JP2022119800A - Laminate, method for manufacturing laminate, and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that can prevent a silicone resin layer from adhering to a substrate when the substrate is peeled off from the silicone resin layer and a support base material.

SOLUTION: Provided is a laminate which is provided with a support base material having a hydroxy group on the surface thereof, a silicone resin layer having a hydroxy group, and a substrate in this order, wherein the substrate is a polyimide resin substrate or a laminated substrate having at least one layer of a polyimide resin substrate and at least one layer of a gas barrier film, and the peeling strength between the silicone resin layer and the substrate is greater than the peeling strength between the support base material and the silicone resin layer.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a laminate, a laminate manufacturing method, and an electronic device manufacturing method.

Electronic devices such as solar cells (PV), liquid crystal panels (LCD), organic EL panels (OLED), receiving sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible light rays, infrared rays, etc. are becoming thinner and lighter. ing. Along with this, substrates such as polyimide resin substrates used in electronic devices are becoming thinner. If the strength of the substrate is insufficient due to the thinning, the handleability of the substrate decreases, and problems may occur in the process of forming electronic device members on the substrate (member forming process).

Therefore, recently, in order to improve the handleability of the substrate, a technique using a laminate having a support base material, a predetermined silicone resin layer, and a substrate in this order has been proposed (Patent Document 1). In this case, first, a predetermined silicone resin layer is formed on the support substrate, and then the substrate is laminated to obtain the laminate. Next, an electronic device member is formed on the substrate of the laminate, and then the substrate (substrate with member) on which the electronic device member is formed is separated from the silicone resin layer and the supporting base material.

Japanese Patent Application Laid-Open No. 2015-104843

In the laminate disclosed in Patent Document 1, the peel strength of each interface between the support substrate, the silicone resin layer and the substrate is not controlled.
As a result of investigation by the present inventors, when the substrate (substrate with member) is peeled from the silicone resin layer and the supporting base material after heat treatment in the manufacturing process of the electronic device, part or all of the silicone resin layer is removed from the substrate. It was found that it may adhere to

The present invention has been made in view of the above points, and it is an object of the present invention to provide a laminate that can suppress adhesion of the silicone resin layer to the substrate when the substrate is peeled off from the silicone resin layer and the supporting substrate. aim.
A further object of the present invention is to provide a method for manufacturing the laminate and a method for manufacturing an electronic device using the laminate.

As a result of extensive studies, the inventors of the present invention have found that the above object can be achieved with the following configuration.

[1] A support base material having a hydroxyl group on its surface, a silicone resin layer having a hydroxyl group, and a substrate are provided in this order, and the substrate is a polyimide resin substrate or a polyimide resin substrate and a gas barrier film, respectively. A laminate, which is a laminated substrate having at least one layer each, wherein the peel strength between the silicone resin layer and the substrate is greater than the peel strength between the support substrate and the silicone resin layer.
[2] The laminate according to [1] above, wherein the supporting substrate is a glass plate or a silicon wafer.
[3] The laminate according to [1] or [2] above, wherein the substrate is the laminated substrate, and the gas barrier film in the laminated substrate is a gas barrier film made of an inorganic material.
[4] The laminate according to any one of [1] to [3] above, wherein a plurality of the substrates and the silicone resin layer are arranged on one supporting substrate.
[5] The laminate according to any one of [1] to [4], wherein the difference in thermal expansion coefficient between the polyimide resin substrate and the supporting substrate is 0 to 90×10 ^-6 /°C.
[6] The laminate according to any one of [1] to [5] above, wherein the silicone resin layer has a thickness of more than 1 μm and not more than 100 μm.
[7] The laminate according to any one of [1] to [6], wherein the peel strength between the silicone resin layer and the substrate is 0.3 N/25 mm or less.
[8] The silicone resin constituting the silicone resin layer contains at least trifunctional organosiloxy units, and the proportion of the trifunctional organosiloxy units is 20 mol% or more and 90 mol% of the total organosiloxy units. The laminate according to any one of [1] to [7] above, wherein:
[9] The laminate according to any one of [1] to [8] above, wherein the substrate-side surface of the silicone resin layer has a surface roughness Ra of 0.1 to 20 nm.
[10] A laminated substrate having at least one layer each of the polyimide resin substrate and the gas barrier film, in order from the side closest to the silicone resin layer: polyimide resin substrate/gas barrier film,
The laminate according to any one of [1] to [9] above, which is laminated in the order gas barrier film/polyimide resin substrate, or gas barrier film/polyimide resin substrate/gas barrier film.
[11] A method for producing a laminate according to any one of [1] to [10] above, comprising: a resin layer forming step of forming the silicone resin layer on the substrate; and a lamination step of obtaining the laminate by laminating the supporting substrate on the substrate.
[12] The resin layer forming step includes applying a curable composition containing a curable silicone to be a silicone resin to the first main surface of the substrate, removing the solvent as necessary to form a coating film, The method for producing a laminate according to [11] above, which includes the step of curing the curable silicone in the coating film to form a silicone resin layer.
[13] The method for producing a laminate according to [12] above, wherein the curable silicone is a mixture of organoalkenylpolysiloxane and organohydrogenpolysiloxane.
[14] The method for producing a laminate according to [12] above, wherein the curable silicone is a hydrolyzable organosilane compound or a partially hydrolyzed condensate obtained by subjecting a hydrolyzable organosilane compound to a hydrolytic condensation reaction. .
[15] A member forming step of forming an electronic device member on the surface of the substrate of the laminate according to any one of [1] to [10] to obtain a laminate with an electronic device member; and a separation step of removing the supporting substrate and the supporting substrate with the silicone resin layer containing the silicone resin layer from the laminate with the device member to obtain an electronic device having the substrate and the electronic device member. How the device is manufactured.
[16] The method for manufacturing an electronic device according to [9] above, wherein the member forming step includes heat treatment.
[17] The method for producing an electronic device according to [15] or [16] above, wherein the heat treatment is performed at 50° C. or higher and 600° C. or lower for 1 to 120 minutes.

ADVANTAGE OF THE INVENTION According to this invention, when peeling a board|substrate from a silicone resin layer and a support base material, it can provide the laminated body which can suppress that a silicone resin layer adheres to a board|substrate.
Furthermore, according to the present invention, it is also possible to provide a method for manufacturing the laminate and a method for manufacturing an electronic device using the laminate.

FIG. 1 is a cross-sectional view schematically showing a laminate. FIG. 2 is a cross-sectional view schematically showing the resin layer forming process. FIG. 3 is a cross-sectional view schematically showing the member forming process. FIG. 4 is a cross-sectional view schematically showing the separation process.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications and replacements can be added to the following embodiments without departing from the scope of the present invention.

<Laminate>
FIG. 1 is a cross-sectional view schematically showing a laminate 10. FIG.
As shown in FIG. 1, the laminate 10 is a laminate comprising a support substrate 12 having hydroxy groups on its surface, a silicone resin layer 14 having hydroxy groups, and a substrate 16 in this order. In other words, laminate 10 is a laminate including support base 12 and substrate 16, and silicone resin layer 14 disposed therebetween. One surface of the silicone resin layer 14 is in contact with the supporting substrate 12 , and the other surface (surface 14 a ) is in contact with the first major surface 16 a of the substrate 16 .

The two-layer portion consisting of the supporting base material 12 and the silicone resin layer 14 (hereinafter also referred to as “supporting base material 18 with silicone resin layer”) functions as a reinforcing plate that reinforces the substrate 16 .

In the laminate 10 , the peel strength y between the silicone resin layer 14 and the substrate 16 is greater than the peel strength x between the supporting substrate 12 and the silicone resin layer 14 . Such a peel strength relationship is realized by, for example, forming the silicone resin layer 14 on the first main surface 16a of the substrate 16 and then laminating the supporting base material 12, as shown in FIG.

Then, by subjecting the laminate 10 to heat treatment, the peel strength is reversed. That is, the peel strength x between the support substrate 12 and the silicone resin layer 14 is greater than the peel strength y between the silicone resin layer 14 and the substrate 16 .
This is because the heat treatment causes the hydroxyl groups of the supporting base material 12 and the hydroxyl groups of the silicone resin layer 14 to bond, thereby increasing the peel strength x between the supporting base material 12 and the silicone resin layer 14, thereby increasing the relative This is probably because the peel strength x is greater than the peel strength y.
As a result, when stress is applied to the laminated body 10 after the heat treatment in a direction in which the supporting base material 12 and the substrate 16 are peeled off, the silicone resin layer 14 and the substrate 16 are peeled off, and the substrate 16 and the silicone are separated. It is separated from the support base material 18 with the resin layer.
In this way, adhesion of the silicone resin layer 14 to the substrate 16 can be suppressed when the substrate 16 is separated from the silicone resin layer 14 and the support base material 12 after the heat treatment.

The heat treatment applied to the laminate 10 may be applied in the member forming step (the step of forming the electronic device member 20 on the substrate 16) described based on FIG. step before the forming step).
The temperature of the heat treatment (heating temperature) is preferably 50° C. or higher, more preferably 100° C. or higher, still more preferably 150° C. or higher, and particularly preferably 200° C. or higher.
The upper limit of the heating temperature is not particularly limited, but if the heating temperature is too high, decomposition may occur depending on the type of the silicone resin layer 14 . Therefore, the heating temperature is preferably 600° C. or lower, more preferably 550° C. or lower, and even more preferably 500° C. or lower.
The heat treatment time (heating time) is preferably 1 to 120 minutes, more preferably 5 to 60 minutes. The heating atmosphere is not particularly limited, and includes an air atmosphere, an inert gas atmosphere (for example, a nitrogen atmosphere, an argon atmosphere), and the like.
The heat treatment may be performed stepwise by changing the temperature conditions.

From the viewpoint of facilitating the reversal of the peel strength due to heat treatment, the peel strength y between the silicone resin layer 14 and the substrate 16 in the laminate 10 is preferably not too large, specifically 0.3 N/ 25 mm or less is preferable, and 0.1 N/25 mm or less is more preferable.
Peel strength can be evaluated by a 90° peel test. That is, the substrate 16 of the laminate 10 is pulled up at 300 mm/min and peeled, and the lifting load (peel strength) can be evaluated as the peel strength.

(Multi-sided pasting mode)
FIG. 1 illustrates a mode in which one substrate is laminated on a support substrate with a silicone resin layer interposed therebetween. However, the laminate of the present invention is not limited to this aspect, and for example, may be an aspect in which a plurality of substrates are laminated on a supporting substrate via a silicone resin layer (hereinafter also referred to as a “multi-sided attachment aspect”). good too.
More specifically, the multi-sided attachment mode is a mode in which all of the plurality of substrates are in contact with the supporting substrate via the silicone resin layer. That is, it is not a mode in which a plurality of substrates are stacked (only one of the plurality of substrates is in contact with the supporting substrate via the silicone resin layer).
In the multi-sided pasting mode, for example, a plurality of silicone resin layers are provided for each individual substrate, and the plurality of substrates and silicone resin layers are arranged on one supporting substrate. However, it is not limited to this, and for example, individual substrates may be arranged on one silicone resin layer (for example, the same size as the supporting substrate) formed on one supporting substrate.

Below, each layer (the support base material 12, the board|substrate 16, and the silicone resin layer 14) which comprises the laminated body 10 is first explained in detail, and after that, the manufacturing method of the laminated body 10 is explained in detail.

<Support base material>
The support base material 12 is a member that supports and reinforces the substrate 16 .
The supporting substrate 12 is not particularly limited as long as it is a member having a hydroxyl group on its surface, and suitable examples thereof include a glass plate and a silicon wafer (Si wafer). The presence or absence of hydroxy groups on the surface of the supporting substrate can be confirmed, for example, by microscopic infrared spectroscopic analysis.
The type of glass for the glass plate is not particularly limited, but alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide glasses containing silicon oxide as a main component are preferred. As the oxide glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
More specifically, the glass plate includes a glass plate made of non-alkali borosilicate glass (manufactured by Asahi Glass Co., Ltd., trade name “AN100”).
The manufacturing method of the glass plate is not particularly limited, and it is usually obtained by melting glass raw materials and forming the 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, a slot down-draw method, and the like.
The thickness of the support base material 12 may be thicker or thinner than the substrate 16 . From the standpoint of handleability of the laminate 10, the thickness of the supporting base material 12 is preferably thicker than that of the substrate 16. FIG.
When the support 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. The thickness of the glass plate is preferably 1.0 mm or less because it is desired to have rigidity such that the glass plate is not cracked and is bent appropriately when the substrate 16 is peeled off.

<Substrate>
The substrate 16 is a polyimide resin substrate or a laminated substrate having at least one polyimide resin substrate and at least one gas barrier film each.

The polyimide resin substrate is a substrate made of polyimide resin, for example, a polyimide film is used, and commercially available products thereof include "Xenomax" manufactured by Toyobo Co., Ltd., "Upilex 25S" manufactured by Ube Industries, Ltd., and the like. be done.
The surface of the polyimide resin substrate is preferably smooth in order to form high-definition wiring of an electronic device on the polyimide resin substrate. Specifically, the surface roughness Ra of the polyimide 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 polyimide resin 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 flexibility, the thickness is preferably 1 mm or less, more preferably 0.2 mm or less.
Regarding the thermal expansion coefficient of the polyimide resin substrate, it is preferable that the thermal expansion coefficient difference between the substrate and the electronic device or the support substrate is small, because warping of the laminate after heating or after cooling can be suppressed. Specifically, the difference in thermal expansion coefficient between the polyimide resin substrate and the supporting substrate is preferably 0 to 90×10 ^-6 /°C, more preferably 0 to 30×10 ^-6 /°C.

The gas barrier film can be appropriately selected depending on the application of the substrate 16, and a gas barrier film made of an inorganic material (inorganic gas barrier film) is preferably used.
Examples of materials for the inorganic gas barrier film include silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), and aluminum oxide (Al ₂ O ₃ ), with silicon nitride (SiNx) being preferred. . Here, x indicates a number of 2.0 or less, and y indicates a number of 4/3 or less.
As a method for forming an inorganic gas barrier film, a known method for forming an inorganic thin film can be applied, and specific examples include a sputtering method, an ion plating method, and a plasma chemical vapor deposition method (hereinafter referred to as plasma CVD method). abbreviated).
The thickness of the inorganic gas barrier film may be appropriately adjusted according to the application of the substrate 16, and is not particularly limited, but is preferably 5 to 2000 nm, more preferably 50 to 500 nm.

Modes of the laminated substrate (hereinafter also simply referred to as "laminated substrate") having at least one layer each of the polyimide resin substrate and the gas barrier film are not particularly limited, but examples thereof include the following modes.
Aspect 1: Polyimide resin substrate/gas barrier film Aspect 2: Gas barrier film/polyimide resin substrate Aspect 3: Gas barrier film/polyimide resin substrate/gas barrier film Aspect 4: Gas barrier film/polyimide resin substrate/gas barrier film/adhesive/ Gas barrier film/polyimide resin substrate/gas barrier film Aspect 5: Polyimide resin substrate/gas barrier film/polyimide resin substrate/gas barrier film Aspect 6: Gas barrier film/polyimide resin substrate/gas barrier film/polyimide resin substrate/gas barrier film Aspects 1 to above 6, they are listed in order from the side closer to the silicone resin layer. For example, Mode 1 is a mode in which the polyimide resin substrate is in contact with the silicone resin layer.
The adhesive in aspect 4 is a conventionally known adhesive, and is not particularly limited.

The polyimide resin substrate in the laminated substrate is usually used as it is after being formed into a film in advance, but is not limited to this, and may be coated with varnish and cured. For example, in the above aspects 5 and 6, first, "gas barrier film/polyimide resin substrate/gas barrier film" is produced using a film-like polyimide resin substrate, and then a varnish is applied on one of the gas barrier films, It may be dried and cured to form a polyimide resin substrate.

The area of the substrate 16 (the area of the main surface) is not particularly limited, but is preferably 300 cm ² or more, more preferably 1000 cm ² or more, and even more preferably 6000 cm ² from the viewpoint of productivity of electronic devices.
The shape of the substrate 16 is also not particularly limited, and may be rectangular or circular. The substrate 16 is formed with an orientation flat (a flat portion formed on the outer periphery of the substrate) and a notch (one or more V-shaped cutouts formed on the outer periphery of the substrate). good too.

<Silicone resin layer>
The silicone resin layer 14 has hydroxy groups.
The silicone resin layer 14 is made of silicone resin, as will be described later. In the silicone resin layer 14, part of the Si--O--Si bond of the T unit, which is one of the organosiloxy units constituting the silicone resin, is broken, and it is believed that this causes the hydroxyl group to appear. .
As will be described later, when condensation-reactive silicone is used as the curable silicone that becomes the silicone resin, the hydroxy groups of the condensation-reactive silicone can become the hydroxy groups of the silicone resin layer 14 .

The thickness of the silicone resin layer 14 is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less. On the other hand, regarding the lower limit, the thickness of the silicone resin layer 14 is preferably more than 1 μm, more preferably 4 μm or more.
When the thickness of the silicone resin layer 14 is within this range, cracks are less likely to occur in the silicone resin layer 14, and even if air bubbles or foreign substances are interposed between the silicone resin layer 14 and the substrate 16, the substrate can be 16 distortion defects can be suppressed.
The above thickness is obtained by measuring the thickness of the silicone resin layer 14 at five or more arbitrary positions with a contact-type film thickness measuring device and averaging the measured values.

The surface roughness Ra of the surface of the silicone resin layer 14 on the substrate 16 side is not particularly limited, but is preferably 0.1 to 20 nm, more preferably 0.1 to 10 nm, from the viewpoint of superior lamination and peelability of the substrate 16. preferable.
The surface roughness Ra is measured in accordance with JIS B 0601-2001, and the arithmetic mean value of Ra measured at five or more arbitrary points corresponds to the surface roughness Ra.

(Silicone resin)
The silicone resin layer 14 is mainly made of silicone resin.
Generally, organosiloxy units include monofunctional organosiloxy units called M units, difunctional organosiloxy units called D units, trifunctional organosiloxy units called T units, and tetrafunctional organosiloxy units called Q units. have units. A 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 (a silicon-containing bonded unit) in the present invention. Monomers forming M units, D units, T units, and Q units are also referred to as M monomers, D monomers, T monomers, and Q monomers, respectively.
By total organosiloxy units is meant the sum of M units, D units, T units and Q units. The ratio of the numbers (molar amounts) of M units, D units, T units, and Q units can be calculated from the peak area ratio values obtained by ²⁹ Si-NMR.

In the organosiloxy unit, the siloxane bond is a bond in which two silicon atoms are bonded via one oxygen atom, so the number of oxygen atoms per silicon atom in the siloxane bond is regarded as 1/2, and the formula 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 a silicon atom in another unit, Its formula is -O _1/2 -(R) ₂ Si-O _1/2 - (R represents a hydrogen atom or an organic group). Due to the presence of 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, an oxygen atom O ^* bonded to another silicon atom is an oxygen atom bonding between two silicon atoms and means an oxygen atom in a bond represented by Si--O--Si. Therefore, one O ^* is present between the silicon atoms of the two organosiloxy units.

M unit means 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) means that three hydrogen atoms or organic groups are bonded to the silicon atom. That is, an M unit has one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom O ^* . More specifically, M units have three hydrogen atoms or organic groups bonded to one silicon atom and an oxygen atom O ^* bonded to one silicon atom.
A D unit means an organosiloxy unit represented by (R) ₂ SiO _2/2 (R represents a hydrogen atom or an organic group). That is, a D unit is a unit having one silicon atom, two hydrogen atoms or organic groups bonded to that silicon atom, and two oxygen atoms O ^* bonded to another silicon atom.
A T unit means an organosiloxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group). That is, a T unit is a unit having one silicon atom, one hydrogen atom or organic group bonded to the silicon atom, and three oxygen atoms O ^* bonded to other silicon atoms.
A Q unit means an organosiloxy unit represented by SiO ₂ . That is, a Q unit is a unit having one silicon atom and four oxygen atoms O ^* bonded to other silicon atoms.
Examples of organic groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group. aralkyl groups such as benzyl group and phenethyl group; halogen-substituted monovalent hydrocarbons such as halogenated alkyl groups (e.g., chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc.) groups. The organic group is preferably an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms (preferably about 1 to 10 carbon atoms).

Although the structure of the silicone resin constituting the silicone resin layer 14 is not particularly limited, it preferably contains at least T units as organosiloxy units.
The proportion of the specific organosiloxy units is preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 60 mol % or more, relative to the total organosiloxy units. Although the upper limit is not particularly limited, it is often 90 mol % or less.

(Curable silicone)
A silicone resin is usually obtained by curing (cross-linking curing) a curable silicone that can be turned into a silicone resin by a curing treatment. In other words, the silicone resin corresponds to a cured product of curable silicone.
Curable silicones are classified into condensation reaction silicones, addition reaction silicones, ultraviolet curing silicones, and electron beam curing silicones according to their curing mechanisms, and any of them can be used.

The condensation-reactive silicone includes a hydrolyzable organosilane compound that is a monomer or a mixture thereof (monomer mixture), or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing a monomer or a monomer mixture. can be preferably used. A mixture of a partial hydrolysis condensate and a monomer may also be used. A monomer may be used individually by 1 type, and may use 2 or more types together.
A silicone resin can be formed by proceeding a hydrolysis/condensation reaction (sol-gel reaction) using this condensation reaction type silicone.

The above 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 hydroxy 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 monomers, the Z group is usually a hydrolyzable group. When there are 2 or 3 R' (when a is 2 or 3), multiple R' may be different.

A curable silicone that is a partial hydrolysis condensate is obtained by a reaction that converts a part of the Z groups of the monomer to oxygen atoms O ^* . When the Z group of the monomer is a hydrolyzable group, the Z group is converted to a hydroxy group by a hydrolysis reaction, followed by a dehydration condensation reaction between two hydroxy groups attached to separate silicon atoms to form two silicon atoms. Atoms are linked through an oxygen atom O ^* . Hydroxy groups (or unhydrolyzed Z groups) remain in the curable silicone, and when the curable silicone is cured, these hydroxy groups and Z groups react and cure in the same manner as described above. A cured product of curable silicone usually becomes a three-dimensionally crosslinked polymer (silicone resin).

When the Z group of the monomer is a hydrolyzable group, the Z group includes alkoxy groups, halogen atoms (eg, chlorine atoms), acyloxy groups, isocyanate groups, and the like. Monomers in which the Z group is an alkoxy group are often used as monomers, and such monomers are also referred to as alkoxysilanes.
An alkoxy group is a hydrolyzable group with relatively low reactivity compared to other hydrolyzable groups such as chlorine atoms, and is a curable silicone obtained using a monomer (alkoxysilane) in which the Z group is an alkoxy group. Among them, unreacted alkoxy groups are often present together with hydroxyl groups as Z groups.

As the condensation-reactive silicone, a partially hydrolyzed condensate (organopolysiloxane) obtained from a hydrolyzable organosilane compound is preferable from the viewpoint of reaction control and handling. A partially hydrolyzed condensate is obtained by partially hydrolyzing and condensing a hydrolyzable organosilane compound. The method of partial hydrolytic condensation is not particularly limited. Usually, it is produced by reacting a hydrolyzable organosilane compound in a solvent in the presence of a catalyst. Catalysts include acid catalysts and alkali catalysts. It is usually preferred to use water for the hydrolysis reaction. The partially hydrolyzed condensate is preferably produced by reacting a hydrolyzable organosilane compound in a solvent in the presence of an acid or alkaline aqueous solution.
A preferred embodiment of the hydrolyzable organosilane compound used includes alkoxysilanes, as described above. That is, one preferred embodiment of curable silicone is curable silicone obtained by hydrolysis reaction and condensation reaction of alkoxysilane.
When alkoxysilane is used, the degree of polymerization of the partially hydrolyzed condensate tends to increase, and the effects of the present invention are more excellent.

As the addition-reactive silicone, a curable composition that contains a main agent and a cross-linking agent and that cures in the presence of a catalyst such as a platinum catalyst can be suitably used. Curing of the addition-reactive silicone is accelerated by heating. The main agent in the addition-reactive silicone is preferably an organopolysiloxane (that is, an organoalkenylpolysiloxane, preferably linear) having an alkenyl group (vinyl group, etc.) bonded to a silicon atom. It becomes a cross-linking point. The cross-linking agent in the addition-reactive silicone is preferably an organopolysiloxane having silicon-bonded hydrogen atoms (hydrosilyl groups) (i.e., organohydrogenpolysiloxane, preferably linear), and hydrosilyl The group or the like becomes a cross-linking point. Addition-reactive silicone cures through an addition reaction between the cross-linking points of the main agent and the cross-linking agent. The molar ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane to the alkenyl groups in the organoalkenylpolysiloxane is preferably 0.5 to 2 in terms of better heat resistance derived from the crosslinked structure.

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 5,000 or more, it is excellent from the viewpoint of coatability, and when Mw is 60,000 or less, it is good from the viewpoint of solubility in a solvent and coatability.

(Curable composition)
A method for manufacturing the silicone resin layer 14 described above is not particularly limited, and a known method can be adopted. Among them, in terms of the productivity of the silicone resin layer 14 being excellent, as a method for manufacturing the silicone resin layer 14, a curable composition containing a curable silicone to be the silicone resin is applied to the first main surface 16a of the substrate 16. Then, if necessary, the solvent is removed, a coating film is formed, and the curable silicone in the coating film is cured to form the silicone resin layer 14 .
As described above, the curable silicone can be a hydrolyzable organosilane compound that is a monomer and/or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing a monomer. Mixtures of organoalkenylpolysiloxanes and organohydrogenpolysiloxanes can also be used as curable silicones.

When an addition reaction type silicone is used as the curable silicone, the curable composition may optionally contain a platinum catalyst as a metal compound containing another metal element.
The platinum catalyst is a catalyst for advancing and accelerating the hydrosilylation reaction between the alkenyl groups in the organoalkenylpolysiloxane and the hydrogen atoms in the organohydrogenpolysiloxane.

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 set to is preferably 1 to 80% by mass, more preferably 1 to 50% by mass.
The solvent is not particularly limited as long as it can easily dissolve the curable silicone under working conditions and can be easily removed by volatilization. Specific examples include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate, diethylene glycol diethyl ether and the like.
Further, as the solvent, commercially available products such as "Isoper G" (manufactured by TonenGeneral Sekiyu K.K.) can also be used.

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

The curable composition may contain a metal compound as an additive.
Metal elements contained in metal compounds include 3d transition metals, 4d transition metals, lanthanide metals, bismuth (Bi), aluminum (Al), and tin (Sn).
The 3d transition metals include transition metals of the fourth period of the periodic table, ie, metals from 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 ).
4d transition metals include transition metals of the fifth period of the periodic table, ie, metals from 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 ).
Lanthanide metals include lanthanum (La) to lutetium (Lu) metals. Specifically, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), and Lutetium (Lu).
The metal compound is preferably a complex. A complex is a group in which ligands (atoms, atomic groups, molecules or ions) are bound to an atom or ion of a metal element. Although the type of ligand contained in the complex is not particularly limited, examples thereof include ligands selected from the group consisting of β-diketones, carboxylic acids, alkoxides, and alcohols.
β-diketones include, for example, acetylacetone, methylacetoacetate, ethylacetoacetate, and benzoylacetone.
Carboxylic acids include, for example, acetic acid, 2-ethylhexanoic acid, naphthenic acid, and neodecanoic acid.
Alkoxides include, for example, methoxide, ethoxide, normal propoxide (n-propoxide), isopropoxide and normal butoxide (n-butoxide).
Alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol.
The content of the metal compound in the curable composition is not particularly limited and is adjusted as appropriate.

<Method for manufacturing laminate>
A preferable method for manufacturing the laminate 10 is to form the silicone resin layer 14 on the first main surface 16a of the substrate 16, as shown in FIG.
Specifically, a curable composition containing curable silicone is applied to the first main surface 16a of the substrate 16, and the obtained coating film is subjected to a curing treatment to obtain the silicone resin layer 14. After that, the silicone is A method of manufacturing the laminate 10 by laminating the support substrate 12 on the surface of the resin layer 14 is preferable.
As a result, the peel strength y between the silicone resin layer 14 and the substrate 16 is greater than the peel strength x between the support substrate 12 and the silicone resin layer 14 .

That is, the method of manufacturing the laminate 10 includes a step of forming a layer of curable silicone on the first main surface 16a of the substrate 16 and forming a silicone resin layer 14 on the first main surface 16a of the substrate 16 (resin layer formation). and a step of laminating the support substrate 12 on the surface of the silicone resin layer 14 to obtain the laminate 10 (lamination step).
The procedure of each of the above steps will be described in detail below.

(Resin layer forming step)
The resin layer forming step is a step of forming a curable silicone layer on the first main surface 16 a of the substrate 16 and forming the silicone resin layer 14 on the first main surface 16 a of the substrate 16 . Through this process, a substrate with a silicone resin layer, which includes the substrate 16 and the silicone resin layer 14 in this order, is obtained.
The substrate with a silicone resin layer is formed by forming the silicone resin layer 14 on the first main surface 16a of the substrate 16 rolled into a roll, and then winding the substrate 16 again into a roll. can be manufactured, and the production efficiency is excellent.
In this step, in order to form a layer of curable silicone on the first main surface 16 a of the substrate 16 , for example, the curable composition described above is applied to the first main surface 16 a of the substrate 16 . Next, it is preferable to form a cured layer by subjecting the curable silicone layer to a curing treatment.
The method of applying the curable composition to the first main surface 16a of the substrate 16 is not particularly limited, and includes known methods. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing and gravure coating.
Next, the curable silicone applied on the first major surface 16a of the substrate 16 is cured to form a cured layer (silicone resin layer 14).
The curing method is not particularly limited, and an optimum treatment is appropriately performed depending on the type of curable silicone used. For example, when condensation reaction type silicone and addition reaction type silicone are used, heat curing treatment is preferable as the curing treatment.
The conditions for the heat curing treatment are within the heat resistance range of the substrate 16. For example, the temperature conditions for heat curing are preferably 50 to 400.degree. C., more preferably 100 to 300.degree. The heating time is generally preferably 10 to 300 minutes, more preferably 20 to 120 minutes.
The mode of the formed silicone resin layer 14 is as described above.

(Lamination process)
The lamination step is a step of obtaining the laminate 10 by laminating the support substrate 12 on the surface of the silicone resin layer 14 . The lamination step is a step of forming the laminate 10 using the substrate with the silicone resin layer and the support base material 12 .
A method for laminating the support base material 12 on the surface of the silicone resin layer 14 is not particularly limited, and a known method can be used.
For example, there is a method of stacking the support substrate 12 on the surface of the silicone resin layer 14 under a normal pressure environment. If necessary, after the support base material 12 is placed on the surface of the silicone resin layer 14, the support base material 12 may be pressure-bonded to the silicone resin layer 14 using a roll or a press. Compression bonding by a roll or a press is preferable because air bubbles entrapped between the silicone resin layer 14 and the supporting substrate 12 can be relatively easily removed.
Compression bonding by a vacuum lamination method or a vacuum press method is preferable because inclusion of air bubbles can be suppressed and a good amount of close contact can be achieved. Press-bonding in a vacuum also has the advantage that even if minute air bubbles remain, the air bubbles are less likely to grow due to the heat treatment.
It should be noted that it is preferable to perform pressure bonding at room temperature because it is easier to maintain the peel strength y between the silicone resin layer 14 and the substrate 16 higher than the peel strength x between the supporting substrate 12 and the silicone resin layer 14 .
When laminating the support base material 12, it is preferable to sufficiently clean the surface of the support base material 12 in contact with the silicone resin layer 14 and perform the lamination in a highly clean environment.

<Application of laminate>
The laminated body 10 can be used for various purposes, for example, it can be used for manufacturing electronic components such as a display device panel, a PV, a thin-film secondary battery, a semiconductor wafer having a circuit formed on its surface, and a receiving sensor panel, which will be described later. mentioned. In these applications, the laminate may be exposed to high temperature conditions (eg, 450° C. or higher) (eg, 20 minutes or longer) in the atmosphere.
Display panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, micro LED display panel, MEMS (Micro Electro Mechanical Systems) shutter panel 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. The substrate used for these receiving sensor panels may be reinforced with a reinforcing sheet such as resin.

<Method for manufacturing electronic device>
Using the laminate 10, an electronic device (member-attached substrate 24) including the substrate 16 and the electronic device member 20 is manufactured.
The method for manufacturing the electronic device is not particularly limited, but after forming the electronic device member 20 on the substrate 16 of the laminate 10 to obtain the electronic device member-attached laminate 22, the obtained electronic device member-attached laminate A preferred method is to separate the body 22 into the electronic device (the member-attached substrate 24) and the silicone resin layer-attached supporting substrate 18 using the interface between the silicone resin layer 14 and the substrate 16 as a peeling surface.
Hereinafter, the process of forming the electronic device member 20 is referred to as the "member forming process", and the process of separating the member-attached substrate 24 and the support substrate 18 with the silicone resin layer is referred to as the "separating step".

If the laminate 10 is not subjected to the heat treatment described above, the member forming step preferably includes the heat treatment described above.

The materials and procedures used in each step are detailed below.

(Member forming process)
The member forming step is a step of forming an electronic device member on the substrate 16 of the laminate 10 . More specifically, as shown in FIG. 3, an electronic device member 20 is formed on the second main surface 16b (exposed surface) of the substrate 16 to obtain a laminate 22 with the electronic device member.
First, the electronic device member 20 used in this process will be described in detail, and then the procedure of the process will be described in detail.

(Electronic device members (functional elements))
The electronic device member 20 is a member that is formed on the substrate 16 in the 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, or an electronic component such as a semiconductor wafer having a circuit formed on its surface, a receiving sensor panel, or the like. Members (for example, members for display devices such as LTPS, members for solar cells, members for thin-film secondary batteries, circuits for electronic components, and members for receiving sensors).

For example, examples of solar cell members include a transparent electrode such as tin oxide for a positive electrode, a silicon layer represented by p-layer/i-layer/n-layer, and a metal for a negative electrode. , dye-sensitized type, quantum dot type, and the like.
Examples of thin-film secondary battery members include transparent electrodes such as positive and negative electrode metals or metal oxides for the lithium ion type, lithium compounds for the electrolyte layer, metals for the current collection layer, resins for the sealing layer, and the like. In addition, various members corresponding to nickel-hydrogen type, polymer type, ceramics electrolyte type, etc. can be mentioned.
Electronic component circuits for CCD and CMOS include metal for conductive parts, silicon oxide and silicon nitride for insulating parts, various sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, flexible printed circuit boards, rigid printed circuit boards, etc. Various members etc. corresponding to a flexible printed circuit board etc. can be mentioned.

(Process procedure)
The method for manufacturing the laminate 22 with the electronic device member described above is not particularly limited. An electronic device member 20 is formed thereon.
The electronic device member 20 is not all of the members finally formed on the second main surface 16b of the substrate 16 (hereinafter referred to as "all members"), but a part of all members (hereinafter referred to as "partial members"). ). The substrate with partial members peeled off from the silicone resin layer 14 can also be made into a substrate with all members (corresponding to an electronic device to be described later) in subsequent steps.
Another electronic device member may be formed on the peeled surface (first main surface 16a) of the substrate with all members that has been peeled off from the silicone resin layer 14 . Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two supporting substrates 18 with silicone resin layers from the laminate with all members to manufacture two substrates 24 with members. can.

For example, in the case of manufacturing an OLED, in order to form an organic EL structure on the surface (second main surface 16b) of the substrate 16 of the laminate 10 opposite to the silicone resin layer 14 side, Forming a transparent electrode, depositing a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, etc. on the surface on which the transparent electrode is formed, forming a back electrode, sealing with a sealing plate, Various layer formation and processing such as are performed. Specific examples of these layer formations and treatments include film formation treatment, vapor deposition treatment, sealing plate adhesion treatment, and the like.

For example, when manufacturing a TFT-LCD, on the second main surface 16b of the substrate 16 of the laminate 10, a TFT formation step of forming a thin film transistor (TFT) using a material such as LTPS, for example, another laminate 10 On the second main surface 16b of the substrate 16 of the CF formation step of forming a color filter (CF) by using a resist solution for pattern formation, and the laminated body with TFT obtained in the TFT formation step and the CF formation step It has various processes such as a bonding process for laminating the obtained laminate with CF.

For example, when manufacturing a micro LED display, at least on the second main surface 16b of the substrate 16 of the laminate 10, a TFT forming step of forming a thin film transistor (TFT) using a material such as LTPS, for example, and forming in the above and an LED mounting step of mounting an LED chip on the TFT. In addition, steps such as planarization, wiring formation, and sealing may be performed.

In the TFT formation process and the CF formation process, TFTs and CFs are formed on the second main surface 16b of the substrate 16 using known photolithography technology, etching technology, or the like. At this time, a resist liquid is used as a coating liquid for pattern formation.
Before forming TFTs and CFs, the second main surface 16b of the substrate 16 may be cleaned, if necessary. As a cleaning method, known dry cleaning or wet cleaning can be used.

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

When forming the electronic device member 20, it is preferable to perform the heat treatment described above. This reverses the peel strength.
That is, as described above, before the heat treatment, the peel strength y between the silicone resin layer 14 and the substrate 16 is greater than the peel strength x between the support substrate 12 and the silicone resin layer 14. After the heat treatment, the peel strength x between the support substrate 12 and the silicone resin layer 14 is greater than the peel strength y between the silicone resin layer 14 and the substrate 16 .

(Separation process)
In the separation step, as shown in FIG. 4, the electronic device member 20 is separated from the laminate 22 with the electronic device member obtained in the member forming step, using the interface between the silicone resin layer 14 and the substrate 16 as a peeling surface. In this step, the laminated substrate 16 (substrate with members 24 ) and the supporting base material 18 with the silicone resin layer are separated to obtain the substrate with members 24 (electronic device) including the electronic device member 20 and the substrate 16 .

As described above, due to the heat treatment in the member forming process, the peel strength x between the support substrate 12 and the silicone resin layer 14 becomes greater than the peel strength y between the silicone resin layer 14 and the substrate 16. ing. Therefore, the silicone resin layer 14 and the substrate 16 are separated.

After separation, the remaining components may be formed on the substrate 16 if the electronic device component 20 on the stripped substrate 16 is part of the formation of all desired components.

A method for separating the substrate 16 and the silicone resin layer 14 is not particularly limited. For example, after inserting a sharp edged object into the interface between the substrate 16 and the silicone resin layer 14 to trigger the separation, the separation can be performed by spraying a mixed fluid of water and compressed air.
Preferably, the laminate 22 with the electronic device member is placed on a surface plate so that the supporting substrate 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 on the surface plate. Vacuum adsorption is performed, and in this state, a cutting tool is first inserted into the interface between the substrate 16 and the silicone resin layer 14 . After that, the supporting base material 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are sequentially raised from the vicinity of the position where the cutting tool is inserted. Then, the supporting substrate 18 with the silicone resin layer can be easily peeled off.

When separating the substrate 24 with members from the laminate 22 with members for an electronic device, the electrostatic adsorption of the pieces of the silicone resin layer 14 to the substrate 24 with members is suppressed by controlling the spraying by the ionizer and the humidity. can be suppressed.

The method for manufacturing the electronic device (substrate with member 24) described above is suitable for manufacturing a small display device. Display devices are mainly LCDs or OLEDs. LCDs include, for example, TN type, STN type, FE type, TFT type, MIM type, IPS type, and VA type LCDs. Basically, it can be applied to both passive drive type and active drive type display devices.

Examples of the member-attached substrate 24 include a display device panel having a display device member, a solar cell having a solar cell member, a thin film secondary battery having a thin film secondary battery member, a receiving sensor panel having a receiving sensor member, and the like. is mentioned.
Display device panels include liquid crystal panels, organic EL panels, plasma display panels, field emission panels, 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.

EXAMPLES The present invention will be specifically described below with reference to examples, etc., but the present invention is not limited to these examples.

In Examples 1 to 9 below, a glass plate made of non-alkali borosilicate glass (linear expansion coefficient 38×10 ⁻⁷ /° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) was used as the support substrate, and polyimide was used as the substrate. A film (linear expansion coefficient 30×10 ⁻⁷ /° C., manufactured by Toyobo Co., Ltd.) was used. Microscopic infrared spectroscopic analysis confirmed the presence of hydroxy groups (OH groups) on the surface of the glass plate before lamination.
Examples 1-7 are working examples, and examples 8-9 are comparative examples.

<Example 1>
(Preparation of curable silicone 1)
A curable silicone 1 was obtained by mixing an organohydrogensiloxane and an alkenyl group-containing siloxane. The composition of curable silicone 1 is such that the molar ratio of M units, D units and T units is 9:59:32, the molar ratio of organic methyl groups to phenyl groups is 44:56, all alkenyl groups and all silicon atoms. was 0.7 and the average number of OX groups was 0.1. The average number of OX groups is a numerical value representing the average number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom.

(Preparation of curable composition 1)
Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (CAS No. 68478-92-2) was added to curable silicone 1 so that the platinum element content was 60 ppm. , to obtain a mixture A. Mixture A (200 g), bismuth 2-ethylhexanoate (“Pcat 25”, manufactured by Nippon Kagaku Sangyo Co., Ltd., metal content 25%) (0.08 g), and diethylene glycol diethyl ether as a solvent (“Hisolve EDE”, (manufactured by Toho Chemical Industry Co., Ltd.) (84.7 g), and the resulting mixture was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition 1.

(Preparation of laminate)
The prepared curable composition 1 is applied to a polyimide film having a thickness of 0.038 mm (trade name "Xenomax" manufactured by Toyobo Co., Ltd.) as a polyimide resin substrate, and heated at 140 ° C. for 10 minutes using a hot plate. Thus, a silicone resin layer was formed on the polyimide resin substrate. The thickness of the silicone resin layer was 10 μm.
The presence of hydroxy groups (OH groups) in the cured silicone resin layer was confirmed by infrared microscopic analysis.
Subsequently, after washing with a water-based glass cleaning agent ("PK-LGC213" manufactured by Parker Corporation), a glass plate "AN100" (supporting substrate) of 200 × 200 mm and 0.5 mm in thickness was washed with pure water. It was placed on the resin layer and bonded together using a bonding device to produce a laminate.

(Evaluation of peeling)
Peel strength and the like were evaluated by performing a 90° peel test. Specifically, the polyimide resin substrate of the produced laminate was pulled up at 300 mm/min and peeled, and the peel interface and its lifting load (peel strength) were evaluated. Peel strength was defined as peel strength (unit: N/25 mm).
The peel strength of a sample that was not heat-treated after lamination, a sample that was heat-treated at 220° C. for 30 minutes in air, and a sample that was heat-treated at 450° C. for 60 minutes under nitrogen was evaluated.

(Evaluation of number of hydroxy groups after heat treatment)
After peeling off the polyimide resin substrate of the laminate that had been heat-treated at 450°C for 60 minutes under nitrogen, the number of hydroxy groups in the silicone resin layer was evaluated by microscopic infrared spectroscopic analysis. was confirmed to be less than before heat treatment.

<Example 2>
(Preparation of curable silicone 2)
A 1 L flask was charged with triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) to obtain a mixture. The obtained mixture was stirred at 25° C. for 20 minutes, then heated to 60° C. and reacted for 12 hours to obtain reaction crude liquid 1. After cooling the obtained reaction crude liquid 1 to 25° C., the reaction crude liquid 1 was washed three times with water (300 g). Chlorotrimethylsilane (70 g) was added to the washed reaction crude liquid 1 and stirred at 25° C. for 20 minutes, then heated to 50° C. and reacted for 12 hours to obtain a reaction crude liquid 2 . After cooling the obtained reaction crude liquid 2 to 25° C., the reaction crude liquid 2 was washed with water (300 g) three times. Toluene was distilled off under reduced pressure from the washed reaction crude liquid 2 to obtain a slurry. The resulting slurry was dried overnight using a vacuum dryer to obtain curable silicone 2, which is a white organopolysiloxane compound. Curable Silicone 2 had a molar ratio of M units to T units of 13:87, all organic groups were methyl groups, and the average number of OX groups was 0.02.

(Preparation of curable composition 2)
Curable silicone 2 (50 g), zirconium tetra-normal propoxide (“Orgatics ZA-45”, manufactured by Matsumoto Fine Chemicals Co., Ltd., metal content 21.1%) (0.24 g) as a metal compound, and Isoper G as a solvent (manufactured by TonenGeneral Sekiyu K.K.) (75 g), and the resulting mixture was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition 2.

(Preparation of laminate)
A laminate was produced in the same manner as in Example 1 using the prepared curable composition 2. The thickness of the silicone resin layer was 4 μm.
Microscopic infrared spectroscopic analysis confirmed the presence of hydroxy groups in the cured silicone resin layer.

(Evaluation of peeling)
The peel strength and the like were evaluated in the same manner as in Example 1. A sample heat treated at 550° C. for 10 minutes under nitrogen was also evaluated.

(Evaluation of number of hydroxy groups after heat treatment)
After peeling off the polyimide resin substrate of the laminate that had been heat-treated at 450°C for 60 minutes under nitrogen, the number of hydroxy groups in the silicone resin layer was evaluated by microscopic infrared spectroscopic analysis. was confirmed to be less than before heat treatment.

<Example 3>
A laminate was produced in the same manner as in Example 1, except that a silicon wafer (Si wafer) was used as the support substrate, and the peel strength and the like were evaluated. The silicon wafer used was washed with pure water and then subjected to corona treatment on the lamination surface. Microscopic infrared spectroscopic analysis confirmed the presence of hydroxy groups (OH groups) on the surface of the silicon wafer before lamination (the same applies hereinafter).

<Example 4>
A laminate was produced in the same manner as in Example 1, except that a polyimide film "Upilex 25S" manufactured by Ube Industries, Ltd. was used as the polyimide resin substrate, and the peel strength and the like were evaluated.

<Example 5>
A laminate was produced in the same manner as in Example 1, except that a gas barrier film was previously formed on the side of the polyimide resin substrate to be coated with the curable composition 1, and the peel strength and the like were evaluated.
The gas barrier film was formed using a sputtering method so that the thickness of the SiNx film was 300 nm.

<Example 6>
A laminate was produced in the same manner as in Example 1, except that a gas barrier film was formed in advance on the side opposite to the side of the polyimide resin substrate to which the curable composition 1 was applied, and the peel strength and the like were evaluated. .
The gas barrier film was formed using a sputtering method so that the thickness of the SiNx film was 300 nm.

<Example 7>
A laminate was produced in the same manner as in Example 1, except that a gas barrier film was previously formed on both surfaces of the polyimide resin substrate, and the peel strength and the like were evaluated.
The gas barrier films were formed on both sides using a sputtering method so that each SiNx film had a thickness of 300 nm.

<Example 8>
(Preparation of curable silicone 3)
A curable silicone 3 was obtained by mixing an organohydrogensiloxane and an alkenyl group-containing siloxane. The composition of curable silicone 3 is as follows: all D units, all organic groups are methyl groups, the molar ratio of all alkenyl groups to all silicon-bonded hydrogen atoms (hydrogen atoms/alkenyl groups) is 0.9, and the average OX The base was 0.

(Preparation of curable composition 3)
A silicon compound (1 part by mass) having an acetylenically unsaturated group represented by the following formula (1) is mixed with curable silicone 3 (100 parts by mass), and a platinum catalyst is added so that the platinum element content is 100 ppm. was added to obtain a mixture B.
HC≡C—C(CH ₃ ) ₂ —O—Si(CH ₃ ) ₃ (1)
Mixture B (50 g), zirconium tetra-normal propoxide (“Orgatics ZA-45”, manufactured by Matsumoto Fine Chemicals Co., Ltd., metal content 21.1%) (0.24 g) as a metal compound, and PMX-0244 as a solvent (manufactured by Dow Corning Toray Co., Ltd.) (50 g), and the resulting mixture was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition 3.

(Preparation of laminate)
A laminate was produced in the same manner as in Example 1 using the prepared curable composition 3. The thickness of the silicone resin layer was 10 μm.
Microscopic infrared spectroscopic analysis confirmed the absence of hydroxyl groups in the cured silicone resin layer.

(Evaluation of peeling)
The peel strength and the like were evaluated in the same manner as in Example 1.

<Example 9>
A laminate was produced in the same manner as in Example 8, except that a silicon wafer was used as the supporting substrate, and the peel strength and the like were evaluated. The silicon wafer used was washed with pure water and then subjected to corona treatment on the lamination surface.

The above evaluation results are summarized in Table 1 below.

In the "peeling interface" in Table 1 above, "support substrate" means that the interface between the silicone resin layer and the supporting substrate was cleanly peeled, and "substrate" means that the interface between the substrate and the silicone resin layer was cleanly peeled. means that Moreover, "decomposition" means that the silicone resin layer was decomposed.

As is clear from the results shown in Table 1 above, in Examples 1 to 7, after heat treatment at 220° C. and 450° C., the interface between the substrate and the silicone resin layer was cleanly separated, and the silicone resin layer adhered to the substrate. I was able to restrain myself from doing it. In Examples 1 and 3 to 7, the thickness of the silicone resin layer was 10 μm, and in Example 2, the thickness of the silicone resin layer was 4 μm.
On the other hand, in Examples 8 and 9, after heat treatment at 220° C. and 450° C., separation occurred at the interface between the silicone resin layer and the supporting substrate, and adhesion of the silicone resin layer to the substrate could not be suppressed.

In the heat treatment at 550° C. of Examples 1 and 3 to 9 using curable silicones 1 and 3, the silicone resin layer decomposed and peeled off during heating, so the peel strength could not be evaluated.

In order to measure the peel strength between the silicone resin layer and the substrate in a laminate that has not been heat-treated, a process of intentionally increasing the peel strength between the supporting substrate and the silicone resin layer during the production process of the laminate. did
That is, the laminate was prepared in the same manner as in Example 1, except that the silicone resin layer was subjected to corona treatment and then the support substrate (glass substrate "AN100") was laminated, and the laminate was peeled off without being subjected to heat treatment. As a result of evaluation, the interface between the substrate and the silicone resin layer was cleanly peeled, and the peel strength was 0.20 N/25 mm.
Similarly, laminates prepared in the same manner as in Examples 2 to 9, except that the silicone resin layer was subjected to corona treatment and then laminated to the support substrate, were evaluated for peeling without heat treatment. , peeled cleanly at the interface between the substrate and the silicone resin layer. Each peel strength was as follows, and all were 0.3 N/25 mm or less.
Example 2: 0.10 N/25 mm, Example 3: 0.20 N/25 mm, Example 4: 0.25 N/25 mm, Example 5: 0.25 N/25 mm, Example 6: 0.20 N/25 mm, Example 7: 0.25 N/25 mm. 25N/25mm, Example 8: 0.15N/25mm, Example 9: 0.15N/25mm

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application 2018-005558 filed on January 17, 2018, the contents of which are incorporated herein by reference.

REFERENCE SIGNS LIST 10 laminate 12 support base 14 silicone resin layer 14a surface of silicone resin layer 16 substrate 16a first main surface of substrate 16b second main surface of substrate 18 support base with silicone resin layer 20 electronic device member 22 electronic device Layered product with member 24 Substrate with member (electronic device)

Claims (17)

A supporting substrate having a hydroxyl group on the surface, a silicone resin layer having a hydroxyl group, and a substrate in this order,
The substrate is a polyimide resin substrate or a laminated substrate having at least one polyimide resin substrate and at least one gas barrier film,
A laminate, wherein the peel strength between the silicone resin layer and the substrate is greater than the peel strength between the supporting substrate and the silicone resin layer. The laminate according to claim 1, wherein the supporting substrate is a glass plate or a silicon wafer. The substrate is the laminated substrate,
3. The laminate according to claim 1, wherein said gas barrier film in said laminated substrate is a gas barrier film made of an inorganic material. 4. The laminate according to any one of claims 1 to 3, wherein a plurality of said substrates and said silicone resin layers are arranged on one said supporting substrate. The laminate according to any one of claims 1 to 4, wherein a difference in thermal expansion coefficient between said polyimide resin substrate and said supporting substrate is 0 to 90 × 10 ^-6 /°C. The laminate according to any one of claims 1 to 5, wherein the silicone resin layer has a thickness of more than 1 µm and not more than 100 µm. 7. The laminate according to any one of claims 1 to 6, wherein the peel strength between said silicone resin layer and said substrate is 0.3 N/25 mm or less. The silicone resin constituting the silicone resin layer contains at least trifunctional organosiloxy units, and the proportion of the trifunctional organosiloxy units is 20 mol% or more and 90 mol% or less with respect to the total organosiloxy units. , The laminate according to any one of claims 1 to 7. The laminate according to any one of claims 1 to 8, wherein the substrate-side surface of the silicone resin layer has a surface roughness Ra of 0.1 to 20 nm. A laminated substrate having at least one layer each of the polyimide resin substrate and the gas barrier film, in order from the side closest to the silicone resin layer: polyimide resin substrate/gas barrier film,
10. The laminate according to claim 1, which is laminated in the order of gas barrier film/polyimide resin substrate, or gas barrier film/polyimide resin substrate/gas barrier film. A method for producing a laminate according to any one of claims 1 to 10,
a resin layer forming step of forming the silicone resin layer on the substrate;
and a lamination step of obtaining the laminate by laminating the support substrate on the surface of the silicone resin layer. In the resin layer forming step, a curable composition containing a curable silicone to be a silicone resin is applied to the first main surface of the substrate, the solvent is removed as necessary, a coating film is formed, and a coating film is formed. 12. The method for producing a laminate according to claim 11, comprising the step of curing the curable silicone of (1) to form a silicone resin layer. 13. The method of making a laminate according to claim 12, wherein the curable silicone is a mixture of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane. 13. The method for producing a laminate according to claim 12, wherein the curable silicone is a hydrolyzable organosilane compound or a partially hydrolyzed condensate obtained by subjecting a hydrolyzable organosilane compound to a hydrolytic condensation reaction. A member forming step of forming an electronic device member on the surface of the substrate of the laminate according to any one of claims 1 to 10 to obtain a laminate with an electronic device member;
a separation step of removing the supporting substrate and the supporting substrate with the silicone resin layer including the silicone resin layer from the laminate with the electronic device member to obtain an electronic device having the substrate and the electronic device member; A method of manufacturing an electronic device comprising: 16. The method of manufacturing an electronic device according to claim 15, wherein said member forming step includes heat treatment. 17. The method of manufacturing an electronic device according to claim 15, wherein the heat treatment is performed at 50° C. or higher and 600° C. or lower for 1 to 120 minutes.

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