[0008] The problem the invention aims to solve

[0009] In recent years, with the increasing functionality and complexity of components for electronic devices, it has become desirable to perform heat treatment in an atmospheric atmosphere and at higher temperatures (e.g., 450°C) when forming components for electronic devices such as oxide semiconductors.

[0010] The inventors prepared the glass laminate described in Patent Document 1 and performed heat treatment under the aforementioned conditions. As a result, they found that whitening and deterioration occurred near the ends of the silicone resin layer in the glass laminate (hereafter referred to as "end deterioration"). Specifically, a top view of the glass laminate subjected to the heat treatment is shown below. Figure 3As shown, deterioration occurs at the end 102 of the silicone resin layer in the glass laminate 100. If gaps are generated near the end of the silicone resin layer along with such end deterioration, the following process defects are likely to occur: chemical reagents used in wet processes may leach into the glass laminate, contaminating the vacuum process equipment subsequently implemented; reagents from previous processes may mix into reagents used in other wet processes, etc.

[0011] In view of the above-mentioned actual situation, the present invention provides a laminate that suppresses end deterioration of the silicone resin layer.

[0012] In addition, the present invention also provides a support substrate with an organosilicon layer, a resin substrate with an organosilicon layer, and a method for manufacturing electronic devices that can be applied to the above-mentioned laminates.

[0013] Solution for solving the problem

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems can be solved by the following configuration.

[0015] (1) A laminate comprising, in sequence, a supporting substrate, an organosilicon resin layer, and a substrate.

[0016] The silicone resin layer contains at least one metal element selected from the group consisting of 3d transition metals, 4d transition metals, lanthanides and bismuth.

[0017] (2) The laminate according to (1), wherein the silicone resin layer contains at least one metal element selected from the group consisting of 3d transition metals, lanthanides and bismuth.

[0018] (3) The laminate according to (1) or (2), wherein the silicone resin layer contains at least one metallic element selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium and bismuth.

[0019] (4) The laminate according to any one of (1) to (3), wherein the silicone resin layer contains at least one metal element selected from the group consisting of iron, manganese, copper, cerium and bismuth.

[0020] (5) The laminate according to any one of (1) to (4), wherein a plurality of substrates are laminated on a support substrate with an organosilicon resin layer sandwiched between them.

[0021] (6) The laminate according to any one of (1) to (5), wherein the substrate is a glass substrate.

[0022] (7) The laminate according to any one of (1) to (5), wherein the substrate is a resin substrate.

[0023] (8) The laminate according to (7), wherein the resin substrate is a polyimide resin substrate.

[0024] (9) The laminate according to any one of (1) to (5), wherein the substrate is a substrate containing semiconductor material.

[0025] (10) The laminate according to (9), wherein the semiconductor material is Si, SiC, GaN, gallium oxide, or diamond.

[0026] (11) A support substrate with an organosilicon resin layer, comprising a support substrate and an organosilicon resin layer in sequence.

[0027] The silicone resin layer contains at least one metal element selected from the group consisting of 3d transition metals, 4d transition metals, lanthanides and bismuth.

[0028] (12) A method for manufacturing an electronic device, comprising:

[0029] In the component forming process, an electronic device component is formed on the surface of the substrate of the laminate as described in any one of (1) to (10), thereby obtaining a laminate with the electronic device component; and

[0030] In the separation process, the support substrate containing the support substrate and the silicone resin layer is removed from the laminate containing the electronic component to obtain an electronic device having a substrate and the electronic component.

[0031] (13) A resin substrate with an organosilicon layer, comprising a resin substrate and an organosilicon layer in sequence.

[0032] The silicone resin layer contains at least one metal element selected from the group consisting of 3d transition metals, 4d transition metals, lanthanides and bismuth.

[0033] (14) A method for manufacturing an electronic device, comprising:

[0034] In the process of forming the laminate, the resin substrate with the silicone resin layer described in (13) and the support substrate are used to form the laminate;

[0035] In the component forming process, an electronic device component is formed on the surface of a resin substrate of a laminate, resulting in a laminate containing the electronic device component; and

[0036] The separation process removes the supporting substrate and silicone resin layer from the laminate containing electronic components to obtain an electronic device having a resin substrate and electronic components.

[0037] The effects of the invention

[0038] According to the present invention, a laminate that suppresses end deterioration of the silicone resin layer can be provided.

[0039] In addition, according to the present invention, a method for manufacturing a support substrate with an organosilicon layer, a resin substrate with an organosilicon layer, and an electronic device that can be applied to the above-mentioned laminate can be provided. Attached Figure Description

[0040] Figure 1 This is a schematic cross-sectional view of one embodiment of the glass laminate of the present invention.

[0041] Figure 2 (A) and Figure 2 (B) is a schematic cross-sectional view showing one embodiment of the manufacturing method of the electronic device of the present invention in accordance with the process sequence.

[0042] Figure 3 A top view showing the end-deterioration that occurs in conventional laminates.

[0043] Explanation of reference numerals in the attached figures

[0044] 10 and 100 glass laminates

[0045] 12 Supporting substrate

[0046] 14. Silicone resin layer

[0047] 14a Surface of silicone resin layer

[0048] 16 Glass substrate

[0049] The first main surface of the 16a glass substrate

[0050] The second main surface of the 16b glass substrate

[0051] 18 Support substrate with resin layer

[0052] 20 Components for electronic devices

[0053] 22 Laminates containing components for electronic devices

[0054] 24 Glass substrates with components

[0055] 102 end

[0056] L End-of-trim length Detailed Implementation

[0057] Hereinafter, the embodiments for carrying out the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

[0058] Figure 1 This is a schematic cross-sectional view of one embodiment of a glass laminate, which is one type of laminate of the present invention.

[0059] like Figure 1 As shown, the glass laminate 10 is a laminate comprising a support substrate 12 and a glass substrate 16, and an organosilicon resin layer 14 disposed therebetween. One side of the organosilicon resin layer 14 is in contact with the support substrate 12, and the other side is in contact with the first main surface 16a of the glass substrate 16.

[0060] 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 support substrate 12. The silicone resin layer 14 peels off from the glass substrate 16, separating into a laminate of the silicone resin layer 14 and the support substrate 12, and the glass substrate 16. In other words, the silicone resin layer 14 is fixed to the support substrate 12, and the glass substrate 16 is peelably laminated onto the silicone resin layer 14.

[0061] The two-layer portion, including the support substrate 12 and the silicone resin layer 14, has the function of reinforcing the glass substrate 16. It should be noted that the two-layer portion, including the support substrate 12 and the silicone resin layer 14, which is pre-manufactured for the purpose of manufacturing the glass laminate 10, is referred to as the support substrate 18 with the silicone resin layer.

[0062] The glass laminate 10 is separated into a glass substrate 16 and a support substrate 18 with an organosilicon layer through the steps described later. The support substrate 18 with the organosilicon layer can be laminated with a new glass substrate 16 and reused as a new glass laminate 10.

[0063] The peel strength between the support substrate 12 and the silicone resin layer 14 is called peel strength (x). If a stress exceeding the peel strength (x) is applied between the support substrate 12 and the silicone resin layer 14 in the peel direction, the support substrate 12 will peel off from the silicone resin layer 14. The peel strength between the silicone resin layer 14 and the glass substrate 16 is called peel strength (y). If a stress exceeding the peel strength (y) is applied between the silicone resin layer 14 and the glass substrate 16 in the peel direction, the silicone resin layer 14 will peel off from the glass substrate 16.

[0064] In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, if stress is applied to the glass laminate 10 in the direction of peeling the support substrate 12 and the glass substrate 16, the glass laminate 10 peels off between the silicone resin layer 14 and the glass substrate 16, separating into the glass substrate 16 and the support substrate 18 with the silicone resin layer.

[0065] The peel strength (x) is preferably sufficiently high compared to the peel strength (y).

[0066] To improve the adhesion of the silicone resin layer 14 to the support substrate 12, it is preferable to cure the curable silicone (described later) on the support substrate 12 to form the silicone resin layer 14. Utilizing the adhesive force during curing, a silicone resin layer 14 bonded to the support substrate 12 with high bonding strength can be formed.

[0067] On the other hand, the adhesion of the cured silicone resin to the glass substrate 16 is generally lower than the adhesion generated during the curing process. Therefore, by forming a silicone resin layer 14 on the support substrate 12 and then stacking the glass substrate 16 on the surface of the silicone resin layer 14, a glass laminate 10 can be manufactured.

[0068] Hereinafter, each layer constituting the glass laminate 10 (supporting substrate 12, glass substrate 16, silicone resin layer 14) will be described in detail first, and then the manufacturing method of the glass laminate will be described in detail.

[0069] <Supporting Substrate>

[0070] The supporting substrate 12 is a component that supports and strengthens the glass substrate 16.

[0071] As the support substrate 12, for example, a glass plate, a plastic plate, a metal plate (e.g., SUS plate), etc. can be used. Generally, the support substrate 12 is preferably formed of a material with a small difference in the coefficient of linear expansion with that of the glass substrate 16, and more preferably of the same material as the glass substrate 16. It is particularly preferred that the support substrate 12 is a glass plate formed of the same glass material as the glass substrate 16.

[0072] The thickness of the support substrate 12 can be thicker or thinner than that of the glass substrate 16. From the perspective of the processability of the glass laminate 10, it is preferable that the thickness of the support substrate 12 is thicker than that of the glass substrate 16.

[0073] When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.03 mm or more for reasons such as ease of handling and resistance to breakage. In addition, for reasons of the requirement of moderate bending without breakage when peeling off the glass substrate, the thickness of the glass plate is preferably 1.0 mm or less.

[0074] The difference in the average coefficient of linear expansion between the support substrate 12 and the glass substrate 16 at 25–300°C is preferably 10 × 10⁻⁶. -7 Below / ℃, more preferably 3×10 -7 Below / ℃, further preferred 1×10 -7 / ℃ below.

[0075] <Glass substrate>

[0076] There are no particular restrictions on the type of glass used for the glass substrate 16, but alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high silica glass, and other oxide-based glasses with silica as the main component are preferred. As an oxide-based glass, glass with a silica content of 40 to 90% by mass, calculated based on oxide content, is preferred.

[0077] More specifically, as a glass substrate 16, a glass substrate used in display devices such as LCDs and OLEDs, and a glass substrate used in sensor panels for receiving electromagnetic waves, X-rays, ultraviolet rays, visible light, infrared rays, etc., can be exemplified by a glass plate made of alkali-free borosilicate glass (manufactured by Asahi Glass Co., Ltd. under the trade name "AN100").

[0078] Regarding the thickness of the glass substrate 16, from the viewpoint of thinning and / or lightweighting, 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. With a thickness of 0.5 mm or less, the glass substrate 16 can be given good flexibility. With a thickness of 0.2 mm or less, the glass substrate 16 can be rolled into a roll.

[0079] In addition, from the perspective of ease of processing of the glass substrate 16, the thickness of the glass substrate 16 is preferably 0.03 mm or more.

[0080] Furthermore, there is no particular limitation on the area (area of ​​the main surface) of the glass substrate 16, but it is preferably 300 cm². 2 above.

[0081] It should be noted that the glass substrate 16 may comprise two or more layers. In this case, the materials forming each layer may be the same or different materials. Furthermore, in this case, "the thickness of the glass substrate 16" refers to the total thickness of all layers.

[0082] There are no particular restrictions on the manufacturing method of the glass substrate 16. Generally, the glass raw material can be melted and the molten glass can be formed into a plate shape. Such forming methods can be common methods, such as float glass, melt glass, slit glass, etc.

[0083] <Organic silicone resin layer>

[0084] The silicone resin layer 14 prevents the glass substrate 16 from shifting position and prevents the glass substrate 16 from breaking due to the separation operation. The surface 14a of the silicone resin layer 14 that contacts the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16.

[0085] It is believed that the silicone resin layer 14 and the glass substrate 16 are bonded by a weak adhesive force, which is a bonding force caused by van der Waals forces.

[0086] Furthermore, the silicone resin layer 14 is bonded to the surface of the support substrate 12 with strong adhesion. 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 specified silicone resin on the support substrate 12), the silicone resin in the silicone resin layer 14 is bonded to the surface of the support substrate 12, resulting in high adhesion. Additionally, performing a treatment that generates strong adhesion between the surface of the support substrate 12 and the silicone resin layer 14 (e.g., treatment using a coupling agent) can further improve the adhesion between the surface of the support substrate 12 and the silicone resin layer 14.

[0087] There is no particular limitation on the thickness of the silicone resin layer 14, but it is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 10 μm or less. There is no particular limitation on the lower limit, and it is mostly 0.001 μm or more. When the thickness of the silicone resin layer 14 is within such a range, cracks are less likely to occur on the silicone resin layer 14, and even if bubbles or foreign matter are trapped between the silicone resin layer 14 and the glass substrate 16, the generation of deformation defects in the glass substrate 16 can be suppressed.

[0088] The aforementioned thickness refers to the average thickness, which is the value obtained by measuring the thickness of the silicone resin layer 14 at more than 5 arbitrary locations using a contact film thickness measuring device and then arithmetically averaging them.

[0089] There is no particular limitation on the surface roughness Ra of the glass substrate 16 side of the silicone resin layer 14. However, from the perspective of improving the lamination and peelability of the glass substrate 16, a roughness of 0.1 to 20 nm is preferred, and 0.1 to 10 nm is more preferred.

[0090] It should be noted that, as a method for measuring surface roughness Ra, the measurement is carried out according to JIS B 0601-2001. The value obtained by arithmetically averaging the Ra values ​​measured at any 5 or more locations is equivalent to the aforementioned surface roughness Ra.

[0091] The silicone resin layer contains at least one metallic element selected from the group consisting of 3d transition metals, 4d transition metals, lanthanides, and bismuth (Bi) (hereinafter collectively referred to as "specific elements"). By including these specific elements, end-point deterioration of the silicone resin layer during high-temperature heat treatment in an atmospheric atmosphere is suppressed. The detailed rationale is unclear, but it can be considered that by including specific elements in the silicone resin layer, oxidation of the silicone resin can be suppressed.

[0092] As 3d transition metals, the transition metals in the fourth period of the periodic table, namely scandium (Sc) to copper (Cu), can be listed. Specifically, these include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu).

[0093] As 4d transition metals, the transition metals in the fifth period of the periodic table, namely yttrium (Y) to silver (Ag), can be listed. Specifically, these include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), and silver (Ag).

[0094] As lanthanide metals, those ranging from lanthanum (La) to lutetium (Lu) can be listed. Specifically, they include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

[0095] In terms of further suppressing end deterioration of the silicone resin layer, the silicone resin layer preferably contains at least one metal element selected from the group consisting of 3d transition metals, lanthanides and bismuth (Bi), more preferably contains at least one metal element selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium and bismuth, even more preferably contains at least one metal element selected from the group consisting of iron, manganese, copper, cerium, chromium and cobalt, and particularly preferably contains at least one metal element selected from the group consisting of iron, manganese, copper, cerium and bismuth.

[0096] It should be noted that the silicone resin layer may contain one of the above-mentioned specific elements, or it may contain two or more of the above-mentioned specific elements.

[0097] There are no particular restrictions on the content of specific elements in the silicone resin layer. However, to further suppress end-deterioration of the silicone resin layer, the content is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, out of 100 parts by mass of the silicone resin layer. It should be noted that there are no particular restrictions on the upper limit of the content of specific elements in the silicone resin layer, but it is preferably 1.0 parts by mass or less, more preferably 0.7 parts by mass or less.

[0098] When the silicone resin layer contains two or more specific elements, it is preferable that their total content is within the above-mentioned range.

[0099] It should be noted that the optimal content for a specific element should be selected based on the type of metal.

[0100] Furthermore, when the silicone resin layer contains at least one metallic element selected from the group consisting of 3d transition metals, lanthanides, and bismuth (Bi) (hereinafter also collectively referred to as "suitable specific elements"), there is no particular limitation on the content of the suitable specific element in the silicone resin layer. However, to further suppress end-deterioration of the silicone resin layer, it is preferable to have at least 0.01 parts by mass, more preferably at least 0.03 parts by mass, in 100 parts by mass of the silicone resin layer. There is no particular limitation on the upper limit of the content of the suitable specific element in the silicone resin layer, but it is preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less.

[0101] When the silicone resin layer contains two or more suitable specific elements, it is preferable that their total content is within the above range.

[0102] The silicone resin layer may contain other metallic elements besides the specific elements mentioned above (e.g., tin, aluminum, platinum).

[0103] Furthermore, the silicone resin layer may contain curing catalysts that promote condensation reactions and curing catalysts that promote addition reactions. Examples of curing catalysts that promote condensation reactions include aluminum chelates such as aluminum triacetylacetonate and aluminum tri(ethylacetoacetate)aluminum, tin compounds such as dibutyltin dilaurate and bis(2-ethylhexanoate)tin(II). Examples of curing catalysts that promote addition reactions include platinum group catalysts.

[0104] It should be noted that when the silicone resin layer contains tin, the peel strength of the glass substrate laminated on the silicone resin layer tends to decrease, while the peeling of the glass substrate is easier. Furthermore, from the perspective of balancing the heat resistance of the silicone resin layer and the peelability of the substrate, it is preferable to use the aforementioned tin and zirconium elements in combination. That is, when the silicone resin layer contains tin, it is preferable to also contain zirconium.

[0105] In addition, when the silicone resin layer contains aluminum, the heat resistance of the silicone resin layer is easily improved.

[0106] The aforementioned specific elements and other metal elements can be in any form within the organosilicon resin layer, including metal, ionic, compound, and complex forms.

[0107] There are no particular limitations on the methods for determining specific elements and other metal elements in the silicone resin layer; well-known methods can be used, such as ICP emission spectrometry (ICP-AES) or ICP mass spectrometry (ICP-MS). Examples of apparatus used in these methods include the PS3520UVDDII inductively coupled plasma atomic emission spectrometry analyzer (Hitachi High-Technologies Corporation) and the Agilent 8800 inductively coupled plasma (triple quadrupole) mass spectrometer (Agilent Technologies Corporation).

[0108] As an example of specific steps based on the above method, firstly, the mass of the silicone resin layer is determined. Next, the silicone resin layer is oxidized and silicated using an oxygen burner or similar method. Then, to remove SiO2 from the oxidized silicone resin layer, it is washed with hydrofluoric acid. The resulting residue is dissolved in hydrochloric acid, and specific elements and / or other metal elements are quantified using the aforementioned ICP emission spectrometry (ICP-AES) or ICP mass spectrometry (ICP-MS). Then, the content of the specific element or other metal element relative to the pre-determined mass of the silicone resin layer is calculated.

[0109] There are no particular limitations on the method for forming an organosilicon resin layer containing a specific element. Examples of methods for forming an organosilicon resin layer include using a curable composition containing a curable organosilicon (described later) and a metal compound containing a specific element.

[0110] It should be noted that, as a method for introducing other metal elements into the silicone resin layer, a method can be listed that, similar to the specific elements mentioned above, uses the above-described curable composition containing curable silicone (described later), a metal compound containing specific elements, and a metal compound containing other metal elements to form the silicone resin layer.

[0111] The details will be described in detail later.

[0112] (Organic silicone resin)

[0113] The silicone resin layer 14 is mainly formed of silicone resin.

[0114] Typically, organosilanooxy units include monofunctional organosilanooxy units (referred to as M units), difunctional organosilanooxy units (referred to as D units), trifunctional organosilanooxy units (referred to as T units), and tetrafunctional organosilanooxy units (referred to as Q units). It should be noted that the Q unit is a unit that does not have an organic group bonded to a silicon atom (but has an organic group bonded to a carbon atom of silicon), but in this invention, it is considered an organosilanooxy unit (containing a silicon-bonded unit). It should also be noted that the monomers forming the M, D, T, and Q units are referred to as M monomers, D monomers, T monomers, and Q monomers, respectively.

[0115] It should be noted that "all organosilanyl units" refers to the total number of M, D, T, and Q units. The ratio of the number (molar amount) of M, D, T, and Q units can be determined based on... 29 The peak area ratio obtained from Si-NMR is used for calculation.

[0116] In an organosiloxane unit, the siloxane bond is a bond formed by two silicon atoms linked by one oxygen atom. Therefore, the oxygen atom in an average silicon atom in a siloxane bond is considered to be half a silicon atom, represented as O in the formula. 1 / 2 More specifically, for example, in a D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to silicon atoms in other units, thus its formula becomes -O. 1 / 2 -(R)2Si-O 1 / 2 -(R represents a hydrogen atom or an organic group). Because there are two O atoms. 1 / 2 Therefore, the D unit is usually represented as (R)2SiO 2 / 2 (In other words, (R)2SiO).

[0117] It should be noted that, in the following explanation, the oxygen atom O bonded to other silicon atoms... ＊ The oxygen atom that bonds the two silicon atoms refers to the oxygen atom in the Si-O-Si bond. Therefore, there is one oxygen atom between the silicon atoms of the two organosilanyl units. ＊ .

[0118] M unit refers to (R)3SiO 1 / 2 The shown unit is an organosilanyloxy unit. Here, R represents a hydrogen atom or an organic group. The number following (R) (3 here) indicates that three hydrogen atoms or organic groups are bonded to a silicon atom. That is, the M unit has one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom O. ＊ More specifically, the M unit has: three hydrogen atoms or organic groups bonded to one silicon atom, and one oxygen atom (O) bonded to one silicon atom. ＊ .

[0119] D unit refers to (R)2SiO 2 / 2 (R represents a hydrogen atom or an organic group) This is an organosilanyloxy unit. That is, the D unit has one silicon atom, two hydrogen atoms or organic groups bonded to that silicon atom, and two oxygen atoms (O) bonded to other silicon atoms. ＊ The unit.

[0120] T unit refers to RSiO 3 / 2 The organosilanooxy unit (R represents a hydrogen atom or an organic group) is shown. That is, the T unit has one silicon atom, one hydrogen atom or organic group bonded to that silicon atom, and three oxygen atoms (O) bonded to other silicon atoms. ＊ The unit.

[0121] The Q unit refers to the organosilasilyloxy unit represented by SiO2. That is, the Q unit has one silicon atom and four oxygen atoms (O) bonded to other silicon atoms. ＊ The unit.

[0122] It should be noted that, as organic groups, examples 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 halogenated monovalent hydrocarbon groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. It should also be noted that, as organic groups, monovalent hydrocarbon groups with 1 to 12 carbon atoms (preferably around 1 to 10 carbon atoms) that are unsubstituted or halogenated are preferred.

[0123] The structure of the silicone resin constituting the silicone resin layer 14 is not particularly limited, but it is preferable to contain a silicone resin selected from (R)3SiO2, which provides a better balance between the lamination and peelability of the glass substrate 16. 1 / 2 The organosilyloxy unit (M unit) and (R)SiO shown 3 / 2 At least one specific organosiloxy unit from the group consisting of the shown organosiloxy units (T units).

[0124] Furthermore, the ratio of the specific organosiloxy units mentioned above, relative to all organosiloxy units, is preferably 60 mol% or more, more preferably 80 mol% or more. There is no particular upper limit, and it is mostly below 100 mol%. It should be noted that the ratio of the number (molar amount) of M units and T units can be determined based on... 29 The peak area ratio obtained from Si-NMR is used for calculation.

[0125] Silicone resins are typically obtained by curing (crosslinking) a curable silicone that can be formed into the silicone resin through a curing process. That is, silicone resin is equivalent to the cured product of a curable silicone.

[0126] Curable silicones are classified according to their curing mechanism into condensation reaction silicones, addition reaction silicones, UV-curable silicones, and electron beam-curable silicones, all of which can be used. Among them, condensation reaction silicones and addition reaction silicones are preferred.

[0127] As a condensation-reaction type organosilicon, a hydrolyzable organosilane compound or a mixture thereof (monomer mixture) can be used as the monomer, or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing the monomer or monomer mixture. Alternatively, a mixture of the partially hydrolyzed condensate and the monomer can also be used. It should be noted that one monomer can be used alone, or two or more monomers can be used in combination. By using this condensation-reaction type organosilicon, a hydrolysis-condensation reaction (sol-gel reaction) can be carried out, thereby forming an organosilicon resin.

[0128] The aforementioned monomers (hydrolyzable organosilane compounds) are typically composed of (R'-) a Si(-Z) 4-a The formula is represented by the symbol . Here, '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, compounds with a = 3 are monomers M, compounds with a = 2 are monomers D, compounds with a = 1 are monomers T, and compounds with a = 0 are monomers Q. In monomers, the Z group is usually a hydrolyzable group. Furthermore, when there are 2 or 3 'R's (when a is 2 or 3), the multiple 'R's can be different.

[0129] Curable organosilicones, as partially hydrolyzed condensates, can be produced by converting a portion of the Z-group of the monomer into oxygen atoms (O). ＊ The reaction is used to obtain it. When the Z-group of the monomer is a hydrolyzable group, the Z-group is converted to a hydroxyl group through a hydrolysis reaction, followed by a dehydration condensation reaction between two hydroxyl groups bonded to other silicon atoms, with the two silicon atoms connected by an oxygen atom (O). ＊ Bonding. Hydroxyl groups (or unhydrolyzed Z groups) remain in the curable silicone. During the curing of the silicone, these hydroxyl and Z groups react in the same way as described above to achieve curing. The cured silicone typically forms a three-dimensionally cross-linked polymer (silicone resin).

[0130] When the Z-group of the monomer is a hydrolyzable group, examples of such Z-groups include alkoxy groups, halogen atoms (e.g., chlorine atoms), acyloxy groups, and isocyanate groups. In most cases, monomers with an alkoxy group as the Z-group are used, and such monomers are also called alkoxysilanes.

[0131] Compared to other hydrolyzable groups such as chlorine atoms, alkoxy groups are less reactive. In cured organosilicones obtained using monomers with alkoxy groups as Z-groups (alkoxysilanes), unreacted alkoxy groups often exist together with hydroxyl groups as Z-groups.

[0132] From the perspective of reaction control and processing, partially hydrolyzed condensates (organopolysiloxanes) obtained from hydrolyzable organosilane compounds are preferred as the aforementioned condensation reaction type organosilicon. Partially hydrolyzed condensates are obtained by partially hydrolyzing and condensing a hydrolyzable organosilane compound. There are no particular limitations on the method of partial hydrolyzing and condensing. Typically, the hydrolyzable organosilane compound is reacted in a solvent in the presence of a catalyst. Examples of catalysts include acid catalysts and base catalysts. Furthermore, water is generally preferred in the hydrolysis reaction. The partially hydrolyzed condensate is preferably a substance produced by reacting a hydrolyzable organosilane compound in a solvent in the presence of an acidic or alkaline aqueous solution.

[0133] As a suitable form of hydrolyzable organosilane compound for use, alkoxysilanes can be listed as described above. That is, as one of the suitable forms of curable organosilicon, curable organosilicon obtained by hydrolysis and condensation reactions of alkoxysilanes can be listed.

[0134] When using alkoxysilanes, the degree of polymerization of the partially hydrolyzed condensate tends to increase, resulting in better performance of the present invention.

[0135] As an addition-reactive organosilicon, 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. Heating treatment can promote the curing of the addition-reactive organosilicon. The main agent in the addition-reactive organosilicon is preferably an organopolysiloxane (i.e., an organoalkenyl polysiloxane; preferably linear) having an alkenyl group (vinyl group, etc.) bonded to a silicon atom, where the alkenyl group serves as a crosslinking point. The crosslinking agent in the addition-reactive organosilicon is preferably an organopolysiloxane (i.e., an organohydrogen polysiloxane; preferably linear) having a hydrogen atom (hydrogen silyl group, etc.) bonded to a silicon atom, where the hydrogen silyl group serves as a crosslinking point.

[0136] Addition-reactive organosilicones are cured by an addition reaction at the crosslinking points of the main agent and the crosslinking agent. It should be noted that, in terms of superior heat resistance derived from the crosslinking structure, the molar ratio of hydrogen atoms bonded to silicon atoms in organohydrogen polysiloxanes to alkenyl groups in organoalkenyl polysiloxanes is preferably 0.5 to 2.

[0137] There are no particular limitations on the weight-average molecular weight (Mw) of curable organosilicones such as condensation-reaction type and addition-reaction type, but 5,000 to 60,000 is preferred, and 5,000 to 30,000 is more preferred. If Mw is 5,000 or more, it is excellent from the viewpoint of coatability, and if Mw is 60,000 or less, it is excellent from the viewpoint of solubility in solvents and coatability.

[0138] There are no particular limitations on the manufacturing method of the aforementioned silicone resin layer 14, and known methods can be used. In particular, regarding the high productivity of the silicone resin layer 14, a preferred manufacturing method is to coat a curable composition containing a curable silicone that forms the aforementioned silicone resin and a metal compound containing a specific element onto a support substrate 12, remove the solvent as needed, form a coating film, and then cure the curable silicone in the coating film to produce the silicone resin layer 14.

[0139] As described above, as a curable silicone, a hydrolyzable organosilane compound as a monomer, and / or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing the monomer can be used. Alternatively, a mixture of organoalkenyl polysiloxanes and organohydrogen polysiloxanes can also be used as a curable silicone.

[0140] The structure of the metal compound containing a specific element in the above-described curable composition is not particularly limited as long as it contains the specified specific element; well-known metal compounds can be listed. It should be noted that, in this specification, the term "complex" is included in the aforementioned metal compounds.

[0141] As a metal compound containing a specific element, a complex containing a specific element is preferred. A complex is an aggregate formed with a metal element atom or ion as the center and ligands (atoms, groups of atoms, molecules or ions) bonded to it.

[0142] There are no particular restrictions on the types of ligands contained in the above complexes. For example, ligands selected from the group consisting of β-diketones, carboxylic acids, alkoxides and alcohols can be listed.

[0143] Examples of β-diketones include acetylacetone, methyl acetoacetate, ethyl acetoacetate, and benzoylacetone.

[0144] Examples of carboxylic acids include acetic acid, 2-ethylhexanoic acid, cycloalkyl acids, and neodecanoic acid.

[0145] Examples of alkoxides include methanol salts, ethanol salts, isopropoxide salts, and butoxide salts.

[0146] Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0147] Specifically, examples of metal compounds containing specific elements include organomanganese compounds such as tris(2,4-pentanedione)manganese(III), organoiron compounds such as tris(2,4-pentanedione)iron(III) and tris(2-ethylhexanoate)iron(III), organocobalt compounds such as bis(2,4-pentanedione)cobalt(II), organonickel compounds such as bis(2,4-pentanedione)nickel(II), organocopper compounds such as copper neodecanoate(II), organobismuth compounds such as bis(2,4-pentanedione)bismuth(III), organozirconium compounds such as tetra(monomethylethanol)zirconium, tetra(monoethylethanol)zirconium, tetra(monobutylethanol)zirconium, and n-propoxidezirconium compounds, organocerium compounds such as tris(2-ethylhexanoate)cerium(III), and organochromium compounds such as tris(2,4-pentanedione)chromium(III).

[0148] There is no particular limitation on the content of the metal compound containing the specific element in the curable composition, but it is preferred to adjust it in a way that the content of the specific element in the above-mentioned silicone resin layer is within an appropriate range.

[0149] When using condensation-reaction type organosilicon as the curable organosilicon, the curable composition may, as needed, contain a curing catalyst that promotes the condensation reaction as a metal compound containing other metal elements. Examples of curing catalysts that promote the condensation reaction include aluminum chelates such as aluminum triacetylacetonate and aluminum tri(ethylacetoacetate), dibutyltin dilaurate, and tin compounds such as bis(2-ethylhexanoate)tin(II).

[0150] When using addition-reaction type organosilicon as the curable organosilicon, the curable composition may, as needed, contain a platinum catalyst as a metal compound containing other metal elements.

[0151] The platinum catalyst is used to promote the hydrosilylation reaction of the alkenyl group in the above-mentioned organoalkenyl polysiloxane with the hydrogen atom in the above-mentioned organohydrogen polysiloxane.

[0152] The curable composition may contain a solvent, in which case the thickness of the coating film can be controlled by adjusting the concentration of the solvent. From the perspective of excellent processability and easier control of the film 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.

[0153] As a solvent, there are no particular restrictions as long as it can easily dissolve curable organosilicon in the working environment and can be easily evaporated and removed. Specifically, examples include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate, octamethylcyclotetrasiloxane, and isoparaffin solvents.

[0154] In addition, the curing composition may contain various additives. For example, it may contain leveling agents. Examples of leveling agents include fluorinated leveling agents such as Megafac F558, Megafac F560, and Megafac F561 (all manufactured by DIC Corporation).

[0155] <Glass Laminates and Their Manufacturing Methods>

[0156] As described above, the glass laminate 10 is a laminate comprising a support substrate 12 and a glass substrate 16, and an organosilicon resin layer 14 disposed therebetween.

[0157] There are no particular limitations on the manufacturing method of the glass laminate 10. In order to obtain a laminate with a peel strength (x) higher than the peel strength (y), it is preferable to form an organosilicon resin layer 14 on the surface of the support substrate 12. Among them, the preferred method is to coat the surface of the support substrate 12 with a curable composition containing a curable organosilicon and a metal compound containing a specific element, cure the obtained coating to obtain the organosilicon resin layer 14, and then laminate a glass substrate 16 on the surface of the organosilicon resin layer 14 to manufacture the glass laminate 10.

[0158] It can be assumed that if the curable silicone is cured on the surface of the support substrate 12, it will bond with the support substrate 12 through interaction during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate 12 will be higher. Therefore, even if the glass substrate 16 and the support substrate 12 are made of the same material, it is possible to design differences in the peel strength between the silicone resin layer 14 and the two.

[0159] The following process is referred to as resin layer forming process 1, which involves forming a curable silicone layer on the surface of the support substrate 12 and forming a silicone resin layer 14 on the surface of the support substrate 12. The process of stacking a glass substrate 16 on the surface of the silicone resin layer 14 to form a glass laminate 10 is referred to as lamination process 1. The steps of each process are described in detail.

[0160] (Resin layer formation process 1)

[0161] In the resin layer forming process 1, a curable organosilicon layer is formed on the surface of the support substrate 12, and an organosilicon resin layer 14 is formed on the surface of the support substrate 12.

[0162] First, in order to form a curable silicone layer on the support substrate 12, the aforementioned curable composition is coated onto the support substrate 12. Next, it is preferable to perform a curing treatment on the curable silicone layer to form a cured layer.

[0163] There are no particular limitations on the method of coating the curable composition on the surface of the support substrate 12, and known methods can be listed. For example, spraying, molding, spin coating, dip coating, roller coating, bar coating, screen printing, gravure coating, etc. can be listed.

[0164] Next, the curable silicone on the support substrate 12 is cured to form a cured layer (silicone resin layer).

[0165] There are no particular restrictions on the curing method; the most suitable treatment can be implemented depending on the type of curable silicone used. For example, when using condensation-reaction silicones and addition-reaction silicones, thermal curing is preferred as the curing treatment.

[0166] The preferred temperature for thermosetting is 150–550°C, more preferably 200–450°C. Additionally, the preferred heating time is typically 10–300 minutes, more preferably 20–120 minutes. It should be noted that the heating conditions can be varied to allow for phased implementation.

[0167] It should be noted that, in the thermosetting process, it is preferable to perform post-curing (formal curing) after pre-curing (preparatory curing). By performing pre-curing, an organosilicon resin layer 14 with excellent heat resistance is obtained.

[0168] (Layering process 1)

[0169] The lamination process 1 is a process of laminating a glass substrate 16 on the surface of the silicone resin layer 14 obtained in the above-mentioned resin layer formation process, thereby obtaining a glass laminate 10 having a support substrate 12, a silicone resin layer 14 and a glass substrate 16 in sequence.

[0170] There are no particular limitations on the method of stacking the glass substrate 16 on the silicone resin layer 14, and well-known methods can be listed.

[0171] For example, a method of laminating a glass substrate 16 onto the surface of a silicone resin layer 14 under normal pressure can be cited. It should be noted that, if necessary, after laminating the glass substrate 16 onto the surface of the silicone resin layer 14, a roller or press can be used to press the glass substrate 16 onto the silicone resin layer 14. Using a roller or press makes it easier to remove air bubbles mixed between the silicone resin layer 14 and the glass substrate 16, which is therefore preferable.

[0172] Vacuum lamination and vacuum pressing methods can suppress the incorporation of air bubbles and achieve a good seal, making them preferred methods. Vacuum pressing also has the following advantages: even if tiny air bubbles remain, they will not grow due to heating and are less likely to cause deformation defects in the glass substrate 16.

[0173] Preferably, the surface of the glass substrate 16 in contact with the silicone resin layer 14 is thoroughly cleaned during the lamination of the glass substrate 16, and the lamination is performed in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 16, so this is preferred.

[0174] It should be noted that after the glass substrate 16 is laminated, a pre-annealing treatment (heat treatment) can be performed as needed. By performing this pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 is improved, and an appropriate peel strength (y) can be achieved.

[0175] It should be noted that the above describes the use of glass substrates as substrates in detail, but there are no particular restrictions on the type of substrate.

[0176] For example, substrates include metal substrates, semiconductor substrates, resin substrates, and glass substrates. Furthermore, a substrate can be, for example, a metal plate made of two different metals, or a substrate made of multiple materials of the same type. Moreover, a substrate can be, for example, a composite substrate made of resin and glass, or a composite substrate made of two or more different materials (e.g., selected from metals, semiconductors, resins, and glass).

[0177] There are no particular limitations on the thickness of the substrate, such as the metal plate or semiconductor substrate. From the viewpoint of thinning and / or lightweighting, a thickness of 0.5 mm or less is preferred, more preferably 0.4 mm or less, and even more preferably 0.2 mm or less. In addition, there are no particular limitations on the lower limit of the thickness, but 0.005 mm or more is preferred.

[0178] Furthermore, there are no particular restrictions on the area of ​​the substrate (the area of ​​the main surface), but from the perspective of electronic device productivity, 300 cm² is preferred. 2 above.

[0179] Furthermore, there are no particular restrictions on the shape of the substrate; it can be rectangular or circular. Additionally, the substrate can have an orientation plane (a flat portion formed on the outer periphery of the substrate) or a notch (one or more V-shaped notches formed on the outer periphery of the substrate).

[0180] <Resin substrate and method for manufacturing laminate using resin substrate>

[0181] As the aforementioned resin substrate, a resin substrate with excellent heat resistance that can withstand the heat treatment during the device manufacturing process is preferred. Examples of resins constituting the resin substrate include polybenzimidazole resin (PBI), polyimide resin (PI), polyetheretherketone resin (PEEK), polyamide resin (PA), fluoropolymer resin, epoxy resin, and polyphenylene sulfide resin (PPS). In particular, from the viewpoints of excellent heat resistance, excellent chemical resistance, low coefficient of thermal expansion, and high mechanical properties, a polyimide resin substrate formed from polyimide resin is preferred.

[0182] Furthermore, in order to form high-precision wiring for electronic devices on the resin substrate, a smooth surface of the resin substrate is preferred. Specifically, the surface roughness Ra of the resin substrate is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.

[0183] Regarding the thickness of the resin substrate, from the viewpoint of processability in the manufacturing process, 1 μm or more is preferred, and 10 μm or more is more preferred. Furthermore, from the viewpoint of flexibility, 1 mm or less is preferred, and 0.2 mm or less is more preferred.

[0184] For the coefficient of thermal expansion of the resin substrate, a smaller difference between the coefficient of thermal expansion and that of the electronic device and the supporting substrate is preferred because it can suppress warping of the laminate after heating or cooling. Specifically, the difference between the coefficients of thermal expansion of the resin substrate and the supporting substrate is preferably 0 to 90 × 10⁻⁶. -6 / ℃, more preferably 0~30×10 -6 / ℃.

[0185] There are no particular limitations on the manufacturing method of the laminate when using a resin substrate as the substrate. For example, the laminate can be manufactured using the same method as in the case where a glass substrate is used. That is, an organosilicon resin layer can be formed on a support substrate, and a resin substrate can be laminated on the organosilicon resin layer to manufacture the laminate.

[0186] It should be noted that the laminate consisting of a supporting substrate, an organosilicon resin layer, and a resin substrate will be referred to as a resin laminate in the future.

[0187] In addition, as another manufacturing method of the resin laminate, it is also preferable to form an organosilicon resin layer on the surface of a resin substrate to manufacture the resin laminate.

[0188] The adhesion of silicone resin layers to resin substrates generally tends to be low. Therefore, when a silicone resin layer is formed on the surface of a resin substrate and the resulting resin substrate with the silicone resin layer is laminated with a support substrate to obtain a resin laminate, 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 strong when a glass plate is used as the support substrate.

[0189] That is, similar to the case of glass laminates, resin laminates can be separated into a resin substrate and a support substrate with an organosilicon resin layer.

[0190] Other manufacturing methods of the above-mentioned resin laminate mainly include: a process of forming a curable organosilicon layer on the surface of a resin substrate and forming an organosilicon resin layer on the surface of the resin substrate (resin layer forming process 2); and a process of laminating a support substrate on the surface of the organosilicon resin layer to form a resin laminate (lamination process 2).

[0191] The steps of each of the above processes are described in detail below.

[0192] (Resin layer formation process 2)

[0193] Resin layer formation step 2 involves forming a curable organosilicon layer on the surface of a resin substrate and forming an organosilicon resin layer on the surface of the resin substrate. Through this step, a resin substrate with an organosilicon resin layer can be obtained, which sequentially comprises a resin substrate and an organosilicon resin layer.

[0194] In this process, in order to form a curable silicone layer on the resin substrate, the aforementioned curable composition is coated onto the resin substrate. Next, it is preferable to perform a curing treatment on the curable silicone layer to form a cured layer.

[0195] There are no particular limitations on the method of coating the curable composition onto the surface of the resin substrate, and known methods can be listed. For example, spray coating, mold coating, spin coating, dip coating, roller coating, bar coating, screen printing, gravure coating, etc.

[0196] Next, the curable silicone on the resin substrate is cured to form a cured layer (silicone resin layer).

[0197] There are no particular restrictions on the curing method; the most suitable treatment can be implemented depending on the type of curable silicone used. For example, when using condensation-reaction silicones and addition-reaction silicones, thermal curing is preferred as the curing treatment.

[0198] The thermosetting conditions are performed within the heat resistance range of the resin substrate. For example, the thermosetting temperature is preferably 50–400°C, more preferably 100–300°C. Furthermore, the heating time is typically preferably 10–300 minutes, more preferably 20–120 minutes.

[0199] The method for forming the silicone resin layer is as described above.

[0200] (Layering process 2)

[0201] Lamination process 2 is a process of forming a resin laminate by laminating a support substrate on the surface of an organosilicon resin layer. That is, this process is a process of forming a resin laminate using a resin substrate with an organosilicon resin layer and a support substrate.

[0202] There are no particular limitations on the method of laminating the support substrate onto the silicone resin layer; known methods can be listed, such as the method described in the description of lamination step 1 in the manufacture of the glass laminate.

[0203] It should be noted that after the support substrate is laminated, heat treatment can be performed as needed. Heat treatment improves the adhesion of the laminated support substrate to the silicone resin layer, achieving an appropriate peel strength (x).

[0204] The preferred temperature for the heat treatment is 50–400°C, more preferably 100–300°C. Additionally, the preferred heating time is typically 1–120 minutes, more preferably 5–60 minutes. It should be noted that the heating conditions can be varied by changing the temperature and implemented in stages.

[0205] Furthermore, if the resin laminate is heated in the process of forming components for electronic devices as described later, the heating process can be omitted.

[0206] From the viewpoint of improving peel strength (x) and adjusting the balance between peel strength (x) and peel strength (y'), it is preferable to perform surface treatment on at least one of the support substrate and the silicone resin layer before laminating the support substrate onto the silicone resin layer, and more preferably to perform surface treatment on the silicone resin layer.

[0207] Examples of surface treatment methods include corona treatment, plasma treatment, and UV ozone treatment, among which corona treatment is preferred.

[0208] Resin substrates with an organosilicon layer can be manufactured using a roll-to-roll method, where an organosilicon layer is formed on the surface of a rolled resin substrate and then it is rolled up again. This method offers excellent production efficiency.

[0209] When a silicone resin layer is formed on a support substrate, and a curable composition is coated onto the support substrate, due to the so-called "coffee ring phenomenon," the thickness of the silicone resin layer at its outer periphery tends to be thicker than that at its center. In this case, it is necessary to cut off and remove the support substrate portion where the silicone resin layer is disposed, which is labor-intensive and costly when the support substrate is a glass plate.

[0210] On the other hand, when an organosilicon resin layer is formed on a resin substrate, the resin substrate generally has excellent processability and cost, so even if the problems mentioned above occur, it is relatively easy to remove the resin substrate portion on the outer periphery where the organosilicon resin layer is disposed.

[0211] <Semiconductor substrate and method for manufacturing laminate using semiconductor substrate>

[0212] Materials used as semiconductor substrates include Si, SiC, GaN, gallium oxide, and diamond. Si substrates are also referred to as Si wafers.

[0213] In order to form high-precision wiring for 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.

[0214] Regarding the thickness of the semiconductor substrate, from the viewpoint of processability in the manufacturing process, 1 μm or more is preferred, and 10 μm or more is more preferred. From the viewpoint of miniaturization of electronic devices, 1 mm or less is preferred, and 0.2 mm or less is more preferred.

[0215] For the coefficient of thermal expansion of the semiconductor substrate, a smaller difference between the coefficient of thermal expansion and that of the electronic device and the supporting substrate is preferred because it can suppress warping of the laminate after heating or cooling. Specifically, the difference between the coefficients of thermal expansion of the semiconductor substrate and the supporting substrate is preferably 0 to 90 × 10⁻⁶. -6 / ℃, more preferably 0~30×10 -6 / ℃.

[0216] There are no particular limitations on the manufacturing method of the laminate when a semiconductor substrate is used as the substrate. For example, the laminate can be manufactured using the same method as in the case where a glass substrate is used. That is, an organosilicon resin layer can be formed on a support substrate, and a semiconductor substrate can be laminated on the organosilicon resin layer to manufacture the laminate.

[0217] The laminate that subsequently contains a supporting substrate, an organosilicon resin layer, and a semiconductor substrate is also called a semiconductor laminate.

[0218] It should be noted that, as described later, end-deterioration is also suppressed in the semiconductor stack.

[0219] (Layered structure)

[0220] The laminate of the present invention (e.g., the glass laminate 10 described above) can be used for various applications, such as manufacturing electronic components like display panels, PV, thin-film secondary batteries, semiconductor wafers with circuits formed on their surfaces, and sensor panels, as described later. It should be noted that in these applications, there are also cases where the laminate is exposed to atmospheric conditions and high temperatures (e.g., 450°C or higher) for (e.g., 20 minutes or more).

[0221] Here, the display 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.

[0222] Here, the receiving sensor panel includes electromagnetic wave receiving sensor panels, X-ray light receiving sensor panels, ultraviolet light receiving sensor panels, visible light receiving sensor panels, infrared light receiving sensor panels, etc. The substrates used in these receiving sensor panels can be reinforced with reinforcing sheets such as resin.

[0223] It should be noted that, Figure 1 The illustration shows a configuration in which a single substrate (e.g., a glass substrate, a resin substrate, or a semiconductor substrate) sandwiches an organosilicon resin layer and is stacked on a support substrate. However, the laminate of the present invention is not limited to this configuration; for example, it may also be a configuration in which multiple substrates sandwiching organosilicon resin layers are stacked on a support substrate (hereinafter also referred to as a "multi-sided bonding configuration").

[0224] More specifically, the multi-sided bonding solution refers to a solution where multiple substrates are sandwiched between a silicone resin layer and a support substrate. That is, it is not a solution where multiple substrates are overlapped (only one of the multiple substrates has a silicone resin layer sandwiched between it and the support substrate).

[0225] In multi-sided bonding solutions, for example, multiple silicone resin layers can be disposed on each of the various substrates, and multiple substrates and silicone resin layers can be disposed on a single support substrate. However, this is not a limitation; for example, the various substrates can be disposed on a single silicone resin layer (e.g., of the same size as the support substrate) formed on a single support substrate.

[0226] <Electronic Devices and Their Manufacturing Methods>

[0227] In this invention, the above-described laminate is used to manufacture an electronic device comprising a substrate and electronic components (hereinafter also appropriately referred to as a "substrate with components").

[0228] The manufacturing method of the electronic device using the glass laminate 10 described above will be described in detail below.

[0229] There are no particular restrictions on the manufacturing method of electronic devices. From the perspective of excellent productivity of electronic devices, the following method is preferred: forming electronic device components on a glass substrate in the above-mentioned glass laminate, manufacturing a laminate with electronic device components, and separating the obtained laminate with electronic device components into electronic devices (substrate with components) and a support substrate with silicone resin layer from the glass substrate side interface of the silicone resin layer as the peeling surface.

[0230] The process of forming electronic device components on the glass substrate in the above-mentioned glass laminate and manufacturing a laminate with electronic device components is called the component forming process; the process of separating the laminate with electronic device components from the glass substrate side interface with the silicone resin layer as the peeling surface into a substrate with components and a support substrate with silicone resin layer is called the separation process.

[0231] The following is a detailed description of the materials and steps used in each process.

[0232] (Component Formation Process)

[0233] The component forming process is a process of forming a component for an electronic device on the glass substrate 16 in the aforementioned glass laminate 10. More specifically, as... Figure 2 As shown in (A), an electronic device component 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16, resulting in a laminate 22 with the electronic device component.

[0234] First, the electronic component 20 used in this process will be described in detail, followed by a detailed description of the steps of the process.

[0235] (Components for electronic devices (functional elements))

[0236] The electronic device component 20 is a component formed on the glass substrate 16 in the glass laminate 10 and constituting at least a part of the electronic device. More specifically, examples of electronic device components 20 include components used in electronic components such as display device panels, solar cells, thin-film secondary batteries, or semiconductor wafers with circuits formed on their surfaces, and sensor receiving panels (e.g., components for display devices, components for solar cells, components for thin-film secondary batteries, circuits for electronic components, and components for sensor receiving).

[0237] For example, as components for solar cells, for silicon-type solar cells, examples include transparent electrodes such as tin oxide for the positive electrode, silicon layers represented by p-layers / i-layers / n-layers, and metals for the negative electrode. In addition, various components corresponding to compound-type, dye-sensitized-type, and quantum dot-type solar cells can be listed.

[0238] In addition, as components for thin-film secondary batteries, for lithium-ion type batteries, examples include transparent electrodes such as metals or metal oxides for positive and negative electrodes, lithium compounds for electrolyte layers, metals for current collector layers, and resins for sealing layers. Furthermore, various components corresponding to nickel-metal hydride type, polymer type, and ceramic electrolyte type batteries can be listed.

[0239] In addition, as electronic components, CCDs and CMOS circuits can include conductive metals, insulating silicon oxide, silicon nitride, etc. Furthermore, various components corresponding to various sensors such as pressure sensors / accelerometers, rigid printed circuit boards, flexible printed circuit boards, and rigid-flexible printed circuit boards can be listed.

[0240] (Steps of the process)

[0241] There are no particular limitations on the manufacturing method of the above-mentioned laminate 22 with electronic device components. Depending on the type of constituent components of the electronic device components, the electronic device components 20 are formed on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by conventionally known methods.

[0242] It should be noted that the component 20 for electronic devices may not be the entirety (hereinafter referred to as "the entire component") of the component ultimately formed on the second main surface 16b of the glass substrate 16, but rather a portion of the entire component (hereinafter referred to as "the partial component"). Alternatively, a substrate with the partial component peeled off from the silicone resin layer 14 may be used as a substrate with the entire component in a subsequent process (equivalent to the electronic device described later).

[0243] Furthermore, for a substrate with all components peeled off from the silicone resin layer 14, other electronic device components can be formed on its peeled surface (first main surface 16a). Alternatively, two laminates with all components can be assembled, and then two support substrates with silicone resin layers can be peeled off from the laminates with all components to manufacture a substrate with components having two glass substrates.

[0244] 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, depositing a hole injection layer / hole transport layer / light emission layer / electron transport layer, forming a back electrode, and sealing with a sealing plate. Specifically, these layer formation and processing include, for example, film deposition, vapor deposition, and bonding of the sealing plate.

[0245] In addition, for example, in the case of manufacturing a TFT-LCD, there are various processes such as the following: TFT formation process, in which a metal film and metal oxide film formed by conventional film formation methods such as CVD and sputtering are patterned on the second main surface 16b of the glass substrate 16 of the glass laminate 10 to form a thin film transistor (TFT); CF formation process, in which a color filter (CF) is formed by using a resist to form a pattern on the second main surface 16b of the glass substrate 16 of another glass laminate 10; and a bonding process, in which the laminate with TFTs obtained in the TFT formation process and the laminate with CFs obtained in the CF formation process are laminated.

[0246] For example, in the manufacture of a micro LED display, the process includes: a TFT formation process, in which a metal film and a metal oxide film formed by conventional film deposition methods such as CVD and sputtering are patterned on at least the second main surface 16b of the glass substrate 16 of the glass laminate 10 using a photoresist to form a thin film transistor (TFT); and an LED mounting process, in which an LED chip is mounted on the formed TFT. In addition, processes such as planarization, wiring formation, and sealing can also be performed.

[0247] In the TFT formation process and the CF formation process, well-known photolithography and etching techniques are used to form TFTs and CFs on the second main surface 16b of the glass substrate 16. At this time, a resist can be used as the coating liquid for pattern formation.

[0248] It should be noted that the second main surface 16b of the glass substrate 16 can be cleaned as needed before forming the TFT and CF. Well-known dry cleaning or wet cleaning methods can be used as cleaning methods.

[0249] In the bonding process, the thin-film transistor forming surface of the TFT-based laminate is aligned with the color filter forming surface of the CF-based laminate, and they are bonded together using a sealant (e.g., a UV-curable sealant for cell formation). Then, liquid crystal material is injected into the cell formed by the TFT-based laminate and the CF-based laminate. Methods for injecting liquid crystal material include, for example, depressurized injection and drop-feed injection.

[0250] It should be noted that the manufacturing of component 20 for electronic devices may include heating at 450°C or higher in an atmospheric atmosphere. When the laminate of the present invention is used, even under the above conditions, end deterioration of the silicone resin layer can be suppressed.

[0251] (Separation process)

[0252] Separation process such as Figure 2 (B) shows the following process: from the laminate 22 with electronic device component obtained in the above component forming process, the interface between the silicone resin layer 14 and the glass substrate 16 is used as the peeling surface to separate the glass substrate 16 (substrate with component) with electronic device component 20 laminated and the support substrate 18 with silicone resin layer, to obtain the substrate (electronic device) 24 with component including electronic device component 20 and glass substrate 16.

[0253] If the electronic component 20 on the glass substrate 16 during the peeling process is part of the formation of all necessary constituent components, the remaining constituent components can also be formed on the glass substrate 16 after separation.

[0254] There are no particular limitations on the method for peeling the glass substrate 16 and the silicone resin layer 14. For example, a sharp knife-like object can be inserted at the interface between the glass substrate 16 and the silicone resin layer 14 to provide a peeling starting point, and then a mixture of water and compressed air can be blown to perform the peeling. Preferably, the laminate 22 with the support substrate 12 of the electronic component component 22 on top and the electronic component component 20 on the bottom is arranged on a flat plate, and the electronic component component 20 side is vacuum-adsorbed onto the flat plate. In this state, the knife is first inserted into the interface between the glass substrate 16 and the silicone resin layer 14. Then, multiple vacuum adsorption pads are used to adsorb the support substrate 12 side, and the vacuum adsorption pads are raised sequentially from the vicinity of the inserted knife. As a result, an air layer is formed at the interface between the silicone resin layer 14 and the glass substrate 16 and at the cohesive breaking surface of the silicone resin layer 14, and this air layer diffuses across the entire interface and cohesive breaking surface, making it easy to peel off the support substrate 18 with the silicone resin layer.

[0255] In addition, the support substrate 18 with the silicone resin layer can be laminated with a new glass substrate to manufacture the glass laminate 10 of the present invention.

[0256] It should be noted that when separating the substrate 24 with electronic components from the laminate 22, by controlling the blowing and humidity based on the ion generator, the electrostatic adsorption of the residue of the silicone resin layer 14 onto the substrate 24 with electronic components can be further suppressed.

[0257] The aforementioned method for manufacturing the substrate 24 with components is suitable for manufacturing small display devices used in mobile terminals such as mobile phones and PDAs. The display devices are primarily LCD or OLED; LCDs include TN, STN, FE, TFT, MIM, IPS, and VA types. Essentially, it is applicable to any display device, whether passively driven or actively driven.

[0258] Examples of substrates 24 with components manufactured by the above method include display panel for display devices having a glass substrate and display device components, solar cell having a glass substrate and solar cell components, thin-film secondary battery having a glass substrate and thin-film secondary battery components, sensor panel having a glass substrate and sensor components, and electronic components having a glass substrate and electronic device components. Display panel for display devices includes liquid crystal panels, organic EL panels, plasma display panels, and field emission panels. Sensor panel for display devices includes electromagnetic wave sensor panels, X-ray light sensor panels, ultraviolet light sensor panels, visible light sensor panels, and infrared light sensor panels.

[0259] It should be noted that the above describes in detail the manufacturing method of electronic devices using glass laminate 10, but when using the above resin laminate, the same steps can also be used to manufacture electronic devices.

[0260] More specifically, as another method of manufacturing electronic devices, an example is a scheme comprising the following steps: a step of forming a resin laminate using a resin substrate with an organosilicon layer and a support 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 support substrate and the organosilicon layer from the laminate with the component for an electronic device to obtain an electronic device having a resin substrate and a component for an electronic device.

[0261] The process of forming a resin laminate can be listed as including the above-mentioned resin layer forming process 2 and lamination process 2.

[0262] The steps for component formation and separation when using resin laminates are the same as those for component formation and separation when using glass laminates.

[0263] It should be noted that, as mentioned above, due to the relatively weak adhesion between the resin substrate and the silicone resin layer, the resin substrate and the silicone resin layer are easier to separate during the separation process than the silicone resin layer and the support substrate. This tendency becomes particularly pronounced when a glass plate is used as the support substrate.

[0264] Furthermore, in the above-described method for manufacturing electronic devices using glass laminate 10, electronic devices can also be manufactured using the same steps with a semiconductor laminate formed by replacing the glass substrate with a semiconductor substrate.

[0265] [Example]

[0266] Hereinafter, the present invention will be specifically described through examples, etc., but the present invention is not limited to these examples. Examples 1 to 18 are examples, and Examples 19 and 20 are comparative examples. Furthermore, Example 21 is an example, Example 22 is a comparative example, Examples 23 to 25 are examples, Examples 26 to 28 are comparative examples, Example 29 is an example, and Example 30 is a comparative example.

[0267] In the following embodiments and comparative examples, a glass plate (240 mm long, 240 mm wide, 0.5 mm thick, and with a coefficient of linear expansion of 38 × 10⁻⁶) made of alkali-free borosilicate glass was used as the supporting substrate. -7 / ℃), as the glass substrate, a glass plate (240mm long, 240mm wide, 0.2mm thick, coefficient of linear expansion 38×10) made of alkali-free borosilicate glass was used. -7 / ℃).

[0268] [Synthesis of Curable Organosilicon 1]

[0269] In a 1L flask, add triethoxymethylsilane (179g), toluene (300g), and acetic acid (5g). Stir the mixture at 25°C for 20 minutes, then heat to 60°C and react for 12 hours. After cooling the crude reaction solution to 25°C, wash the solution three times with water (300g).

[0270] 70 g of trichlorosilane was added to the cleaned crude reaction solution. The mixture was stirred at 25 °C for 20 minutes, and then heated to 50 °C for 12 hours. The resulting crude reaction solution was cooled to 25 °C and washed three times with water (300 g).

[0271] Toluene was removed from the cleaned crude reaction liquid by vacuum distillation, resulting in a slurry. This slurry was then dried overnight in a vacuum dryer to obtain a white organopolysiloxane compound, namely, cured organosilicon 1. For cured organosilicon 1, the molar ratio of T units to M units was 87:13.

[0272] <Example 1>

[0273] After dissolving the curable organosilicon 1 in an isoalkane solvent (Isoper G (manufactured by Tonen General Sekiyu KK)), the resulting solution was then mixed with the metal compound and additives in the amounts specified in Table 1 for 5 minutes using a mix rotor. It should be noted that the concentration of the curable organosilicon 1 in the resulting composition X is 50% by mass.

[0274] Next, composition X is applied to the support substrate by spin coating to achieve a cured silicone resin layer thickness of 4 μm. Then, a heat treatment is performed at 100°C for 10 minutes to form a coating film.

[0275] Next, the support substrate with the coating is heat-treated at 250°C for 30 minutes to form an organosilicon resin layer.

[0276] Then, the silicone resin layers of the glass substrate and the supporting substrate are bonded together at room temperature using a roller laminator to obtain a glass laminate.

[0277] In the resulting glass laminate, the supporting substrate and glass substrate are tightly bonded to the silicone resin layer without air bubbles or deformation defects. Furthermore, in the glass laminate, the peel strength at the interface between the silicone resin layer and the supporting substrate layer is greater than the peel strength at the interface between the glass substrate layer and the silicone resin layer.

[0278] <Examples 2~17>

[0279] As shown in Tables 1 to 3, the types and amounts of metal compounds and additives used were changed, and the glass laminate was obtained by following the same steps as in Example 1.

[0280] It should be noted that the tetra-n-propoxide zirconium used is "Orgatics ZA-45" (manufactured by Matsumoto Fine Chemical Co. Ltd., with a metal content of 21.1%).

[0281] In addition, bis(2-ethylhexanoate)tin(II) uses "Neostann U-28" (manufactured by Nitto Kasei Corporation, with a metal content of 29%).

[0282] In addition, bismuth neodecanoate (III) uses "bismuth neodecanoate 16%" (manufactured by Nippon Kagaku Sangyo Co., Ltd., metal content 16%).

[0283] <Example 18>

[0284] [Synthesis of Curable Organosilicon 2]

[0285] (Synthesis of organohydrosiloxanes)

[0286] 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. While stirring the mixture, 11.0 g of concentrated sulfuric acid was slowly added to the mixture, followed by the addition of 3.3 g of water dropwise over 1 hour. The mixture was stirred for 8 hours while maintaining a temperature of 10–20°C. Toluene was then added to the mixture, followed by water washing and waste acid separation until the siloxane layer became neutral. The neutralized siloxane layer was concentrated under reduced pressure to remove low-boiling fractions such as toluene, yielding an organohydrosiloxane with k = 40 and l = 40 in formula (1).

[0287]

[0288] (Synthesis of alkenylsiloxanes)

[0289] A silicate of potassium hydroxide 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 20000 / 1 (mol). The mixture was then subjected to an equilibrium reaction at 150 °C for 6 hours under a nitrogen atmosphere. Next, 2 mol of 2-chloroethanol relative to potassium (K) was added, and the mixture was neutralized at 120 °C for 2 hours. The resulting mixture was then subjected to a heating and bubbling treatment at 160 °C and 666 Pa for 6 hours to remove volatile components, yielding an alkenyl-containing siloxane with an average alkenyl equivalent number La = 0.9 and a Mw of 26000 per 100 g.

[0290] Organosilicon 2 was prepared by mixing organohydrosiloxane and alkenyl siloxane in such a way that the molar ratio of all alkenyl groups to all hydrogen atoms bonded to silicon atoms (hydrogen atoms / alkenyl groups) was 0.9. In this cured organosilicon, 1 part by mass of a silicon compound with alkynyl unsaturated groups as shown in formula (2) was mixed in 100 parts by mass of the cured organosilicon. A platinum catalyst was added in such a way that the contents were as shown in Table 3 to obtain mixture A.

[0291] HC≡CC(CH3)2-O-Si(CH3)3 (2)

[0292] After dissolving mixture A in octamethyltetracyclosiloxane (manufactured by Dow Corning Toray Co., Ltd., XIAMETERPMX-0244), the metal compound was added to the resulting solution in the amounts described in Table 3, and the mixture was stirred for 5 minutes using a stirring rotor. It should be noted that the concentration of curable organosilicon 2 in the resulting composition Y is 30% by mass.

[0293] Next, composition Y is applied to the support substrate by spin coating to achieve a cured silicone resin layer thickness of 8 μm. Then, a heat treatment is performed at 140°C for 10 minutes to form a coating film.

[0294] Next, the support substrate with the coating is heat-treated at 220°C for 30 minutes to form an organosilicon resin layer.

[0295] Then, the silicone resin layers of the glass substrate and the supporting substrate are bonded together at room temperature using a roller laminator to obtain a glass laminate.

[0296] In the resulting glass laminate, the supporting substrate and glass substrate are tightly bonded to the silicone resin layer without air bubbles or deformation defects. Furthermore, the peel strength at the interface between the silicone resin layer and the supporting substrate layer is greater than the peel strength at the interface between the glass substrate layer and the silicone resin layer.

[0297] <Examples 18x~18z>

[0298] As shown in Table 4, the type of metal compound used was changed, and the glass laminate was obtained by following the same steps as in Example 18.

[0299] <Example 19>

[0300] Except for the absence of metal compounds, the glass laminate was obtained following the same steps as in Example 1. It should be noted that the silicone resin layer of the glass laminate in Example 19 does not contain any specific elements.

[0301] <Example 20>

[0302] Without using the specified metal compound, the temperature was changed from 140°C to 100°C and from 220°C to 250°C. Otherwise, the glass laminate was obtained following the same steps as in Example 18. It should be noted that the silicone resin layer of the glass laminate in Example 20 does not contain any specific element.

[0303] [Edge Deterioration Evaluation]

[0304] Cut the glass laminates obtained in each example to obtain 50×50 mm samples. Place each sample into an electric furnace preheated to 450°C and heat-treat for 1 hour before removing the samples. It should be noted that the atmosphere in the electric furnace is atmospheric.

[0305] Using a microscope, observe the end of the extracted sample and determine the maximum length of the whitened portion originating from that end. It should be noted that "maximum length" refers to... Figure 3 The maximum value of the length L of the whitened end shown. A shorter length L indicates better results.

[0306] The results are summarized in Tables 1 to 4.

[0307] [Table 1]

[0308]

[0309] [Table 2]

[0310]

[0311] [Table 3]

[0312]

[0313] [Table 4]

[0314]

[0315] As shown in Tables 1 to 4, the laminates of the present invention exhibit the desired effects.

[0316] When the silicone resin layer contains iron, manganese, copper, cerium, or bismuth as specific elements, superior performance has been confirmed.

[0317] On the other hand, in Examples 19 and 20, where the silicone resin layer does not contain specific elements, the effect is poor.

[0318] It should be noted that, after the above-mentioned end-deterioration evaluation was performed, in the glass laminates of Examples 1 to 16, after inserting a 0.1 mm thick stainless steel tool into the interface between the glass substrate and the silicone resin layer to form a peeling cut, the glass substrate was completely fixed, and the glass substrate could be easily peeled off by lifting the support substrate.

[0319] On the other hand, regarding Example 17, which has added tetra-n-propoxide zirconium but not bis(2-ethylhexanoate)tin(II), the peel strength is high, and when the glass substrate is completely fixed and the support substrate is lifted after the notch is formed, the support substrate sometimes cracks.

[0320] <Examples 21 and 22>

[0321] Using the glass laminates of Examples 18 and 20, the temperature for [end deterioration evaluation] was changed from 450°C to 400°C. Otherwise, the end deterioration evaluation described above was performed following the same steps.

[0322] It should be noted that the silicone resin layer of the glass laminate in Example 22 does not contain any specific elements. The results are shown in Table 5.

[0323] It should be noted that Table 5 shows the temperature and time required for the evaluation of end-stage deterioration.

[0324] [Table 5]

[0325]

[0326] As shown in Table 5, it was confirmed that, even when evaluated at 400°C, the laminate of the present invention (Example 21) exhibited advantageous effects compared to the laminate (Example 22) in which the silicone resin layer does not contain specific elements and does not meet the requirements of the present invention.

[0327] Examples 23 to 28 below illustrate the use of a resin substrate, namely a polyimide resin substrate, as a substrate to fabricate a resin laminate.

[0328] As the polyimide resin substrate, a polyimide film (0.038 mm thick, manufactured by Toyobo Co., Ltd. under the trade name "XENOMAX") is used.

[0329] <Example 23>

[0330] Using a polyimide resin substrate instead of a glass substrate, and otherwise following the same steps as in Example 6, a resin laminate comprising a support substrate, an organosilicon resin layer and a polyimide resin substrate is obtained.

[0331] <Example 24>

[0332] Using a polyimide resin substrate instead of a glass substrate, and otherwise following the same steps as in Example 18, a resin laminate having a support substrate, an organosilicon resin layer and a polyimide resin substrate in sequence is obtained.

[0333] <Example 25>

[0334] The composition Y, prepared in the same manner as in Example 18, was applied to a polyimide resin substrate by a molding process, with the thickness of the cured silicone resin layer being 8 μm. The substrate was then subjected to a heat treatment at 140°C for 10 minutes using a hot plate to form a coating film.

[0335] Next, the polyimide resin substrate with the coating is subjected to a heat treatment at 220°C for 30 minutes to form an organosilicon resin layer.

[0336] Next, the support substrate is placed on the silicone resin layer and laminated using a roller laminator to obtain a resin laminate.

[0337] <Example 26>

[0338] Without using the specified metal compound, the resin laminate was obtained following the same steps as in Example 23. It should be noted that the silicone resin layer of the resin laminate in Example 26 does not contain any specific element.

[0339] <Example 27>

[0340] Without using the specified metal compound, the temperature was changed from 140°C to 100°C and from 220°C to 250°C, and the resin laminate was obtained following the same steps as in Example 24. It should be noted that the silicone resin layer of the resin laminate in Example 27 does not contain any specific element.

[0341] <Example 28>

[0342] Without using the specified metal compound, the temperature was changed from 140°C to 100°C and from 220°C to 250°C, and the resin laminate was obtained following the same steps as in Example 25. It should be noted that the silicone resin layer of the resin laminate in Example 28 does not contain the specific element.

[0343] [Edge Deterioration Evaluation]

[0344] The resin laminates obtained in each example were cut to obtain samples of 50×50 mm. Each sample was then placed in an electric furnace preheated to 400℃ or 450℃ and heated for 1 hour before being removed. It should be noted that the atmosphere in the electric furnace was atmospheric.

[0345] Using a microscope, observe the end of the extracted sample and determine the maximum length of the whitened portion originating from that end. It should be noted that "maximum length" refers to... Figure 3 The maximum value of the length L of the whitened end shown. A shorter length L indicates better results.

[0346] The results are summarized in Table 6.

[0347] It should be noted that in Table 6, the "Formed Surface" column indicates which surface of the support substrate and the polyimide resin substrate is used to form the silicone resin layer before fabricating the resin laminate.

[0348] The "Evaluation Conditions" section indicates the temperature and time used for evaluation in the end-stage deterioration evaluation.

[0349] In addition, in Table 6, the “400℃-1h and 450℃-1h” in the “Evaluation Conditions” column of Examples 24 and 25 means that the “end-deterioration length” is “0.0 mm” under either the condition of “1 hour at 400℃” or “1 hour at 450℃”.

[0350] [Table 6]

[0351]

[0352] As shown in Table 6, it is confirmed that the laminate of the present invention exhibits the desired effect even when the substrate is a resin substrate.

[0353] Furthermore, it has been confirmed that when the laminate of the present invention is manufactured by forming an organosilicon resin layer on the surface of a resin substrate, the desired effect is also observed.

[0354] On the other hand, in Examples 26-28, where the silicone resin layer does not contain specific elements, the effect is poor.

[0355] <Example 29>

[0356] Instead of the glass substrate with a length of 240 mm, a width of 240 mm, and a thickness of 0.2 mm used in Example 18, a laminate was fabricated by bonding a Si wafer with a diameter of 150 mm and a thickness of 625 μm. The end-deterioration of this laminate was evaluated under the same conditions as in Example 18, and the end-deterioration length was found to be 0.0 mm.

[0357] <Example 30>

[0358] Instead of the glass substrate with a length of 240 mm, a width of 240 mm, and a thickness of 0.2 mm used in Example 20, a laminate was fabricated by bonding a Si wafer with a diameter of 150 mm and a thickness of 625 μm. The end-deterioration of this laminate was evaluated under the same conditions as in Example 20, and the end-deterioration length was found to be 3.0 mm.

[0359] In the resin laminates obtained in any of Examples 23 to 28, the supporting substrate and the polyimide resin substrate are tightly bonded to the silicone resin layer without generating bubbles or deforming defects.

[0360] In addition, in any of the resin laminates in each example, before and after the end-deterioration evaluation, the peel strength of the interface between the silicone resin layer and the supporting substrate layer is greater than the peel strength of the interface between the polyimide resin substrate layer and the silicone resin layer.

[0361] It should be noted that: after inserting a 0.1 mm thick stainless steel tool into the interface between the polyimide resin substrate and the silicone resin layer in each resin laminate of Examples 23 to 25 to form a peeling cut, the polyimide resin substrate was completely fixed, the support substrate was lifted, and the polyimide resin substrate was peeled off. As a result, the silicone resin layer did not adhere to the peeled polyimide resin substrate.

[0362] Furthermore, in the laminate formed by stacking Si wafers in Example 29, the silicone resin layer and the Si wafer are tightly bonded without generating bubbles, and there are no deformation defects. It was also confirmed that after inserting a 0.1 mm thick stainless steel tool into the interface between the Si wafer and the silicone resin layer in Example 29 to form a peeling cut, and then completely fixing the Si wafer and lifting the support substrate to peel off the Si wafer, the silicone resin layer did not adhere to the peeled Si wafer.

[0363] This application is based on Japanese Patent Application No. 2016-255155, filed on December 28, 2016; Japanese Patent Application No. 2017-120816, filed on June 20, 2017; and Japanese Patent Application No. 2017-186225, filed on September 27, 2017, the contents of which are incorporated herein by reference.

Claims

1. A curable composition which is a curable composition for releasably attaching a glass, wherein the curable composition comprises a curable silicone and a manganese element as a metal component, the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of a silicone resin layer formed from the curable composition, 2. A curable composition which is a curable composition for releasably attaching a glass, wherein the curable composition comprises a curable silicone and a cobalt element as a metal component, The curable organosilicon is cured to form an organosilicon resin comprising at least one specific organosiloxyl unit selected from the group consisting of (R)3SiO 1 / 2 (R)2SiO 3 / 2 (R)2SiO 1 / 2 (R)2SiO 2 / 2 (R)2SiO 3 / 2 (R)2SiO the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of a silicone resin layer formed from the curable composition, the content of the metal component is 0.01 to 0.7 parts by mass with respect to 100 parts by mass of a silicone resin layer formed from the curable composition. the metal component is contained in the form of a metal compound. The curable organosilicon is cured to form an organosilicon resin comprising at least one specific organosiloxyl unit selected from the group consisting of (R)3SiO 1 / 2 (R)2SiO 3 / 2 (R)2SiO 1 / 2 (R)2SiO 2 / 2 (R)2SiO 3 / 2 (R)2SiO 3. The curable composition according to claim 1 or 2, wherein, the metal compound is a complex.

4. The curable composition according to claim 1 or 2, wherein, the weight average molecular weight of the curable silicone is 5000 to 60000.

5. The curable composition according to claim 4, wherein, the curable composition is used for releasably attaching a substrate containing a semiconductor material to a glass.

6. The curable composition according to claim 1 or 2, wherein, 8. A laminate comprising a substrate containing a semiconductor material, and a glass releasably provided on the substrate via a silicone resin layer, 7. The curable composition according to claim 1 or 2, wherein, the silicone resin layer comprises a silicone resin and a manganese element as a metal component, the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of the silicone resin layer, 9. A laminate comprising a substrate containing a semiconductor material, and a glass releasably provided on the substrate via a silicone resin layer, the silicone resin layer comprises a silicone resin and a cobalt element as a metal component, The silicone resin contains at least one specific organosiloxy unit selected from the group consisting of (R)3SiO 1 / 2 (R)2SiO 3 / 2 (R)2SiO 1 / 2 (R)2SiO 2 / 2 (R)2SiO 3 / 2 (R)2SiO the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of the silicone resin layer, the content of the metal component is 0.01 to 0.7 parts by mass with respect to 100 parts by mass of the silicone resin layer. the thickness of the silicone resin layer is 0.001 to 50 μm. The silicone resin contains at least one specific organosiloxy unit selected from the group consisting of (R)3SiO 1 / 2 (R)2SiO 3 / 2 (R)2SiO 1 / 2 (R)2SiO 2 / 2 (R)2SiO 3 / 2 (R)2SiO 10. The laminate according to claim 8 or 9, wherein the thickness of the silicone resin layer is 0.001 to 10 μm.

11. The laminate according to claim 8 or 9, wherein the substrate contains an LED.

12. The laminate according to claim 8 or 9, wherein 14. A glass with a silicone resin layer comprising a releasably attached silicone resin layer and a glass, 13. The laminate according to claim 8 or 9, wherein the silicone resin layer comprises a silicone resin and a manganese element as a metal component, the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of the silicone resin layer, 15. A glass with a silicone resin layer comprising a releasably attached silicone resin layer and a glass, the silicone resin layer comprises a silicone resin and a cobalt element as a metal component, the silicone resin comprises at least one specific organosiloxy unit selected from the group consisting of (R)3SiO 1 / 2 the organosiloxy unit represented by (R)2SiO 3 / 2 the organosiloxy unit represented by (R)2SiO 1 / 2 the organosiloxy unit represented by (R)2SiO 2 / 2 the organosiloxy unit represented by (R)2SiO 3 / 2 the organosiloxy unit represented by (R)2SiO the content of the metal component is 0.001 to 1 parts by mass with respect to 100 parts by mass of the silicone resin layer, the content of the metal component is 0.01 to 0.7 parts by mass with respect to 100 parts by mass of the silicone resin layer. the thickness of the silicone resin layer is 0.001 to 50 μm. The silicone resin contains at least one specific organosiloxy unit selected from the group consisting of (R)3SiO 1 / 2 (R)2SiO 3 / 2 (R)2SiO 1 / 2 (R)2SiO 2 / 2 (R)2SiO 3 / 2 (R)2SiO 16. The glass with a silicone resin layer according to claim 14 or 15, wherein, the thickness of the silicone resin layer is 0.001 to 10 μm.

17. The glass with a silicone resin layer according to claim 14 or 15, wherein, ​ 18. The glass with a silicone resin layer according to claim 14 or 15, wherein, ​

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