JP6946901B2 - Method for manufacturing laminate, support base material with silicone resin layer, resin substrate with silicone resin layer, electronic device - Google Patents

Description

The present invention relates to a laminate, a support base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for manufacturing an electronic device.

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), organic EL panels (OLEDs), receiving sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. have become thinner. Weight reduction is progressing, and substrates such as glass substrates used for these devices are being thinned. If the strength of the substrate is insufficient due to the thinning of the plate, the handleability of the substrate is lowered in the device manufacturing process.
Recently, in order to deal with the above problems, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared, a member for an electronic device such as a display device is formed on the glass substrate of the glass laminate, and then the glass substrate is formed. A method of separating the reinforcing plate from the glass has been proposed (for example, Patent Document 1). The reinforcing plate has a support plate and a silicone resin layer fixed on the support plate, and the silicone resin layer and the glass substrate are detachably adhered to each other in the glass laminate.

International Publication No. 2007/018028

In recent years, with the increasing functionality and complexity of electronic device members, when forming electronic device members such as oxide semiconductors, heat treatment is performed in an atmospheric atmosphere under higher temperature conditions (for example, 450 ° C.). Implementation is desired.
When the present inventors prepared the glass laminate described in Patent Document 1 and performed heat treatment under the above conditions, the vicinity of the end portion of the silicone resin layer in the glass laminate was whitened and deteriorated. It was found that such alteration occurs (hereinafter, such alteration is also referred to as "edge alteration"). Specifically, as shown in FIG. 3, which is a top view of the heat-treated glass laminate, deterioration occurs at the end 102 of the silicone resin layer of the glass laminate 100. If a gap is created near the end of the silicone resin layer due to such end alteration, the chemicals used in the wet process infiltrate into the glass laminate and contaminate the vacuum process equipment to be carried out thereafter. In addition, process inconveniences such as the chemicals used in the previous process being mixed with the chemicals used in other wet processes are likely to occur.

In view of the above circumstances, the present invention provides a laminate in which the end alteration of the silicone resin layer is suppressed.
The present invention also provides a support base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for manufacturing an electronic device, which can be applied to the laminate.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

(1) A support base material, a silicone resin layer, and a substrate are provided in this order.
A laminate in which the silicone resin layer contains elements of a metal selected from the group consisting of 3d transition metals, 4d transition metals, lanthanoid metals, and bismuth.
(2) The laminate according to (1), wherein the silicone resin layer contains an element of a metal selected from the group consisting of a 3d transition metal, a lanthanoid metal, and bismuth.
(3) The laminate according to (1) or (2), wherein the silicone resin layer contains a metal element selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth. ..
(4) The laminate according to any one of (1) to (3), wherein the silicone resin layer contains a metal element selected from the group consisting of iron, manganese, copper, cerium, and bismuth.
(5) The laminate according to any one of (1) to (4), wherein a plurality of substrates are laminated on a support base material via a silicone resin layer.
(6) The laminate according to any one of (1) to (5), wherein the substrate is a glass substrate.
(7) The laminate according to any one of (1) to (5), wherein the substrate is a resin substrate.
(8) The laminate according to (7), wherein the resin substrate is a polyimide resin substrate.
(9) The laminate according to any one of (1) to (5), wherein the substrate is a substrate containing a semiconductor material.
(10) The laminate according to (9), wherein the semiconductor material is Si, SiC, GaN, gallium oxide, or diamond.
(11) A support base material and a silicone resin layer are provided in this order.
A supporting base material with a silicone resin layer, wherein the silicone resin layer contains an element of a metal selected from the group consisting of a 3d transition metal, a 4d transition metal, a lanthanoid metal, and bismuth.
(12) A member forming step of forming a member for an electronic device on the surface of the substrate of the laminate according to any one of (1) to (10) to obtain a laminate with a member for an electronic device.
An electronic device comprising a separation step of removing a support base material and a support base material with a silicone resin layer including a silicone resin layer from a laminate with a member for an electronic device to obtain an electronic device having a substrate and a member for the electronic device. Production method.
(13) A resin substrate and a silicone resin layer are provided in this order.
A resin substrate with a silicone resin layer, wherein the silicone resin layer contains an element of a metal selected from the group consisting of a 3d transition metal, a 4d transition metal, a lanthanoid metal, and bismuth.
(14) A step of forming a laminate using the resin substrate with the silicone resin layer and the supporting base material according to (13).
A member forming step of forming a member for an electronic device on the surface of a resin substrate of a laminated body to obtain a laminated body with a member for an electronic device.
A method for manufacturing an electronic device, comprising a separation step of removing a supporting base material and a silicone resin layer from a laminate with a member for an electronic device to obtain an electronic device having the resin substrate and the member for the electronic device.

According to the present invention, it is possible to provide a laminated body in which deterioration of the end portion of the silicone resin layer is suppressed.
Further, according to the present invention, it is possible to provide a support base material with a silicone resin layer, a resin substrate with a silicone resin layer, and a method for manufacturing an electronic device, which can be applied to the laminate.

It is a schematic cross-sectional view of one Embodiment of the glass laminate which concerns on this invention. It is a schematic cross-sectional view which shows one Embodiment of the manufacturing method of the electronic device which concerns on this invention in process order. It is a top view which shows the mode in which the end part deterioration occurred in the conventional laminated body.

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments and does not deviate from the scope of the present invention. Can be modified and substituted in various ways.

FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate, which is an aspect of the laminate according to the present invention.
As shown in FIG. 1, the glass laminate 10 is a laminate including a support base material 12, a glass substrate 16, and a silicone resin layer 14 arranged between them. One surface of the silicone resin layer 14 is in contact with the supporting base material 12, and the other surface is in contact with the first main surface 16a of the glass substrate 16.
In the glass laminate 10, the peel strength between the silicone resin layer 14 and the glass substrate 16 is lower than the peel strength between the silicone resin layer 14 and the supporting base material 12, and the silicone resin layer 14 and the glass substrate 16 are separated from each other. It is peeled off and separated into a laminate of the silicone resin layer 14 and the supporting base material 12 and a glass substrate 16. In other words, the silicone resin layer 14 is fixed on the support base material 12, and the glass substrate 16 is releasably laminated on the silicone resin layer 14.
The two-layer portion composed of the support base material 12 and the silicone resin layer 14 has a function of reinforcing the glass substrate 16. The two-layer portion composed of the support base material 12 and the silicone resin layer 14 manufactured in advance for the production of the glass laminate 10 is referred to as a support base material 18 with a silicone resin layer.

The glass laminate 10 is separated into a glass substrate 16 and a support base material 18 with a silicone resin layer by a procedure described later. The support base material 18 with a silicone resin layer is laminated with a new glass substrate 16 and can be reused as a new glass laminate 10.

The peel strength between the support base material 12 and the silicone resin layer 14 is the peel strength (x), and the stress in the peeling direction exceeding the peel strength (x) between the support base material 12 and the silicone resin layer 14 When added, the support base material 12 and the silicone resin layer 14 are peeled off. The peel strength between the silicone resin layer 14 and the glass substrate 16 is the peel strength (y), and a stress in the peeling direction exceeding the peel strength (y) is applied between the silicone resin layer 14 and the glass substrate 16. And the silicone resin layer 14 and the glass substrate 16 are peeled off.
In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, when a stress is applied to the glass laminate 10 in the direction of peeling the support base material 12 and the glass substrate 16, the glass laminate 10 is peeled between the silicone resin layer 14 and the glass substrate 16, and the glass is separated. The substrate 16 and the support base material 18 with a silicone resin layer are separated.

The peel strength (x) is preferably sufficiently higher than the peel strength (y).
In order to increase the adhesive force of the silicone resin layer 14 to the support base material 12, it is preferable to cure the curable silicone described later on the support base material 12 to form the silicone resin layer 14. The silicone resin layer 14 that is bonded to the supporting base material 12 with a high bonding force can be formed by the adhesive force at the time of curing.
On the other hand, the bonding force of the cured silicone resin to the glass substrate 16 is usually lower than the bonding force generated during the curing. Therefore, the glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the support base material 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14.

In the following, first, each layer (support base material 12, glass substrate 16, silicone resin layer 14) constituting the glass laminate 10 will be described in detail, and then a method for manufacturing the glass laminate 10 will be described in detail.

<Supporting base material>
The support base material 12 is a member that supports and reinforces the glass substrate 16.
As the supporting base material 12, for example, a glass plate, a plastic plate, a metal plate (for example, a SUS plate) or the like is used. Usually, the supporting base material 12 is preferably formed of a material having a small difference in linear expansion coefficient from that of the glass substrate 16, and more preferably formed of the same material as the glass substrate 16. In particular, the support base material 12 is preferably a glass plate made of the same glass material as the glass base material 16.

The thickness of the support base material 12 may be thicker or thinner than that of the glass substrate 16. From the viewpoint of handleability of the glass laminate 10, the thickness of the support base material 12 is preferably thicker than that of the glass substrate 16.
When the supporting base material 12 is a glass plate, the thickness of the glass plate is preferably 0.03 mm or more because it is easy to handle and hard to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because it is desired to have rigidity such that the glass substrate is appropriately bent without being broken when the glass substrate is peeled off.

Difference in average linear expansion coefficient at 25 to 300 ° C. with the substrate 12 and the glass substrate 16 is preferably 10 × 10 ^-7 / ℃ less, more preferably 3 × 10 ^-7 / ℃ below 1 × 10 ^{- 7} / ° C. or lower is more preferable.

<Glass substrate>
The type of glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glass containing silicon oxide as a main component are preferable. As the oxide-based glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
The glass substrate 16 is made of non-alkali borosilicate glass as a glass substrate for display devices such as LCDs and OLEDs, and a glass substrate for receiving sensor panels for electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. A glass plate (trade name "AN100" manufactured by Asahi Glass Co., Ltd.) can be mentioned.

The thickness of the glass substrate 16 is preferably 0.5 mm or less, more preferably 0.4 mm or less, further preferably 0.2 mm or less, and particularly preferably 0.10 mm or less, from the viewpoint of thinning and / or weight reduction. When it is 0.5 mm or less, it is possible to give good flexibility to the glass substrate 16. When it is 0.2 mm or less, the glass substrate 16 can be wound into a roll.
The thickness of the glass substrate 16 is preferably 0.03 mm or more from the viewpoint that the glass substrate 16 can be easily handled.
Further, the area of the glass substrate 16 (the area of the main surface) is not particularly limited, but is preferably ^{300 cm 2 or more.}

The glass substrate 16 may be composed of two or more layers, and in this case, the materials forming the respective layers may be the same type of material or different materials. Further, in this case, the "thickness of the glass substrate 16" means the total thickness of all the layers.

The method for manufacturing the glass substrate 16 is not particularly limited, and it is usually obtained by melting a glass raw material and molding molten glass into a plate shape. Such a molding method may be a general one, and examples thereof include a float method, a fusion method, and a slot down draw method.

<Silicone resin layer>
The silicone resin layer 14 prevents the glass substrate 16 from being displaced and prevents the glass substrate 16 from being damaged by the separation operation. The surface 14a of the silicone resin layer 14 in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16.

It is considered that the silicone resin layer 14 and the glass substrate 16 are bonded by a weak adhesive force or a bonding force due to the Van der Waals force.
Further, the silicone resin layer 14 is bonded to the surface of the supporting base material 12 with a strong bonding force, and a known method can be adopted as a method for improving the adhesion between the two. For example, as will be described later, the silicone resin layer 14 is formed on the surface of the support base material 12 (more specifically, a curable silicone (organopolysiloxane) capable of forming a predetermined silicone resin) is formed on the support base material 12. By (curing with), the silicone resin in the silicone resin layer 14 is adhered to the surface of the supporting base material 12, and a high bonding force can be obtained. Further, a treatment for generating a strong bonding force between the surface of the support base material 12 and the silicone resin layer 14 (for example, a treatment using a coupling agent) is performed between the surface of the support base material 12 and the silicone resin layer 14. It is possible to increase the binding force of.

The thickness of the silicone resin layer 14 is not particularly limited, but is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 10 μm or less. The lower limit is not particularly limited, but it is often 0.001 μm or more. When the thickness of the silicone resin layer 14 is within such a range, cracks are unlikely to occur in the silicone resin layer 14, and even if air bubbles or foreign matter may intervene between the silicone resin layer 14 and the glass substrate 16. The occurrence of distortion defects in the glass substrate 16 can be suppressed.
The thickness is intended to be an average thickness, and the thickness of the silicone resin layer 14 at any position of 5 points or more is measured by a contact-type film thickness measuring device, and they are arithmetically averaged.
The surface roughness Ra of the surface of the silicone resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably 0.1 to 20 nm, preferably 0.1 to 10 nm, from the viewpoint of better stackability and peelability of the glass substrate 16. Is more preferable.
The surface roughness Ra is measured according to JIS B 0601-2001, and the arithmetic mean value of Ra measured at any five or more points corresponds to the surface roughness Ra. ..

The silicone resin layer contains a metal element selected from the group consisting of 3d transition metal, 4d transition metal, lanthanoid metal, and bismuth (Bi) (hereinafter, these are collectively referred to as "specific element"). .. By containing these specific elements, alteration of the edges of the silicone resin layer is suppressed during high-temperature heat treatment in the atmosphere. The details of the reason are unknown, but it is considered that the oxidation of the silicone resin is suppressed by the inclusion of a specific element in the silicone resin layer.

Examples of the 3d transition metal include transition metals of the 4th period of the periodic table, that is, metals of scandium (Sr) to copper (Cu). Specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). ).
Examples of the 4d transition metal include transition metals of the fifth period of the periodic table, that is, metals of yttrium (Y) to silver (Ag). Specifically, yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), and silver (Ag). ).
Examples of the lanthanoid metal include lanthanum (La) to lutetium (Lu) metals. Specifically, lantern (La), cerium (Ce), placeodim (Pr), neodym (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), Examples thereof include gadolinium (Dy), formium (Ho), elbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

Among them, the silicone resin layer contains an element of a metal selected from the group consisting of 3d transition metal, lanthanoid metal, and bismuth (Bi) in that the end alteration of the silicone resin layer is further suppressed. Is preferable, and it is more preferable to contain an element of a metal selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth, and iron, manganese, copper, cerium, chromium, and cobalt are more preferable. It is more preferable to contain a metal element selected from the group consisting of, and particularly preferably to contain a metal element selected from the group consisting of iron, manganese, copper, cerium, and bismuth.
The silicone resin layer may contain one type of the above-mentioned specific element, or may contain two or more types.

The content of the specific element in the silicone resin layer is not particularly limited, but 0.001 part by mass or more is preferable in 100 parts by mass of the silicone resin layer, and 0 More preferably, it is 0.01 part by mass or more. The upper limit of the content of the specific element in the silicone resin layer is not particularly limited, but is preferably 1.0 part by mass or less, and more preferably 0.7 part by mass or less.
When the silicone resin layer contains two or more specific elements, the total of them is preferably within the above range.
As for the content of the specific element, the optimum content is appropriately selected depending on the type of metal.

When the silicone resin layer contains a metal element selected from the group consisting of a 3d transition metal, a lanthanoid metal, and bismuth (Bi) (hereinafter, these are collectively referred to as "suitable specific element"). The content of the preferred specific element in the silicone resin layer is not particularly limited, but 0.01 part by mass or more is preferable in 100 parts by mass of the silicone resin layer in that the end alteration of the silicone resin layer is further suppressed. More preferably 0.03 parts by mass or more. The upper limit of the content of the preferred specific element in the silicone resin layer is not particularly limited, but is preferably 0.7 parts by mass or less, and more preferably 0.5 parts by mass or less.
When the silicone resin layer contains two or more suitable specific elements, the total of them is preferably within the above range.

The silicone resin layer may contain a metal element other than the above-mentioned specific element (for example, tin element, aluminum element, platinum element).
Further, the silicone resin layer may contain a curing catalyst that promotes the condensation reaction and a curing catalyst that promotes the addition reaction. Examples of the curing catalyst for promoting the condensation reaction include aluminum chelate compounds such as aluminum trisacetylacetonate and aluminumtrisethylacetacetate, and tin compounds such as dibutyltin dilaurate and tin (2-ethylhexanoic acid) tin (II). Can be mentioned. Examples of the curing catalyst that promotes the addition reaction include platinum-based catalysts.
When the silicone resin layer contains a tin element, the peel strength of the glass substrate arranged on the silicone resin layer tends to decrease, and the glass substrate can be easily peeled off. Further, from the viewpoint of the balance between the heat resistance of the silicone resin layer and the peelability of the substrate, it is preferable that the tin element is used in combination with the zirconium element. That is, when the silicone resin layer contains a tin element, it is preferable that the silicone resin layer also contains a zirconium element.
Further, when the silicone resin layer contains an aluminum element, the heat resistance of the silicone resin layer is likely to be improved.

The specific element and the other metal element may be in the form of a metal, an ion, a compound, or a complex in the silicone resin layer.
The method for measuring the specific element and the other metal element in the silicone resin layer is not particularly limited, and a known method can be adopted, for example, ICP emission spectroscopic analysis (ICP-AES) or ICP mass spectrometry (ICP). -MS). Examples of the apparatus used in the above method include an inductively coupled plasma emission spectrophotometer PS3520U VDDII (Hitachi High-Technologies Corporation) and an inductively coupled plasma (triple quadrupole) mass spectrometer Agilent 8800 (Agilent technologies).
As an example of a specific procedure by the above method, first, the mass of the silicone resin layer is measured. Next, the silicone resin layer is oxidized to silica using an oxygen burner or the like. Then, _{in order to remove the SiO 2} component from the oxidized silicone resin layer, the oxidized silicone resin layer is washed with hydrofluoric acid. The obtained residue is dissolved in hydrochloric acid, and a predetermined specific element and / or other metal element is quantified by the above-mentioned ICP emission spectroscopic analysis method (ICP-AES) or ICP mass analysis method (ICP-MS). conduct. Then, the content of the specific element or other metal element is calculated with respect to the mass of the silicone resin layer measured in advance.

The method for forming the silicone resin layer containing the specific element is not particularly limited, and examples thereof include a method for forming the silicone resin layer using a curable composition containing a curable silicone and a metal compound containing the specific element, which will be described later.
As a method for introducing another metal element into the silicone resin layer, the same as the above-mentioned specific element, the above-mentioned curable silicone, a metal compound containing a specific element, and a metal compound containing another metal element are included. Examples thereof include a method of forming a silicone resin layer using a curable composition.
Details will be described in detail later.

(Silicone resin)
The silicone resin layer 14 is mainly made of a silicone resin.
Generally, the organosiloxy units include monofunctional organosiloxy units called M units, bifunctional organosiloxy units called D units, trifunctional organosiloxy units called T units, and tetrafunctional organosiloxy units called Q units. There is a unit. The Q unit is a unit that does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as an organosiloxy unit (silicon-containing bond unit) in the present invention. The monomers forming the M unit, D unit, T unit, and Q unit are also referred to as M monomer, D monomer, T monomer, and Q monomer, respectively.
The total organosiloxy unit is intended to be the sum of M unit, D unit, T unit, and Q unit. The ratio of the number (molar amount) of M unit, D unit, T unit, and Q unit can be calculated from the value of the peak area ratio by ^{29 Si-NMR.}

In the organosiloxy unit, since the siloxane bond is a bond in which two silicon atoms are bonded via one oxygen atom, the oxygen atom per silicon atom in the siloxane bond is regarded as 1/2, and the formula is used. Expressed as medium O _1/2. More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to another unit of silicon atom. its formula _{-O 1/2 - (R) 2 Si} -O 1/2 - (R represents a hydrogen atom or an organic group) and a. Since _{there are two O 1/2} , the D unit is usually expressed as _{(R) 2} SiO _2/2 (in other words, (R) _{2 SiO).}
In the following description, the oxygen atom O ^* bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is intended to be an oxygen atom in a bond represented by Si—O—Si. do. Therefore, there ^{is one O *} between the silicon atoms of the two organosiloxy units.

The M unit is intended to be an organosiloxy unit represented by _{(R) 3} SiO _1/2. Here, R represents a hydrogen atom or an organic group. The number after (R) (here, 3) is intended that a hydrogen atom or an organic group is bonded to three silicon atoms. 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 an oxygen atom O ^* bonded to one silicon atom.
The D unit is _{intended to be an organosiloxy unit represented by (R) 2} SiO _2/2 (R represents a hydrogen atom or an organic group). That is, the D unit is a unit having one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and two ^{oxygen atoms O * bonded to another silicon atom.}
The T unit is _{intended to be an organosiloxy unit represented by RSiO 3/2} (R represents a hydrogen atom or an organic group). That is, the T unit is a unit having one silicon atom, one hydrogen atom or an organic group bonded to the silicon atom, and three ^{oxygen atoms O * bonded to another silicon atom.}
The Q unit is intended to be an organosiloxy unit represented by _{SiO 2.} That is, the Q unit is a unit having one silicon atom and four ^{oxygen atoms O * bonded to other silicon atoms.}
Examples of the organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and a heptyl group; a phenyl group, a tolyl group, a xsilyl group and a naphthyl group. Alaryl group; aralkyl group such as benzyl group and phenethyl group; monovalent halogen substitution such as alkyl halide group (for example, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc.) Examples include hydrocarbon groups. As the organic group, an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms (preferably about 1 to 10 carbon atoms) is preferable.

The structure of the silicone resin constituting the silicone resin layer 14 is not particularly limited, but the organosiloxy unit represented by _{(R) 3} SiO _{1/2 is more excellent in the balance between the stackability and the peelability of the glass substrate 16.} It is preferable to include at least one specific organosiloxy unit selected from the group consisting of the organosiloxy units (T units) represented by (M units) and (R) SiO _3/2.
Further, the ratio of the specific organosiloxy units is preferably 60 mol% or more, more preferably 80 mol% or more, based on the total organosiloxy units. The upper limit is not particularly limited, but in many cases it is 100 mol% or less.
The ratio of the number of M units and T units (molar amount) can be calculated from the value of the peak area ratio by ^{29 Si-NMR.}

The silicone resin is usually obtained by curing (crosslink curing) a curable silicone that can be the silicone resin by a curing treatment. That is, the silicone resin corresponds to a cured product of curable silicone.
Curable silicones are classified into condensation reaction type silicones, addition reaction type silicones, ultraviolet curable silicones and electron beam curable silicones according to the curing mechanism, and any of them can be used. Of these, condensation reaction type silicone and addition reaction type silicone are preferable.

The condensation reaction type silicone is a hydrolyzable organosilane compound or a mixture thereof (monomer mixture) which is a monomer, or a partial hydrolysis condensation product (organopolysiloxane) obtained by partially hydrolyzing and condensing a monomer or a monomer mixture. Can be preferably used. Further, it may be a mixture of a partially hydrolyzed condensate and a monomer. The monomer may be used alone or in combination of two or more.
A silicone resin can be formed by advancing a hydrolysis / condensation reaction (sol-gel reaction) using this condensation reaction type silicone.

The above-mentioned monomer (hydrolyzable organosilane compound) is usually represented by (R'-) _a Si (-Z) _4-a . However, a is an integer of 0 to 3, R'is a hydrogen atom or an organic group, and Z is a hydroxyl group or a hydrolyzable group. In this chemical formula, the compound with a = 3 is the M monomer, the compound with a = 2 is the D monomer, the compound with a = 1 is the T monomer, and the compound with a = 0 is the Q monomer. In the monomer, the Z group is usually a hydrolyzable group. Further, when there are 2 or 3 R'(when a is 2 or 3), the plurality of R'may be different.

The curable silicone, which is a partially hydrolyzed condensate, is obtained by a reaction of converting a part of the Z group of the monomer into an oxygen atom O ^*. When the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted into a hydroxyl group by a dehydration condensation reaction between two hydroxyl groups bonded to different silicon atoms. Bonds via the oxygen atom O ^*. Hydroxyl groups (or Z groups that have not been hydrolyzed) remain in the curable silicone, and when the curable silicone is cured, these hydroxyl groups and Z groups react in the same manner as described above to cure. The cured product of curable silicone is usually a three-dimensionally crosslinked polymer (silicone resin).

When the Z group of the monomer is a hydrolyzable group, examples of the Z group include an alkoxy group, a halogen atom (for example, a chlorine atom), an acyloxy group, and an isocyanate group. In many cases, a monomer having an alkoxy group with a Z group is used as the monomer, and such a monomer is also referred to as an alkoxysilane.
The alkoxy group is a hydrolyzable group having a relatively low reactivity as compared with other hydrolyzable groups such as chlorine atom, and is a curable silicone obtained by using a monomer (alkoxysilane) in which the Z group is an alkoxy group. In many cases, an unreacted alkoxy group is present together with a hydroxyl group as a Z group.

As the condensation reaction type silicone, a partially hydrolyzed condensate (organopolysiloxane) obtained from a hydrolyzable organosilane compound is preferable from the viewpoint of reaction control and handling. The partially hydrolyzed condensate is obtained by partially hydrolyzing and condensing a hydrolyzable organosilane compound. The method of partially hydrolyzing and condensing is not particularly limited. Usually, it is produced by reacting a hydrolyzable organosilane compound in a solvent in the presence of a catalyst. Examples of the catalyst include an acid catalyst and an alkali catalyst. In addition, it is usually preferable to use water for the hydrolysis reaction. As the partially hydrolyzed condensate, a product produced by reacting a hydrolyzable organosilane compound in the presence of an acid or alkaline aqueous solution in a solvent is preferable.
Preferred embodiments of the hydrolyzable organosilane compound used include alkoxysilanes, as described above. That is, one of the preferred embodiments of the curable silicone is a curable silicone obtained by a hydrolysis reaction and a condensation reaction of alkoxysilane.
When alkoxysilane is used, the degree of polymerization of the partially hydrolyzed condensate tends to increase, and the effect of the present invention is more excellent.

As the addition reaction type silicone, a curable composition containing a main agent and a cross-linking agent and cured in the presence of a catalyst such as a platinum catalyst can be preferably used. Curing of the addition reaction type silicone is promoted by heat treatment. The main agent in the addition reaction type silicone is preferably an organopolysiloxane having an alkenyl group (vinyl group or the like) bonded to a silicon atom (that is, an organoalkenyl polysiloxane, preferably linear), and an alkenyl group. Etc. are the cross-linking points. The cross-linking agent in the addition reaction type silicone is preferably an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (that is, an organohydrogenpolysiloxane, preferably in a linear shape). Hydrosilyl groups and the like serve as cross-linking points.
The addition reaction type silicone is cured by the addition reaction between the cross-linking points of the main agent and the cross-linking agent. In addition, in that the heat resistance derived from the crosslinked structure is more excellent, the molar ratio of the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane to the alkenyl group of the organoalkenyl polysiloxane is 0.5 to 2. preferable.

The weight average molecular weight (Mw) of the curable silicone such as the condensation reaction type silicone and the addition reaction type silicone is not particularly limited, but is preferably 5,000 to 60,000, more preferably 5,000 to 30,000. When Mw is 5000 or more, it is excellent in terms of coatability, and when Mw is 60,000 or less, it is excellent in terms of solubility in a solvent and coatability.

The method for producing the silicone resin layer 14 described above is not particularly limited, and a known method can be adopted. Among them, in that the productivity of the silicone resin layer 14 is excellent, as a method for producing the silicone resin layer 14, a curable silicone that becomes the silicone resin and a metal compound containing a specific element are contained on the support base material 12. It is preferable to apply the composition, remove the solvent if necessary to form a coating film, and cure the curable silicone in the coating film to form the silicone resin layer 14.
As described above, as the curable silicone, a hydrolyzable organosilane compound which is a monomer and / or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing the monomer can be used. Further, as the curable silicone, a mixture of organoalkenyl polysiloxane and organohydrogen polysiloxane can also be used.

The structure of the metal compound containing a specific element contained in the curable composition is not particularly limited as long as the specific element is contained, and known metal compounds can be mentioned. In addition, in this specification, a so-called complex is included in the said metal compound.
As the metal compound containing a specific element, a complex containing the specific element is preferable. A complex is an aggregate in which an atom or an ion of a metal element is centered and a ligand (atom, atomic group, molecule or ion) is bonded to the atom or ion.
The type of ligand contained in the complex is not particularly limited, and examples thereof include a ligand selected from the group consisting of β-diketone, carboxylic acid, alkoxide, and alcohol.
Examples of the β-diketone include acetylacetone, methylacetate acetate, ethylacetacetate, benzoylacetone and the like.
Examples of the carboxylic acid include acetic acid, 2-ethylhexanoic acid, naphthenic acid, neodecanoic acid and the like.
Examples of the alkoxide include methoxide, ethoxide, isopropoxide, butoxide and the like.
Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like.

Specific examples of the metal compound containing the specific element include organic manganese compounds such as tris (2,4-pentandionato) manganese (III), tris (2,4-pentandionato) iron (III), and the like. Organic iron compounds such as tris (2-ethylhexanoic acid) iron (III), organic cobalt compounds such as bis (2,4-pentandionato) cobalt (II), bis (2,4-pentandionato) nickel ( Organic nickel compounds such as II), organic copper compounds such as copper neodecanoate (II), organic bismuth compounds such as bismuth neodecanoate (III), zirconium tetra (monomethylethoxydo), zirconium tetra (monoethylethoxydo), zirconium Organic zirconium compounds such as tetra (monobutylethoxydo) and zirconium normal propylate, organic cerium compounds such as tris (2-ethylhexanoic acid) cerium (III), tris (2,4-pentandionato) chromium (III). And other organic chromium compounds.

The content of the metal compound containing the specific element in the curable composition is not particularly limited, but it is preferably adjusted so as to be within a preferable range of the content of the specific element in the above-mentioned silicone resin layer.

When a condensation reaction type silicone is used as the curable silicone, the curable composition may contain a curing catalyst that promotes the condensation reaction as a metal compound containing other metal elements, if necessary. Examples of the curing catalyst for promoting the condensation reaction include aluminum chelate compounds such as aluminum trisacetylacetonate and aluminumtrisethylacetacetate, and tin compounds such as dibutyltin dilaurate and tin (2-ethylhexanoic acid) tin (II). Can be mentioned.

When an addition reaction type silicone is used as the curable silicone, the curable composition may contain a platinum catalyst as a metal compound containing other metal elements, if necessary.
The platinum catalyst is a catalyst for advancing and promoting the hydrosilylation reaction between the alkenyl group in the organoalkenyl polysiloxane and the hydrogen atom in the organohydrogen polysiloxane.

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. Among them, the content of the curable silicone in the curable composition containing the curable silicone is based on the total mass of the composition because it is easy to handle and the film thickness of the silicone resin layer 14 can be easily controlled. Therefore, 1 to 80% by mass is preferable, and 1 to 50% by mass is more preferable.
The solvent is not particularly limited as long as it can easily dissolve the curable silicone in a working environment and can be easily volatilized and removed. Specific examples thereof include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate, octamethylcyclotetrasiloxane, and isoparaffinic solvents.

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

<Glass laminate and its manufacturing method>
As described above, the glass laminate 10 is a laminate including a support base material 12 and a glass substrate 16 and a silicone resin layer 14 arranged between them.
The method for producing the glass laminate 10 is not particularly limited, but a method of forming the silicone resin layer 14 on the surface of the supporting base material 12 in order to obtain a laminate having a peel strength (x) higher than the peel strength (y) is available. preferable. Above all, a curable composition containing a curable silicone and a metal compound containing a specific element is applied to the surface of the supporting base material 12, and the obtained coating film is cured to obtain a silicone resin layer. Next, a method of laminating the glass substrate 16 on the surface of the silicone resin layer 14 to manufacture the glass laminate 10 is preferable.
When the curable silicone is cured on the surface of the supporting base material 12, it is considered that the silicone resin adheres to the surface of the supporting base material 12 due to the interaction with the surface of the supporting base material 12 during the curing reaction, and the peel strength between the silicone resin and the surface of the supporting base material 12 becomes high. Therefore, even if the glass substrate 16 and the supporting base material 12 are made of the same material, it is possible to provide a difference in peel strength between the silicone resin layer 14 and the two.
Hereinafter, the steps of forming a curable silicone layer on the surface of the support base material 12 and forming the silicone resin layer 14 on the surface of the support base material 12 are described in the resin layer forming step 1, and the glass substrate 16 on the surface of the silicone resin layer 14. The step of laminating the above to form the glass laminate 10 is referred to as laminating step 1, and the procedure of each step will be described in detail.

(Resin layer forming step 1)
In the resin layer forming step 1, a curable silicone layer is formed on the surface of the support base material 12, and the silicone resin layer 14 is formed on the surface of the support base material 12.
First, in order to form a layer of curable silicone on the support base material 12, the above-mentioned curable composition is applied onto the support base material 12. Next, it is preferable that the curable silicone layer is subjected to a curing treatment to form a cured layer.

The method of applying the curable composition on the surface of the supporting base material 12 is not particularly limited, and known methods can be mentioned. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, a gravure coating method and the like can be mentioned.

Next, the curable silicone on the support base material 12 is cured to form a cured layer (silicone resin layer).
The curing method is not particularly limited, and the optimum treatment is appropriately carried out depending on the type of curable silicone used. For example, when a condensation reaction type silicone and an addition reaction type silicone are used, a thermosetting treatment is preferable as the curing treatment.
The temperature condition for thermosetting is preferably 150 to 550 ° C, more preferably 200 to 450 ° C. The heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 minutes. The heating conditions may be changed stepwise by changing the temperature conditions.

In the thermosetting treatment, it is preferable to perform pre-curing (pre-curing) and then curing (main curing). By performing precure, a silicone resin layer 14 having excellent heat resistance can be obtained.

(Laminating process 1)
In the laminating step 1, a glass substrate 16 is laminated on the surface of the silicone resin layer 14 obtained in the above resin layer forming step, and the supporting base material 12, the silicone resin layer 14, and the glass substrate 16 are provided in this order. This is a step of obtaining the laminated body 10.

The method of laminating the glass substrate 16 on the silicone resin layer 14 is not particularly limited, and known methods can be mentioned.
For example, a method of stacking the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned. If necessary, the glass substrate 16 may be laminated on the surface of the silicone resin layer 14, and then the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 by using a roll or a press. Crimping with a roll or press is preferable because air bubbles mixed between the silicone resin layer 14 and the glass substrate 16 are relatively easily removed.

Crimping by a vacuum laminating method or a vacuum pressing method is preferable because it suppresses the mixing of air bubbles and can realize a good amount of adhesion. By crimping under vacuum, even if minute bubbles remain, the bubbles do not grow due to heating, and there is an advantage that it is unlikely to lead to distortion defects of the glass substrate 16.

When laminating the glass substrate 16, it is preferable that the surface of the glass substrate 16 in contact with the silicone resin layer 14 is sufficiently washed and then laminated in an environment with a high degree of cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16, which is preferable.

After laminating the glass substrates 16, a pre-annealing treatment (heat treatment) may be performed if necessary. By performing the 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 obtained.

In the above, the case where a glass substrate is used as the substrate has been described in detail, but the type of the substrate is not particularly limited.
For example, examples of the substrate include a metal substrate, a semiconductor substrate, a resin substrate, and a glass substrate. Further, the substrate may be a substrate composed of a plurality of the same materials, such as a metal plate composed of two different metals. Further, the substrate is a composite substrate of dissimilar materials (eg, two or more materials selected from metal, semiconductor, resin, and glass), such as a substrate composed of resin and glass. You may.
The thickness of the substrate such as a metal plate or a semiconductor substrate is not particularly limited, but from the viewpoint of thinning and / or weight reduction, it is preferably 0.5 mm or less, more preferably 0.4 mm or less, and further preferably 0.4 mm or less. It is 0.2 mm or less. The lower limit of the thickness is not particularly limited, but is preferably 0.005 mm or more.
The area of the substrate (area of the main surface) is not particularly limited, but is preferably ^{300 cm 2 or more from the viewpoint of productivity of the electronic device.}
Further, the shape of the substrate is not particularly limited, and may be rectangular or circular. Further, the substrate is formed with an orientation flat (so-called orientation flat, which is a flat portion formed on the outer periphery of the substrate) and a notch (one or more V-shaped notches formed on the outer peripheral edge of the substrate). You may.

<Manufacturing method of resin substrate and laminate using resin substrate>
As the resin substrate, it is preferable to use a resin substrate having excellent heat resistance that can withstand heat treatment in the device manufacturing process. Examples of the resin constituting the resin substrate include polybenzoimidazole resin (PBI), polyimide resin (PI), polyetheretherketone resin (PEEK), polyamide resin (PA), fluororesin, epoxy resin, and polyphenylene sulfide resin (polyphenylene sulfide resin). PPS) and the like. In particular, a polyimide resin substrate made of a polyimide resin is preferable from the viewpoints of excellent heat resistance, excellent chemical resistance, low coefficient of thermal expansion, high mechanical properties, and the like.
Further, in order to form high-definition wiring or the like of an electronic device on the resin substrate, it is preferable that the surface of the resin substrate is smooth. 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.
The thickness of the resin substrate is preferably 1 μm or more, more preferably 10 μm or more, from the viewpoint of handleability in the manufacturing process. Further, from the viewpoint of flexibility, 1 mm or less is preferable, and 0.2 mm or less is more preferable.
As for the coefficient of thermal expansion of the resin substrate, it is preferable that the difference in coefficient of thermal expansion from that of the electronic device or the supporting base material is small because the warp of the laminated body after heating or cooling can be suppressed. Specifically, the difference in the coefficient of thermal expansion between the resin substrate and the supporting substrate ^{is preferably 0 to 90 × 10 -6} / ° C, more preferably 0 to 30 × 10 ^{-6 / ° C.}

The method for producing the laminate when the resin substrate is used as the substrate is not particularly limited, and for example, the laminate can be produced by the same method as when the glass substrate is used as described above. That is, the silicone resin layer can be formed on the supporting base material, and the resin substrate can be laminated on the silicone resin layer to manufacture the laminated body.
A laminate having a supporting base material, a silicone resin layer, and a resin substrate in this order is hereinafter also referred to as a resin laminate.

Further, as another method for producing the resin laminate, a method of forming a silicone resin layer on the surface of the resin substrate to produce the resin laminate is also preferable.
The adhesion of the silicone resin layer to the resin substrate generally tends to be low. Therefore, even when a silicone resin layer is formed on the surface of the resin substrate and the obtained resin substrate with the silicone resin layer and the support base material are laminated to obtain a resin laminate, the support base material and the silicone resin layer are used. The peel strength (x) between them tends to exceed the peel strength (y ′) between the silicone resin layer and the resin substrate. In particular, when a glass plate is used as the supporting base material, this tendency is strong.
That is, the resin laminate can be separated into a resin substrate and a support base material with a silicone resin layer, as in the case of the glass laminate.

Other methods for producing the resin laminate described above mainly include a step of forming a curable silicone layer on the surface of the resin substrate and forming a silicone resin layer on the surface of the resin substrate (resin layer forming step 2). It has a step (lamination step 2) of laminating a support base material on the surface of a silicone resin layer to form a resin laminate.
Hereinafter, the procedure of each of the above steps will be described in detail.

(Resin layer forming step 2)
The resin layer forming step 2 is a step of forming a curable silicone layer on the surface of the resin substrate and forming the silicone resin layer on the surface of the resin substrate. By this step, a resin substrate with a silicone resin layer including a resin substrate and a silicone resin layer in this order can be obtained.
In this step, in order to form a curable silicone layer on the resin substrate, the above-mentioned curable composition is applied onto the resin substrate. Next, it is preferable that the curable silicone layer is subjected to a curing treatment to form a cured layer.

The method of applying the curable composition on the surface of the resin substrate is not particularly limited, and known methods can be mentioned. For example, a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, a gravure coating method and the like can be mentioned.

Next, the curable silicone on the resin substrate is cured to form a cured layer (silicone resin layer).
The curing method is not particularly limited, and the optimum treatment is appropriately carried out depending on the type of curable silicone used. For example, when a condensation reaction type silicone and an addition reaction type silicone are used, a thermosetting treatment is preferable as the curing treatment.
The conditions of the thermosetting treatment are carried out within the range of heat resistance of the resin substrate. For example, the temperature condition for thermosetting is preferably 50 to 400 ° C, more preferably 100 to 300 ° C. The heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 minutes.
The mode of the silicone resin layer formed is as described above.

(Laminating process 2)
The laminating step 2 is a step of laminating a supporting base material on the surface of the silicone resin layer to form a resin laminate. That is, this step is a step of forming a resin laminate using a resin substrate with a silicone resin layer and a supporting base material.

The method of laminating the support base material on the silicone resin layer is not particularly limited, and examples thereof include known methods, and examples thereof include the methods described in the above-described description of the laminating step 1 in the production of the glass laminate.

After laminating the supporting base materials, heat treatment may be performed if necessary. By performing the heat treatment, the adhesion of the laminated support base material to the silicone resin layer is improved, and an appropriate peel strength (x) can be obtained.
The temperature condition of the heat treatment is preferably 50 to 400 ° C., more preferably 100 to 300 ° C. ° C. The heating time is usually preferably 1 to 120 minutes, more preferably 5 to 60 minutes. The heating conditions may be changed stepwise by changing the temperature conditions.
Further, when the resin laminate is heated in the step of forming the electronic device member described later, the heat treatment may be omitted.

From the viewpoint of improving the peel strength (x) and adjusting the balance between the peel strength (x) and the peel strength (y'), before laminating the support base material on the silicone resin layer, the support base material and the silicone resin It is preferable to apply a surface treatment to at least one of the layers, and it is more preferable to apply a surface treatment to the silicone resin layer.
Examples of the surface treatment method include corona treatment, plasma treatment, UV ozone treatment, and the like, and corona treatment is particularly preferable.

A resin substrate with a silicone resin layer is manufactured by a so-called roll-to-roll method in which a silicone resin layer is formed on the surface of a resin substrate wound in a roll shape and then wound again in a roll shape. It is possible and has excellent production efficiency.

When the silicone resin layer is formed on the supporting base material, when the curable composition is applied to the supporting base material, the thickness of the outer peripheral portion of the silicone resin layer is compared with the thickness of the central portion due to the so-called coffee ring phenomenon. It tends to be thicker. In this case, it is necessary to cut and remove the support base material portion on which the outer peripheral portion of the silicone resin layer is arranged, but when the support substrate is a glass substrate, the labor and cost are large.
On the other hand, when the silicone resin layer is formed on the resin substrate, the resin substrate is generally excellent in handleability and cost. Therefore, even if the above problems occur, the outer peripheral portion of the silicone resin layer is arranged on the resin substrate portion. Resection is relatively easy.

<Semiconductor substrate and method for manufacturing a laminate using a semiconductor substrate>
Examples of the material of the semiconductor substrate include Si, SiC, GaN, gallium oxide, diamond and the like. A Si substrate is also called a Si wafer.
In order to form high-definition wiring and the like of an electronic device on the semiconductor substrate, it is preferable that the surface of the semiconductor substrate is smooth. Specifically, the surface roughness Ra of the semiconductor substrate is preferably 50 nm or less, more preferably 30 nm or less, still more preferably 10 nm or less.
The thickness of the semiconductor substrate is preferably 1 μm or more, more preferably 10 μm or more, from the viewpoint of handleability in the manufacturing process. From the viewpoint of miniaturization of the electronic device, 1 mm or less is preferable, and 0.2 mm or less is more preferable.
As for the coefficient of thermal expansion of the semiconductor substrate, it is preferable that the difference in coefficient of thermal expansion from that of the electronic device or the supporting base material is small because the warp of the laminated body after heating or cooling can be suppressed. Specifically, the difference in the coefficient of thermal expansion between the semiconductor substrate and the supporting base material ^{is preferably 0 to 90 × 10 -6} / ° C, more preferably 0 to 30 × 10 ^{-6 / ° C.}

The method for producing the laminate when a semiconductor substrate is used as the substrate is not particularly limited, and for example, the laminate can be produced by the same method as when the glass substrate is used as described above. That is, the silicone resin layer can be formed on the supporting base material, and the semiconductor substrate can be laminated on the silicone resin layer to manufacture the laminated body.
A laminate having a supporting base material, a silicone resin layer, and a semiconductor substrate in this order is hereinafter also referred to as a semiconductor laminate.
As will be described later, even in the semiconductor laminate, the end alteration is suppressed.

(Laminated body)
The laminate of the present invention (for example, the glass laminate 10 described above) can be used for various purposes, for example, a display device panel, PV, a thin film secondary battery, a semiconductor wafer having a circuit formed on the surface, which will be described later. Examples include applications for manufacturing electronic components such as receiver sensor panels. In this application, the laminate may be exposed to high temperature conditions (for example, 450 ° C. or higher) (for example, 20 minutes or longer) in an air atmosphere.
Here, the display device panel includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a micro LED display panel, a MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.
Here, the receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible light receiving sensor panel, an infrared receiving sensor panel, and the like. The substrate used for these receiving sensor panels may be reinforced with a reinforcing sheet such as resin.

Note that FIG. 1 illustrates a mode in which one substrate (for example, a glass substrate or a resin substrate) is laminated on a supporting base material via a silicone resin layer. However, the laminate of the present invention is not limited to this embodiment, and is, for example, a mode in which a plurality of substrates are laminated on a support base material via a silicone resin layer (hereinafter, also referred to as a “multi-sided attachment mode”). May be good.
More specifically, the multi-sided mounting mode is a mode in which all of the plurality of substrates are in contact with the supporting base material via the silicone resin layer. That is, it is not a mode in which a plurality of substrates are overlapped (only one of the plurality of substrates is in contact with the supporting base material via the silicone resin layer).
In the multi-sided attachment mode, for example, a plurality of silicone resin layers are provided for each individual substrate, and the plurality of substrates and the silicone resin layer are arranged on one supporting base material. However, the present invention is not limited to this, and individual substrates may be arranged, for example, on one silicone resin layer (for example, the same size as the supporting substrate) formed on one supporting substrate.

<Electronic device and its manufacturing method>
In the present invention, an electronic device including a substrate and an electronic device member (hereinafter, also appropriately referred to as a “member-attached substrate”) is manufactured using the above-mentioned laminate.
Hereinafter, a method for manufacturing an electronic device using the above-mentioned glass laminate 10 will be described in detail.
The method for manufacturing the electronic device is not particularly limited, but from the viewpoint of excellent productivity of the electronic device, a member for the electronic device is formed on the glass substrate in the glass laminate to manufacture the laminate with the member for the electronic device. A method of separating the obtained laminate with a member for an electronic device into an electronic device (a substrate with a member) and a supporting base material with a silicone resin layer by using the glass substrate side interface of the silicone resin layer as a peeling surface is preferable.
Hereinafter, the process of forming a member for an electronic device on the glass substrate in the glass laminate to manufacture the laminate with the member for the electronic device is a member forming step, and the glass substrate of the silicone resin layer from the laminate with the member for the electronic device The step of separating the substrate with a member and the supporting substrate with a silicone resin layer using the side interface as a peeling surface is called a separation step.
The materials and procedures used in each step are described in detail below.

(Member forming process)
The member forming step is a step of forming a member for an electronic device on the glass substrate 16 in the glass laminate 10. More specifically, as shown in FIG. 2A, the electronic device member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain the electronic device member-attached laminate 22. ..
First, the electronic device member 20 used in this step will be described in detail, and then the procedure of the step will be described in detail.

(Members for electronic devices (functional elements))
The electronic device member 20 is a member formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, the electronic device member 20 is used for a display device panel, a solar cell, a thin film secondary battery, an electronic component such as a semiconductor wafer having a circuit formed on its surface, a receiving sensor panel, or the like. Examples thereof include members (for example, display device members, solar cell members, thin film secondary battery members, electronic component circuits, and reception sensor members).

For example, as a member for a solar cell, in the silicon type, a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by a p-layer / i-layer / n-layer, a metal of a negative electrode, and the like can be mentioned. , Various members corresponding to the dye-sensitized type, the quantum dot type, and the like can be mentioned.
Further, as the member for the thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer and the like are used. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
Examples of circuits for electronic components include metals in conductive parts, silicon oxide and silicon nitride in insulating parts in CCD and CMOS, and other sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, and flexible printed circuit boards. , Various members corresponding to rigid flexible printed circuit boards and the like can be mentioned.

(Process procedure)
The method for manufacturing the above-mentioned laminated body 22 with a member for an electronic device is not particularly limited, and a second main body of the glass substrate 16 of the glass laminated body 10 is used by a conventionally known method according to the type of the constituent members of the electronic device member. The electronic device member 20 is formed on the surface 16b.
The electronic device member 20 is not all the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter, referred to as “all members”), but a part of all the members (hereinafter, “parts”). It may be called "member"). The substrate with partial members peeled off from the silicone resin layer 14 can be made into a substrate with all members (corresponding to an electronic device described later) in a subsequent step.
Further, on the substrate with all members peeled from the silicone resin layer 14, other electronic device members may be formed on the peeled surface (first main surface 16a). Further, the laminated body with all members is assembled using two sheets, and then the support base material with two silicone resin layers is peeled off from the laminated body with all members to manufacture a substrate with members having two glass substrates. You can also do it.

For example, in the case of manufacturing an OLED, an organic EL is formed on the surface of the glass substrate 16 of the glass laminate 10 opposite to the silicone resin layer 14 side (corresponding to the second main surface 16b of the glass substrate 16). In order to form a structure, a transparent electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are vapor-deposited on the surface on which the transparent electrode is formed, a back surface electrode is formed, and a seal is formed. Various layers are formed and treated, such as sealing with a plate. Specific examples of these layer formations and treatments include a film forming process, a thin film deposition process, and a sealing plate bonding process.

Further, for example, in the case of manufacturing a TFT-LCD, a resist liquid is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method and a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film to be formed, and a pattern of a resist liquid on a second main surface 16b of a glass substrate 16 of another glass laminate 10. Various types such as a CF forming step of forming a color filter (CF) used for forming, and a laminating step of laminating a laminate with a TFT obtained in the TFT forming step and a laminate with CF obtained in the CF forming step. Has a process.

For example, in the case of manufacturing a micro LED display, it is formed on at least the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film transistor method such as a CVD method and a sputtering method using a resist solution. It has a TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film to be formed, and an LED mounting step of mounting an LED chip on the formed TFT. In addition, steps such as flattening, wiring formation, and sealing may be performed.

In the TFT forming step and the CF forming step, the TFT and CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist liquid is used as a coating liquid for pattern formation.
If necessary, the second main surface 16b of the glass substrate 16 may be washed before forming the TFT or CF. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

In the bonding step, the thin film transistor-forming surface of the TFT-equipped laminate and the color filter-forming surface of the CF-equipped laminate are opposed to each other and bonded using a sealant (for example, an ultraviolet curable sealant for cell formation). After that, the liquid crystal material is injected into the cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a dropping injection method.

The electronic device member 20 may include a condition of heating at 450 ° C. or higher in an atmospheric atmosphere. With the laminate of the present invention, deterioration of the end portion of the silicone resin layer is suppressed even under the above conditions.

(Separation process)
In the separation step, as shown in FIG. 2 (B), from the laminate 22 with the member for the electronic device obtained in the member forming step, the interface between the silicone resin layer 14 and the glass substrate 16 is used as a peeling surface, and the electronic device is used. A glass substrate 16 (a substrate with a member) on which the members 20 are laminated and a support base material with a silicone resin layer are separated to obtain a substrate with a member (electronic device) 24 including the member 20 for an electronic device and the glass substrate 16. It is a process.
When the electronic device member 20 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after the separation.

The method of peeling the glass substrate 16 and the silicone resin layer 14 is not particularly limited. For example, a sharp blade-like object can be inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to give a trigger for peeling, and then the mixed fluid of water and compressed air can be sprayed to peel the glass substrate 16. .. Preferably, the support base material 12 of the laminate 22 with the electronic device member 22 is installed on the surface plate so that the support base material 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is evacuated on the surface plate. In this state, the cutting tool is first made to penetrate into the interface between the glass substrate 16-silicone resin layer 14 by adsorption. Then, after that, the support base material 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed on the interface between the silicone resin layer 14 and the glass substrate 16 and the agglomerated fracture surface of the silicone resin layer 14, and the air layer spreads over the entire interface and the agglomerated fracture surface, and the supporting base material 18 with the silicone resin layer Can be easily peeled off.
Further, the support base material 18 with a silicone resin layer can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

When separating the member-attached substrate 24 from the electronic device member-attached laminate 22, the fragments of the silicone resin layer 14 are electrostatically adsorbed on the member-attached substrate 24 by controlling the spraying and humidity by the ionizer. Can be further suppressed.

The method for manufacturing the member-attached substrate 24 described above is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, a MIM type, an IPS type, a VA type and the like. Basically, it can be applied to both passive drive type and active drive type display devices.

The member-attached substrate 24 manufactured by the above method includes a display device panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, and a glass substrate and a thin film secondary battery member. Examples thereof include a thin-film secondary battery, a receiving sensor panel having a glass substrate and a member for a receiving sensor, and an electronic component having a glass substrate and a member for an electronic device. The display device panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like. The receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible light receiving sensor panel, an infrared receiving sensor panel, and the like.

Although the method for manufacturing the electronic device using the glass laminate 10 has been described in detail above, the electronic device can be manufactured by the same procedure even when the resin laminate described above is used.
More specifically, as another aspect of the method for manufacturing an electronic device, a step of forming a resin laminate using a resin substrate with a silicone resin layer and a supporting base material, and on the surface of the resin substrate of the resin laminate. A member forming step of forming a member for an electronic device to obtain a laminate with a member for an electronic device, and removing a support base material and a silicone resin layer from the laminate with a member for an electronic device to obtain a resin substrate and a member for the electronic device. An embodiment including a separation step for obtaining an electronic device having the above can be mentioned.
Examples of the step of forming the resin laminate include a step including the resin layer forming step 2 and the laminating step 2 described above.
Examples of the procedure of the member forming step and the separating step when the resin laminate is used include the same procedure as the member forming step and the separating step when the glass laminate is used.
As described above, since the adhesion between the resin substrate and the silicone resin layer is relatively weak, in the separation step, between the resin substrate and the silicone resin layer rather than between the silicone resin layer and the supporting base material. Easy to separate. In particular, when a glass plate is used as the supporting base material, this tendency becomes remarkable.
Further, in the method for manufacturing an electronic device using the glass laminate 10 in the above description, the electronic device can be manufactured by the same procedure for a semiconductor laminate formed by using a semiconductor substrate instead of the glass substrate.

Hereinafter, the present invention will be specifically described with reference to Examples and the like, but the present invention is not limited to these examples. Examples 1 to 18 are Examples, and Examples 19 and 20 are Comparative Examples. Further, 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.

In the following examples and comparative examples, the supporting base material is a glass plate made of non-alkali borosilicate glass (length 240 mm, width 240 mm, plate thickness 0.5 mm, coefficient of linear expansion 38 × 10 ^-7 / ° C.). As the glass substrate, a glass plate made of non-alkali borosilicate glass (length 240 mm, width 240 mm, plate thickness 0.2 mm, coefficient of linear expansion 38 × 10 ^-7 / ° C.) was used.

[Synthesis of curable silicone 1]
Triethoxymethylsilane (179 g), toluene (300 g) and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25 ° C. for 20 minutes and then heated to 60 ° C. for 12 hours. The obtained crude reaction solution was cooled to 25 ° C., and then the crude reaction solution was washed 3 times with water (300 g).
Chlorotrimethylsilane (70 g) was added to the washed crude reaction solution, and the mixture was stirred at 25 ° C. for 20 minutes and then heated to 50 ° C. for 12 hours. The obtained crude reaction solution was cooled to 25 ° C., and then the crude reaction solution was washed 3 times with water (300 g).
Toluene was distilled off from the washed crude reaction solution under reduced pressure to form a slurry, which was then dried overnight in a vacuum dryer to obtain curable silicone 1 which is a white organopolysiloxane compound. The number of T units: the number of M units = 87:13 (molar ratio) of the curable silicone 1.

<Example 1>
After dissolving the curable silicone 1 in an isoparaffin solvent (Isoper G (manufactured by TonenGeneral Sekiyu KK)), the metal compound and the addition were added to the obtained solution so as to have the addition amounts shown in Table 1. The agent was added and stirred using a mix rotor for 5 minutes. The concentration of the curable silicone 1 in the obtained composition X was 50% by mass.
Next, the composition X was applied onto the supporting substrate by a spin coating method so that the thickness of the cured silicone resin layer was 4 μm, and then heat treatment was performed at 100 ° C. for 10 minutes. A coating film was formed.
Next, the supporting base material on which the coating film was formed was heat-treated at 250 ° C. for 30 minutes to form a silicone resin layer.
Then, the glass substrate and the silicone resin layer surface of the supporting base material were bonded together at room temperature by a roll bonding machine to obtain a glass laminate.
In the obtained glass laminate, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion-like defect. Further, in the glass laminate, the peel strength at the interface between the silicone resin layer and the support base material layer was larger than the peel strength at the interface between the glass substrate layer and the silicone resin layer.

<Examples 2 to 17>
A glass laminate was obtained according to the same procedure as in Example 1 except that the types and amounts of the metal compounds and additives used were changed as shown in Tables 1 to 3.
As the zirconium tetranormal propoxide, "Organix ZA-45" (manufactured by Matsumoto Fine Chemical Co., Ltd., metal content 21.1%) was used.
As bis (2-ethylhexanoic acid) tin (II), "Neostan U-28" (manufactured by Nitto Kasei Co., Ltd., metal content 29%) was used.
As the bismuth neodecanoate (III), "bismuth neodecanoate 16%" (manufactured by Nihon Kagaku Sangyo Co., Ltd., metal content 16%) was used.

<Example 18>
[Synthesis of curable silicone 2]
(Synthesis of organohydrogensiloxane)
A mixture of 1,1,3,3-tetramethyldisiloxane (5.4 g), tetramethylcyclotetrasiloxane (96.2 g), and octamethylcyclotetrasiloxane (118.6 g) is cooled to 5 ° C. and mixed. Was slowly added to the mixture while stirring, and then 3.3 g of water was further added dropwise to the mixture over 1 hour. After stirring for 8 hours while keeping the temperature of the mixed solution at 10 to 20 ° C., toluene was added to the mixed solution, and washing with water and separation of waste acid were carried out until the siloxane layer became neutral. The neutralized siloxane layer was concentrated by heating under reduced pressure to remove low boiling point fractions such as toluene, and organohydrogensiloxanes having k = 40 and l = 40 were obtained in the following formula (1).

(Synthesis of alkenyl group-containing siloxane)
1,3-Divinyl-1,1,3,3-tetramethyldisiloxane (3.7 g), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (41) .4 g), octamethylcyclotetrasiloxane (355.9 g) was added with a siliconate of potassium hydroxide in an amount of Si / K = 20000/1 (mol ratio), and an equilibrium reaction was carried out at 150 ° C. for 6 hours in a nitrogen atmosphere. Then, 2 mol of ethylene chlorohydrin was added to K (potassium), and the mixed solution was neutralized at 120 ° C. for 2 hours. Then, the obtained mixed solution was heated and bubbled at 160 ° C. and 666 Pa for 6 hours to cut off volatile components, and the alkenyl equivalent number La = 0.9 per 100 g and Mw: 26,000 alkenyl group-containing siloxane. Got

Organohydrogensiloxane and alkenyl group-containing siloxane are mixed so that the molar ratio (hydrogen atom / alkenyl group) of the total alkenyl group and the hydrogen atom bonded to the total silicon atom is 0.9, and the curable silicone 2 To 100 parts by mass of this curable silicone, 1 part by mass of a silicon compound having an acetylene-based unsaturated group represented by the following formula (2) was mixed so that the content of the platinum catalyst was as shown in Table 3. In addition, mixture A was obtained.
HC≡CC (CH ₃ ) _2- O-Si (CH ₃ ) ₃ (2)

After dissolving the mixture A in octamethyltetracyclosiloxane (XIAMETER PMX-0244, manufactured by Dow Corning), a metal compound was added to the obtained solution so as to have the amount shown in Table 3. , Stirred for 5 minutes using a mix rotor. The concentration of the curable silicone 2 in the obtained composition Y was 30% by mass.
Next, the composition Y was applied onto the supporting substrate by a spin coating method so that the thickness of the cured silicone resin layer was 8 μm, and then heat treatment was performed at 140 ° C. for 10 minutes. A coating film was formed.
Next, the supporting base material on which the coating film was formed was heat-treated at 220 ° C. for 30 minutes to form a silicone resin layer.
Then, the glass substrate and the silicone resin layer surface of the supporting base material were bonded together at room temperature by a roll bonding machine to obtain a glass laminate.
In the obtained glass laminate, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion-like defect. Further, in the glass laminate, the peel strength at the interface between the silicone resin layer and the support base material layer was larger than the peel strength at the interface between the glass substrate layer and the silicone resin layer.

<Examples 18x-18z>
A glass laminate was obtained according to the same procedure as in Example 18 except that the types of metal compounds used were changed as shown in Table 4.

<Example 19>
A glass laminate was obtained according to the same procedure as in Example 1 except that no metal compound was used. The silicone resin layer of the glass laminate of Example 19 did not contain a specific element.

<Example 20>
A glass laminate was obtained according to the same procedure as in Example 18 except that the temperature of 140 ° C. was changed to 100 ° C. and the temperature of 220 ° C. was changed to 250 ° C. without using a predetermined metal compound. The silicone resin layer of the glass laminate of Example 20 did not contain a specific element.

[Evaluation of edge alteration]
The glass laminates obtained in each example were cut out to obtain a sample of 50 × 50 mm. Each of the obtained samples was placed in an electric furnace preheated to 450 ° C., heat-treated for 1 hour, and then the samples were taken out. The atmosphere in the electric furnace was an atmospheric atmosphere.
Using a microscope, the edge of the sample taken out was observed, and the maximum length of the whitened portion from the edge was observed. The maximum length is intended to be the maximum value of the length L of the whitened end portion as shown in FIG. The shorter the length of L, which represents the end alteration, the better the effect.
The results are summarized in Tables 1 to 4.

As shown in Tables 1 to 4, it was confirmed that the laminate of the present invention exhibited a desired effect.
In particular, it was confirmed that when the silicone resin layer contains iron, manganese, copper, cerium, or bismuth as a specific element, the effect is more excellent.
On the other hand, in Examples 19 and 20 in which the silicone resin layer did not contain a specific element, the effect was inferior.

A 0.1 mm thick stainless steel blade is inserted into the interface between the glass substrate and the silicone resin layer in the glass laminates of Examples 1 to 16 after the above-mentioned end deterioration evaluation is performed to make a cutout portion for peeling. After forming, it was confirmed that the glass substrate can be easily peeled off by completely fixing the glass substrate and pulling up the supporting base material.
On the other hand, in Example 17 in which zirconium tetranormal propoxide was added and bis (2-ethylhexanoic acid) tin (II) was not added, the peel strength was high, and after forming the notch, the glass substrate was completely formed. When fixing and pulling up the supporting base material, cracking of the supporting base material may occur.

<Examples 21 and 22>
Using the glass laminates of Examples 18 and 20, the above-mentioned edge alteration evaluation was carried out according to the same procedure except that the temperature of [edge alteration evaluation] was changed from 450 ° C. to 400 ° C.
The silicone resin layer of the glass laminate of Example 22 did not contain a specific element.
The results are shown in Table 5.
In Table 5, the evaluation conditions indicate the temperature and time at which the evaluation was performed in the edge alteration evaluation.

As shown in Table 5, even when evaluated at 400 ° C., the laminate of the present invention (Example 21) is compared with the laminate (Example 22) in which the silicone resin layer does not contain a specific element and does not satisfy the requirements of the present invention. It was confirmed that it showed a favorable effect.

In the following Examples 23 to 28, an example in which a resin laminate is produced using a polyimide resin substrate which is a resin substrate as a substrate will be described.
As the polyimide resin substrate, a polyimide film (thickness 0.038 mm, trade name "Zenomax" manufactured by Toyobo Co., Ltd.) was used.

<Example 23>
A resin laminate having a supporting base material, a silicone resin layer, and a polyimide resin substrate in this order was obtained according to the same procedure as in Example 6 except that a polyimide resin substrate was used instead of the glass substrate.

<Example 24>
A resin laminate having a supporting base material, a silicone resin layer, and a polyimide resin substrate in this order was obtained according to the same procedure as in Example 18 except that a polyimide resin substrate was used instead of the glass substrate.

<Example 25>
The composition Y prepared in the same manner as in Example 18 is applied to the polyimide resin substrate by the die coating method so that the thickness of the cured silicone resin layer is 8 μm, and heat-treated at 140 ° C. for 10 minutes using a hot plate. This was carried out to form a coating film.
Next, the polyimide resin substrate on which the coating film was formed was heat-treated at 220 ° C. for 30 minutes to form a silicone resin layer.
Next, the supporting base material was placed on the silicone resin layer and bonded using a roll bonding machine to obtain a resin laminate.

<Example 26>
A resin laminate was obtained according to the same procedure as in Example 23 except that the predetermined metal compound was not used. The silicone resin layer of the resin laminate of Example 26 did not contain a specific element.

<Example 27>
A resin laminate was obtained according to the same procedure as in Example 24 except that the temperature at 140 ° C. was changed to 100 ° C. and the temperature at 220 ° C. was changed to 250 ° C. without using a predetermined metal compound. The silicone resin layer of the resin laminate of Example 27 did not contain a specific element.

<Example 28>
A resin laminate was obtained according to the same procedure as in Example 25, except that the temperature at 140 ° C. was changed to 100 ° C. and the temperature at 220 ° C. was changed to 250 ° C. without using a predetermined metal compound. The silicone resin layer of the resin laminate of Example 28 did not contain a specific element.

[Evaluation of edge alteration]
The resin laminate obtained in each example was cut out to obtain a sample having a size of 50 × 50 mm. Each of the obtained samples was placed in an electric furnace preheated to 400 ° C. or 450 ° C., heat-treated for 1 hour, and then the samples were taken out. The atmosphere in the electric furnace was an atmospheric atmosphere.
Using a microscope, the edge of the sample taken out was observed, and the maximum length of the whitened portion from the edge was observed. The maximum length is intended to be the maximum value of the length L of the whitened end portion as shown in FIG. The shorter the length of L, which represents the end alteration, the better the effect.
The results are summarized in Table 6.

In Table 6, the “Formed surface” column indicates on which surface of the supporting base material or the polyimide resin substrate the silicone resin layer was formed before the resin laminate was produced.
The "evaluation condition" column indicates the temperature and time evaluated in the edge alteration evaluation.
Further, in Table 6, "400 ° C-1h and 450 ° C-1h" shown in the "evaluation conditions" column of Examples 24 and 25 is either "400 ° C for 1 hour" or "450 ° C for 1 hour". It is shown that the "end alteration length" was "0.0 mm" even under the condition of.

As shown in Table 6, it was confirmed that the laminate of the present invention exhibits a desired effect even when the substrate is a resin substrate.
Further, it was confirmed that the laminate of the present invention exhibits a desired effect even when a silicone resin layer is formed on the surface of the resin substrate to produce the resin laminate.
On the other hand, in Examples 26 to 28 in which the silicone resin layer did not contain a specific element, the effect was inferior.

<Example 29>
In Example 18, a laminate was prepared by laminating a Si wafer having a diameter of 150 mm and a thickness of 625 μm instead of a glass substrate having a length of 240 mm, a width of 240 mm, and a thickness of 0.2 mm. When this laminate was evaluated for end alteration under the same conditions as in Example 18, the end alteration length was 0.0 mm.

<Example 30>
In Example 20, a laminated body was prepared by laminating a Si wafer having a diameter of 150 mm and a thickness of 625 μm instead of a glass substrate having a length of 240 mm, a width of 240 mm, and a thickness of 0.2 mm. When this laminate was evaluated for end alteration under the same conditions as in Example 20, the end alteration length was 3.0 mm.

In the resin laminates obtained in any of Examples 23 to 28, the supporting base material and the polyimide resin substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion-like defect. ..
Further, in any of the resin laminates of each example, the peel strength at the interface between the silicone resin layer and the support base material layer is the interface between the polyimide resin substrate layer and the silicone resin layer before and after the edge deterioration evaluation. It was larger than the peel strength of.
In addition, after inserting a stainless steel blade having a thickness of 0.1 mm into the interface between the polyimide resin substrate and the silicone resin layer in each of the resin laminates of Examples 23 to 25 to form a notch for peeling, the polyimide resin substrate is completely completed. When the polyimide resin substrate was peeled off by fixing to and pulling up the supporting base material, it was confirmed that the silicone resin layer did not adhere to the peeled polyimide resin substrate.
Further, in the laminated body in which the Si wafers of Example 29 are laminated, the silicone resin layer and the Si wafer are in close contact with each other without generating bubbles, and there is no distortion defect. Further, after inserting a stainless blade having a thickness of 0.1 mm at the interface between the Si wafer of Example 29 and the silicone resin layer to form a notch for peeling, the Si wafer is completely fixed and the supporting base material is pulled up. As a result, when the Si wafer is peeled off, it is confirmed that the silicone resin layer is not attached to the peeled Si wafer.

10,100 Glass laminate 12 Support base material 14 Silicone resin layer 16 Glass substrate 18 Support base material with resin layer 20 Electronic device members 22 Laminates with electronic device members 24 Glass substrate with members 102 Ends

Claims (11)

A support base material, a silicone resin layer, and a substrate are provided in this order.
The silicone resin layer is, iron, manganese, copper, cerium, cobalt, nickel, chromium, and, viewed contains at least one metal element selected from the group consisting of bismuth,
A laminate in which the substrate is a glass substrate. A support base material, a silicone resin layer, and a substrate are provided in this order.
The silicone resin layer contains an element of at least one metal selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth.
A laminate in which the substrate is a resin substrate. The laminate according to claim 2 , wherein the resin substrate is a polyimide resin substrate. A support base material, a silicone resin layer, and a substrate are provided in this order.
The silicone resin layer contains an element of at least one metal selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth.
A laminate in which the substrate is a substrate containing a semiconductor material. The laminate according to claim 4 , wherein the semiconductor material is Si, SiC, GaN, gallium oxide or diamond. The laminate according to any one of claims 1 to 5, wherein the silicone resin layer contains an element of at least one metal selected from the group consisting of iron, manganese, copper, cerium, and bismuth. The laminate according to any one of claims 1 to 6, wherein a plurality of the substrates are laminated on the support base material via the silicone resin layer. A support base material and a silicone resin layer are provided in this order.
The silicone resin layer contains an element of at least one metal selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth.
Wherein either the support substrate is a glass plate Ranaru, silicone resin layer with the supporting substrate. A member forming step of forming a member for an electronic device on the surface of the substrate of the laminate according to any one of claims 1 to 7 to obtain a laminate with a member for an electronic device.
A separation step of removing the support base material and the support base material with a silicone resin layer including the silicone resin layer from the laminate with the member for the electronic device to obtain an electronic device having the substrate and the member for the electronic device. A method of manufacturing an electronic device comprising. A resin substrate and a silicone resin layer are provided in this order.
A resin substrate with a silicone resin layer, wherein the silicone resin layer contains an element of at least one metal selected from the group consisting of iron, manganese, copper, cerium, cobalt, nickel, chromium, and bismuth. A step of forming a laminate by using the resin substrate with a silicone resin layer according to claim 10 and a supporting base material.
A member forming step of forming a member for an electronic device on the surface of the resin substrate of the laminated body to obtain a laminated body with a member for an electronic device.
A method for manufacturing an electronic device, comprising a separation step of removing the supporting base material and the silicone resin layer from the laminate with a member for an electronic device to obtain an electronic device having the resin substrate and the member for the electronic device.

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