JPWO2019142750A1 - Laminates, methods for manufacturing laminates, and methods for manufacturing electronic devices - Google Patents

Abstract

A supporting base material having a hydroxy group on the surface, a silicone resin layer having a hydroxy group, and a substrate are provided in this order, and the substrate is a polyimide resin substrate or at least one layer each of a polyimide resin substrate and a gas barrier film. It is a laminate having each, and the peel strength between the silicone resin layer and the substrate is larger than the peel strength between the support base material and the silicone resin layer. Provided is a laminate capable of suppressing the silicone resin layer from adhering to the substrate when the silicon resin layer and the supporting base material are peeled off.

Description

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

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. are becoming thinner and lighter. ing. Along with this, thinning of substrates such as polyimide resin substrates used for electronic devices is also progressing. If the strength of the substrate is insufficient due to the thinning of the plate, the handleability of the substrate is lowered, and a problem may occur in a step of forming a member for an electronic device on the substrate (member forming step).

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

Japanese Patent Application Laid-Open No. 2015-104843

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

The present invention has been made in view of the above points, and provides a laminate capable of suppressing the silicone resin layer from adhering to the substrate when the substrate is peeled from the silicone resin layer and the supporting base material. The purpose.
A further object of the present invention is to provide a method for producing the above-mentioned laminate and a method for producing an electronic device using the above-mentioned laminate.

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

[1] A supporting base material having a hydroxy group on the surface, a silicone resin layer having a hydroxy group, and a substrate are provided in this order, and the substrate comprises a polyimide resin substrate or a polyimide resin substrate and a gas barrier film, respectively. A laminated substrate having at least one layer at a time, wherein the peeling strength between the silicone resin layer and the substrate is greater than the peeling strength between the supporting base material and the silicone resin layer.
[2] The laminate according to the above [1], wherein the supporting base material is a glass plate or a silicon wafer.
[3] The laminate according to the above [1] or [2], wherein the substrate is the laminated substrate, and the gas barrier film in the laminated substrate is a gas barrier membrane made of an inorganic material.
[4] The laminate according to any one of [1] to [3] above, wherein the plurality of the substrates and the silicone resin layer are arranged on one of the supporting substrates.
[5] The laminate according to any one of [1] to [4] above, 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 thickness of the silicone resin layer is more than 1 μm and 100 μm or less.
[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 ratio of the trifunctional organosiloxy units is 20 mol% or more and 90 mol% with respect to the total organosiloxy units. The laminate according to any one of the above [1] to [7], which is as follows.
[9] The laminate according to any one of [1] to [8] above, wherein the surface roughness Ra of the surface of the silicone resin layer on the substrate side is 0.1 to 20 nm.
[10] The polyimide resin substrate / gas barrier film, from the side closer to the silicone resin layer, is a laminated substrate having at least one layer each of the polyimide resin substrate and the gas barrier film.
The laminate according to any one of [1] to [9] above, wherein the gas barrier film / polyimide resin substrate or the gas barrier film / polyimide resin substrate / gas barrier membrane is laminated in this order.
[11] The method for producing the laminate according to any one of the above [1] to [10], wherein the resin layer forming step of forming the silicone resin layer on the substrate and the surface of the silicone resin layer. A method for producing a laminate, comprising a lamination step of obtaining the laminate by laminating the support base material on the silicon resin.
[12] 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 if necessary, and a coating film is formed. The method for producing a laminate according to the above [11], which comprises a step of curing a curable silicone in a coating film to form a silicone resin layer.
[13] The method for producing a laminate according to the above [12], wherein the curable silicone is a mixture of an organoalkenyl polysiloxane and an organohydrogen polysiloxane.
[14] The method for producing a laminate according to the above [12], wherein the curable silicone is a partially hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable organosilane compound or a hydrolyzable organosilane compound. ..
[15] 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 the above [1] to [10] to obtain a laminate with a member for an electronic device, and the above-mentioned electron. An electron comprising 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 device to obtain the substrate and the electronic device having the member for the electronic device. How to make the device.
[16] The method for manufacturing an electronic device according to the above [9], wherein the member forming step is a step including a heat treatment.
[17] The method for manufacturing an electronic device according to the above [15] or [16], wherein the heat treatment is performed at 50 ° C. or higher and 600 ° C. or lower for 1 to 120 minutes.

According to the present invention, it is possible to provide a laminate capable of suppressing the silicone resin layer from adhering to the substrate when the substrate is peeled from the silicone resin layer and the supporting base material.
Further, according to the present invention, it is also possible to provide a method for producing the above-mentioned laminate and a method for producing an electronic device using the above-mentioned laminate.

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

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 substitutions can be made to the following embodiments without departing from the scope of the present invention.

<Laminated body>
FIG. 1 is a cross-sectional view schematically showing the laminated body 10.
As shown in FIG. 1, the laminate 10 is a laminate including a support base material 12 having a hydroxy group on its surface, a silicone resin layer 14 having a hydroxy group, and a substrate 16 in this order. In other words, the laminate 10 is a laminate including a support base material 12 and a 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 (surface 14a) is in contact with the first main surface 16a of the substrate 16.

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

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

Then, by applying the heat treatment to the laminated body 10, the peel strength is reversed. That is, the peel strength x between the support base material 12 and the silicone resin layer 14 is larger than the peel strength y between the silicone resin layer 14 and the substrate 16.
This is because the hydroxy group of the support base material 12 and the hydroxy group of the silicone resin layer 14 are bonded by the heat treatment, so that the peel strength x between the support base material 12 and the silicone resin layer 14 is increased, and the relative strength x is increased. It is considered that the peel strength x is larger than the peel strength y.
As a result, when a stress is applied to the laminate 10 after the heat treatment in the direction of peeling the supporting base material 12 and the substrate 16, 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 a resin layer.
In this way, it is possible to prevent the silicone resin layer 14 from adhering to the substrate 16 when the substrate 16 is peeled from the silicone resin layer 14 and the supporting base material 12 after the heat treatment.

The heat treatment applied to the laminate 10 may be performed in a member forming step (a step of forming the electronic device member 20 on the substrate 16) described with reference to FIG. 3, or another step (for example, a member). It may be applied in the 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, further 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 examples thereof include an atmospheric atmosphere and an inert gas atmosphere (for example, a nitrogen atmosphere and an argon atmosphere).
The heat treatment may be carried out stepwise by changing the temperature conditions.

From the viewpoint of facilitating the reversal of the peel strength due to the 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, and specifically, 0.3 N / It is preferably 25 mm or less, and more preferably 0.1 N / 25 mm or less.
The peel strength can be evaluated by a 90 ° peel test. That is, the substrate 16 of the laminated body 10 is pulled up at 300 mm / min and peeled off, and the pulling load (peeling strength) can be evaluated as the peeling strength.

(Multi-sided pasting mode)
FIG. 1 illustrates a mode in which one substrate is laminated on a supporting substrate 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 bonding 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 substrate 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 substrate. 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.

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

<Supporting base material>
The support base material 12 is a member that supports and reinforces the base material 16.
The supporting base material 12 is not particularly limited as long as it is a member having a hydroxy group on its surface, and 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 base material can be confirmed by, for example, microinfrared spectroscopic analysis.
The type of glass on the glass plate 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.
More specific examples of the glass plate include a glass plate made of non-alkali borosilicate glass (trade name "AN100" manufactured by Asahi Glass Co., Ltd.).
The method for producing a glass plate 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.
The thickness of the support base material 12 may be thicker or thinner than that of the substrate 16. From the viewpoint of handleability of the laminate 10, the thickness of the support base material 12 is preferably thicker than that of the 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. The thickness of the glass plate is preferably 1.0 mm or less because it is desired to have rigidity that allows the substrate 16 to flex appropriately without cracking when the substrate 16 is peeled off.

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

The polyimide resin substrate is a substrate made of a polyimide resin. For example, a polyimide film is used, and examples of commercially available products thereof include "Zenomax" manufactured by Toyobo Industries, Ltd. and "UPIREX 25S" manufactured by Ube Industries, Ltd. Be done.
In order to form high-definition wiring or the like of an electronic device on the polyimide resin substrate, it is preferable that the surface of the polyimide resin substrate is smooth. Specifically, the surface roughness Ra of the polyimide resin substrate is preferably 50 nm or less, more preferably 30 nm or less, still 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, 1 mm or less is preferable, and 0.2 mm or less is more preferable.
As for the coefficient of thermal expansion of the polyimide 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 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 membrane can be appropriately selected depending on the use of the substrate 16, but a gas barrier membrane made of an inorganic material (inorganic gas barrier membrane) is preferably mentioned.
The material of the inorganic gas barrier layer, for example, silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), and aluminum oxide _(Al 2 _{O 3)} can be mentioned, silicon nitride (SiNx) is 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 the inorganic gas barrier film, a known method for forming an inorganic thin film can be applied. Specifically, for example, 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 intended use of the substrate 16, and is not particularly limited, but is preferably 5 to 2000 nm, more preferably 50 to 500 nm.

The embodiment of the laminated substrate having at least one layer each of the polyimide resin substrate and the gas barrier film (hereinafter, also simply referred to as “laminated substrate”) is not particularly limited, and examples thereof include the following aspects.
-Aspect 1: Polygon resin substrate / Gas barrier film-Aspect 2: Gas barrier film / Polygon resin substrate-Aspect 3: Gas barrier film / Polygon resin substrate / Gas barrier film-Aspect 4: Gas barrier film / Polygon resin substrate / Gas barrier film / Adhesive / Gas barrier film / polyimide resin substrate / gas barrier film-Aspect 5: Polygon resin substrate / Gas barrier film / Polygon resin substrate / Gas barrier film-Aspect 6: Gas barrier film / Polygon resin substrate / Gas barrier film / Polygon resin substrate / Gas barrier film In No. 6, the description is made in order from the one closest to the silicone resin layer. For example, the first aspect is a mode in which the polyimide resin substrate is in contact with the silicone resin layer.
The adhesive material in the above 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 formed into a film in advance, but the present invention is not limited to this, and a varnish may be applied and cured. For example, in the above aspects 5 to 6, first, a "gas barrier film / polyimide resin substrate / gas barrier film" is produced using a film-shaped polyimide resin substrate, and then a varnish is applied onto one of the gas barrier films. It may be dried and cured to form a polyimide resin substrate.

Area of the substrate 16 (the area of the main surface) is not particularly limited, from the viewpoint of productivity of the electronic device, preferably 300 cm ² or more, 1000 cm ² or more, and still more preferably 6000 cm ^2.
The shape of the substrate 16 is not particularly limited, and may be rectangular or circular. The substrate 16 is formed with an orientation flat (so-called orientation flat, 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). May be good.

<Silicone resin layer>
The silicone resin layer 14 has a hydroxy group.
The silicone resin layer 14 is made of a silicone resin, as will be described later. In the silicone resin layer 14, a 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 considered that a hydroxy group appears due to this. ..
As will be described later, when the condensation reaction type silicone is used as the curable silicone to be the silicone resin, the hydroxy group of the condensation reaction type silicone can be the hydroxy group 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, and 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 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 substrate 16, the substrate The occurrence of 16 distortion defects can be suppressed.
The thickness is obtained by measuring the thickness of the silicone resin layer 14 at any position of 5 points or more with a contact-type film thickness measuring device and arithmetically averaging them.

The surface roughness Ra of the surface of the silicone resin layer 14 on the substrate 16 side is not particularly limited, but 0.1 to 20 nm is preferable, and 0.1 to 10 nm is more preferable from the viewpoint of better stackability and peelability of the substrate 16. 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.

(Silicone resin)
The silicone resin layer 14 is mainly made of a silicone resin.
Generally, the organosiloxy unit includes a monofunctional organosiloxy unit called an M unit, a bifunctional organosiloxy unit called a D unit, a trifunctional organosiloxy unit called a T unit, and a tetrafunctional organosiloxy unit called a Q unit. 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 means 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 Expressed as medium O _1/2 . More specifically, for example, in one D unit, that 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 means an oxygen atom in a bond represented by Si—O—Si. Therefore, there is one O ^* between the silicon atoms of the two organosiloxy units.

The 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 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 means 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 means 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 means 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; and an aryl group such as a phenyl group, a trill group, a xsilyl group and a naphthyl group. Aralkyl groups such as benzyl group and phenethyl group; Monovalent hydrocarbons substituted with halogen such as alkyl halide groups (eg, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc.) The group is mentioned. 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 it is preferable that the silicone resin contains at least a T unit as the organosiloxy unit.
The ratio of the specific organosiloxy units is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 60 mol% or more, based on the total organosiloxy units. The upper limit is not particularly limited, but it is often 90 mol% or less.

(Curable silicone)
The silicone resin is usually obtained by curing (crosslink curing) a curable silicone that can become a 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.

The condensation reaction type silicone is a hydrolyzable organosilane compound which is a monomer or a mixture thereof (monomer mixture), or a partial hydrolysis condensation product (organopolysiloxane) obtained by partially hydrolyzing and condensing a monomer or a monomer mixture. Can be preferably used. 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 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 the monomer, the Z group is usually a hydrolyzable group. If there are 2 or 3 R's (2 or 3 a), the plurality of R's 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 to a hydroxy group by a hydrolysis reaction, and then two silicons are subjected to a dehydration condensation reaction between two hydroxy groups bonded to different silicon atoms. Atoms are bonded via the oxygen atom O ^* . Hydroxy groups (or Z groups that have not been hydrolyzed) remain in the curable silicone, and when the curable silicone is cured, these hydroxy 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 having 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 hydroxy 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. 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 heating. 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 the alkenyl group or the like is preferable. It becomes a cross-linking point. 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 linear), and is preferably a hydrosilyl. The group or the like becomes the cross-linking point. The addition reaction type silicone is cured by performing an addition reaction at the cross-linking points of the main agent and the cross-linking agent. The molar ratio of the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane to the alkenyl group of the organoalkenyl polysiloxane is preferably 0.5 to 2 in that the heat resistance derived from the crosslinked structure is more excellent.

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 in terms of coatability, and when Mw is 60,000 or less, it is good in terms of solubility in a solvent and coatability.

(Curable composition)
The method for producing the silicone resin layer 14 described above is not particularly limited, and a known method can be adopted. Among them, the silicone resin layer 14 is excellent in productivity, and as a method for producing the silicone resin layer 14, a curable composition containing the 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 to form a coating film, and the curable silicone in the coating film is cured 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. As the curable silicone, a mixture of organoalkenyl polysiloxane and organohydrogen polysiloxane can also be used.

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 is a solvent that 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, diethylene glycol diethyl ether and the like.
Further, as the solvent, a commercially available product such as "Isoper G" (manufactured by TonenGeneral Sekiyu Co., Ltd.) can also be used.

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 Mega Fvck F558, Mega Fvck F560, and Mega Fvck F561 (all manufactured by DIC Corporation).

The curable composition may contain a metal compound as an additive.
Examples of the metal element contained in the metal compound include 3d transition metal, 4d transition metal, lanthanoid metal, bismuth (Bi), aluminum (Al), tin (Sn) and the like.
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, ittrium (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), erbium (Er), thulium (Tm), ytterbium (Yb), and lutethium (Lu).
The metal compound is preferably a complex. 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, ethylacetate acetate and benzoylacetone.
Examples of the carboxylic acid include acetic acid, 2-ethylhexanoic acid, naphthenic acid, and neodecanoic acid.
Examples of the alkoxide include methoxide, ethoxide, normal propoxide (n-propoxide), isopropoxide, and normal butoxide (n-butoxide).
Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol.
The content of the metal compound in the curable composition is not particularly limited and is appropriately adjusted.

<Manufacturing method of laminated body>
As a method for producing the laminated body 10, as shown in FIG. 2, a method of forming the silicone resin layer 14 on the first main surface 16a of the substrate 16 is preferable.
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 cured to obtain a silicone resin layer 14, and then silicone. A method of manufacturing the laminated body 10 by laminating the supporting base material 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 larger than the peel strength x between the support base material 12 and the silicone resin layer 14.

That is, the method for producing the laminate 10 is a step of forming a curable silicone layer on the first main surface 16a of the substrate 16 and forming the silicone resin layer 14 on the first main surface 16a of the substrate 16 (resin layer formation). A step (step) and a step (lamination step) of laminating the support base material 12 on the surface of the silicone resin layer 14 to obtain the laminate 10 are provided.
Hereinafter, the procedure of each of the above steps will be described in detail.

(Resin layer forming process)
The resin layer forming step is a step of forming a curable silicone layer on the first main surface 16a of the substrate 16 and forming the silicone resin layer 14 on the first main surface 16a of the substrate 16. By this step, a substrate with a silicone resin layer including the substrate 16 and the silicone resin layer 14 in this order can be obtained.
The substrate with a silicone resin layer is a so-called roll-to-roll method in which the silicone resin layer 14 is formed on the first main surface 16a of the rolled substrate 16 and then wound again in a roll shape. Is possible and has excellent production efficiency.
In this step, in order to form a curable silicone layer on the first main surface 16a of the substrate 16, for example, the above-mentioned curable composition is applied to the first main surface 16a 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 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, and a gravure coating method can be mentioned.
Next, the curable silicone applied on the first main 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 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 substrate 16, and 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 aspect of the silicone resin layer 14 to be formed is as described above.

(Laminating process)
The laminating step is a step of obtaining the laminated body 10 by laminating the supporting base material 12 on the surface of the silicone resin layer 14. The laminating step is a step of forming the laminated body 10 by using the substrate with the silicone resin layer and the supporting base material 12.
The method of laminating the support base material 12 on the surface of the silicone resin layer 14 is not particularly limited, and known methods can be mentioned.
For example, a method of stacking the support base material 12 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned. If necessary, the support base material 12 may be laminated on the surface of the silicone resin layer 14, and then the support base material 12 may be pressure-bonded to the silicone resin layer 14 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 supporting base material 12 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, there is an advantage that even if minute bubbles remain, the bubbles are unlikely to grow due to the heat treatment.
It is preferable that the pressure bonding is performed at room temperature because the peel strength y between the silicone resin layer 14 and the substrate 16 can be easily maintained higher than the peel strength x between the support base material 12 and the silicone resin layer 14.
When laminating the support base material 12, it is preferable that the surface of the support base material 12 in contact with the silicone resin layer 14 is sufficiently washed and then laminated in an environment with a high degree of cleanliness.

<Use of laminated body>
The laminate 10 can be used for various purposes, for example, for manufacturing electronic components such as display device panels, PVs, thin-film secondary batteries, semiconductor wafers having circuits formed on the surface, and receiving sensor panels, which will be described later. Can be mentioned. In these applications, the laminate may be exposed to high temperature conditions (eg, 450 ° C. or higher) (eg, 20 minutes or longer) in an air atmosphere.
Display device panels include LCDs, OLEDs, electronic papers, plasma display panels, field emission panels, quantum dot LED panels, micro LED display panels, MEMS (Micro Electro Mechanical Systems) shutter 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. The substrate used for these receiving sensor panels may be reinforced with a reinforcing sheet such as resin.

<Manufacturing method of electronic devices>
An electronic device (a substrate with a member 24) including a substrate 16 and a member 20 for an electronic device is manufactured by using the laminate 10.
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 laminate 22 with the electronic device member, the obtained laminate with the electronic device member is obtained. A method of separating the electronic device (the substrate with a member 24) and the supporting base material 18 with the silicone resin layer from the body 22 with the interface between the silicone resin layer 14 and the substrate 16 as a peeling surface is preferable.
Hereinafter, the step of forming the member 20 for the electronic device is referred to as a "member forming step", and the step of separating the substrate with the member 24 and the supporting base material 18 with the silicone resin layer is referred to as a "separation step".

When the above-mentioned heat treatment is not applied to the laminate 10, the member forming step is preferably a step including the above-mentioned heat treatment.

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 substrate 16 of the laminated body 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 laminated body 22 with an electronic device member.
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 substrate 16 in the laminated body 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 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, 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.
Examples of the member for a thin-film secondary battery include transparent electrodes such as metals or metal oxides of positive and negative electrodes, lithium compounds in the electrolyte layer, metals in the current collector layer, and resins as sealing layers in the lithium ion type. 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 various sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, flexible printed circuit boards, and rigid circuits. Various members and the like corresponding to the flexible printed circuit board and the like can be mentioned.

(Process procedure)
The method for manufacturing the laminated body 22 with the electronic device member described above is not particularly limited, and the second main surface 16b of the substrate 16 of the laminated body 10 is used by a conventionally known method according to the type of the constituent member of the electronic device member. A member 20 for an electronic device is formed on the top.
The member 20 for an electronic device is not a whole member (hereinafter referred to as "all members") finally formed on the second main surface 16b of the substrate 16, but a part of all members (hereinafter referred to as "partial member"). ) May be. The substrate with partial members peeled off from the silicone resin layer 14 can be used as a substrate with all members (corresponding to an electronic device described later) in a subsequent step.
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, it is also possible to assemble the laminated body with all members using two sheets, and then peel off the support base material 18 with the silicone resin layer from the laminated body with all members to manufacture the substrate 24 with two members. it 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, A transparent electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and a sealing plate is used for sealing. Various layer formations and treatments such as are performed. Specific examples of these layer formations and treatments include film formation treatment, thin film deposition treatment, and sealing plate adhesion treatment.

For example, in the case of manufacturing a TFT-LCD, a TFT forming step of forming a thin film transistor (TFT) on a second main surface 16b of a substrate 16 of a laminated body 10 using a material such as LTPS, another laminated body 10 In the CF forming step of forming a color filter (CF) on the second main surface 16b of the substrate 16 using the resist liquid for pattern forming, and the TFT-equipped laminate and the CF forming step obtained in the TFT forming step. It has various steps such as a laminating step of laminating the obtained laminated body with CF.

For example, in the case of manufacturing a micro LED display, a TFT forming step of forming a thin film transistor (TFT) on at least the second main surface 16b of the substrate 16 of the laminate 10 using a material such as LTPS, and the above-mentioned formation. It has an LED mounting step of mounting an LED chip on the 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 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 substrate 16 may be washed before forming the TFT or CF. As the cleaning method, 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.

When forming the member 20 for an electronic device, it is preferable that the above-mentioned heat treatment is performed. As a result, the peel strength is reversed.
That is, as described above, before the heat treatment, the peel strength y between the silicone resin layer 14 and the substrate 16 is larger than the peel strength x between the support base material 12 and the silicone resin layer 14. After the heat treatment, the peel strength x between the supporting base material 12 and the silicone resin layer 14 is larger 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 electronic device member-attached laminate 22 obtained in the member forming step with the interface between the silicone resin layer 14 and the substrate 16 as a peeling surface. This is a step of separating the laminated substrate 16 (substrate with a member 24) and the supporting substrate 18 with a silicone resin layer to obtain a substrate 24 with a member (electronic device) including the member 20 for an electronic device and the substrate 16.

As described above, due to the heat treatment in the member forming step, the peel strength x between the supporting base material 12 and the silicone resin layer 14 becomes larger 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 peeled off.

When the electronic device member 20 on the peeled substrate 16 is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the substrate 16 after the separation.

The method of peeling the substrate 16 and the silicone resin layer 14 is not particularly limited. For example, a sharp blade-like object is inserted into the interface between the substrate 16 and the silicone resin layer 14, a trigger for peeling is given, and then a mixed fluid of water and compressed air is sprayed to peel the resin.
Preferably, the laminate 22 with the electronic device member 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 on the surface plate. Vacuum adsorption is performed, and in this state, the blade is first penetrated into the interface between the substrate 16 and the silicone resin layer 14. 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, the support base material 18 with the silicone resin layer can be easily peeled off.

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

The method for manufacturing an electronic device (board with a member 24) described above is suitable for manufacturing a small display device. The display device is mainly an LCD or an OLED. The LCD includes, for example, a TN type, an STN type, an FE type, a TFT type, a MIM type, an IPS type, and a VA type LCD. Basically, it can be applied to both passive drive type and active drive type display devices.

The substrate 24 with a member includes 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. Can be mentioned.
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.

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.

In Examples 1 to 9 below, a glass plate made of non-alkali borosilicate glass (coefficient of linear expansion 38 × 10 ^-7 / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) is used as a supporting base material, and polyimide is used as a substrate. A film (coefficient of linear expansion 30 × 10 ^-7 / ° C., manufactured by Toyo Boseki Co., Ltd.) was used. It was confirmed by microinfrared spectroscopic analysis that hydroxy groups (OH groups) were present on the surface of the glass plate before lamination.
Examples 1 to 7 are examples, and examples 8 to 9 are comparative examples.

<Example 1>
(Preparation of curable silicone 1)
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 unit, D unit and T unit is 9:59:32, the molar ratio of methyl group to phenyl group of organic group is 44:56, total alkenyl group and total silicon atom. The molar ratio (hydrogen atom / alkenyl group) with the hydrogen atom bonded to was 0.7, and the average number of OX groups was 0.1. The average number of OX groups is a numerical value indicating how many OX groups (X is a hydrogen atom or a hydrocarbon group) are bonded to one Si atom on average.

(Preparation of curable composition 1)
Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldiolefin (CAS No. 68478-92-2) was added to the curable silicone 1 so that the platinum element content was 60 ppm. , Mixture A was obtained. Mixture A (200 g), bismuth 2-ethylhexanoate ("Pucat 25", manufactured by Nippon Kagaku Sangyo Co., Ltd., metal content 25%) (0.08 g), and diethylene glycol diethyl ether ("High Solve EDE") as a solvent. The mixture was mixed with Toho Kagaku Kogyo Co., Ltd. (84.7 g), and the obtained mixture was filtered using a filter having 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 (trade name "Xenomax" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 0.038 mm as a polyimide resin substrate, and heated at 140 ° C. for 10 minutes using a hot plate. As a result, a silicone resin layer was formed on the polyimide resin substrate. The thickness of the silicone resin layer was 10 μm.
It was confirmed by microinfrared spectroscopic analysis that a hydroxy group (OH group) was present in the cured silicone resin layer.
Subsequently, after cleaning with a water-based glass cleaning agent (“PK-LGC213” manufactured by Parker Corporation), a 200 × 200 mm, 0.5 mm thick glass plate “AN100” (supporting base material) washed with pure water is silicone. It was placed on a resin layer and bonded using a bonding device to prepare a laminated body.

(Evaluation of peeling)
The 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 off, and the peeling interface and its pulling load (peeling strength) were evaluated. The peel strength was defined as the peel strength (unit: N / 25 mm).
The peel strength of each of the sample which was not heat-treated after laminating, the sample which was heat-treated at 220 ° C. in the air for 30 minutes, and the sample which was heat-treated at 450 ° C. for 60 minutes under nitrogen was evaluated.

(Evaluation of the 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. under nitrogen for 60 minutes, the number of hydroxy groups in the silicone resin layer was evaluated by microinfrared spectroscopy. As a result, the spectral intensity due to the hydroxy groups was evaluated. Was confirmed to be less than before the heat treatment.

<Example 2>
(Preparation of curable silicone 2)
To a 1 L flask, triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added 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 a crude reaction solution 1. The obtained reaction crude solution 1 was cooled to 25 ° C., and then the reaction crude solution 1 was washed 3 times with water (300 g). Chlorotrimethylsilane (70 g) was added to the washed crude reaction solution 1, and the mixture was stirred at 25 ° C. for 20 minutes, then heated to 50 ° C. and reacted for 12 hours to obtain a crude reaction solution 2. The obtained crude reaction solution 2 was cooled to 25 ° C., and then the crude reaction solution 2 was washed 3 times with water (300 g). Toluene was distilled off under reduced pressure from the washed crude reaction solution 2 to obtain a slurry. The obtained slurry was dried overnight using a vacuum dryer to obtain curable silicone 2 which is a white organopolysiloxane compound. The curable silicone 2 had a molar ratio of M units and 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 tetranormal propoxide ("Organix ZA-45", manufactured by Matsumoto Fine Chemicals Co., Ltd., metal content 21.1%) (0.24 g) as a metal compound, and IsoperG as a solvent. (Made by TonenGeneral Sekiyu Co., Ltd.) (75 g) was mixed, and the obtained mixed solution was filtered using a filter having a pore size of 0.45 μm to obtain a curable composition 2.

(Preparation of laminate)
Using the prepared curable composition 2, a laminate was prepared in the same manner as in Example 1. The thickness of the silicone resin layer was 4 μm.
It was confirmed by microinfrared spectroscopic analysis that a hydroxy group was present 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. Samples that had been heat-treated at 550 ° C. under nitrogen for 10 minutes were also evaluated.

(Evaluation of the 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. under nitrogen for 60 minutes, the number of hydroxy groups in the silicone resin layer was evaluated by microinfrared spectroscopy. As a result, the spectral intensity due to the hydroxy groups was evaluated. Was confirmed to be less than before the heat treatment.

<Example 3>
A laminate was prepared in the same manner as in Example 1 except that a silicon wafer (Si wafer) was used as the supporting base material, and the peel strength and the like were evaluated. The silicon wafer used was one in which the laminated surface was corona-treated after being washed with pure water. It was confirmed by microinfrared spectroscopic analysis that hydroxy groups (OH groups) were present on the surface of the silicon wafer before stacking (hereinafter, the same applies).

<Example 4>
A laminate was prepared in the same manner as in Example 1 except that the polyimide film "UPIREX 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 prepared in the same manner as in Example 1 except that a gas barrier film was formed in advance on the surface 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 by a sputtering method so that the thickness of the SiNx film was 300 nm.

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

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

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

(Preparation of curable composition 3)
A silicon compound (1 part by mass) having an acetylene-based unsaturated group represented by the following formula (1) is mixed with curable silicone 3 (100 parts by mass), and a platinum catalyst is prepared so that the content of platinum element is 100 ppm. Was added to obtain Mixture B.
HC≡CC (CH ₃ ) _2- O-Si (CH ₃ ) ₃ (1)
Mixture B (50 g), zirconium tetranormal propoxide (“Organix 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. (Made by Toray Dow Corning Co., Ltd.) (50 g) was mixed, and the obtained mixed solution was filtered using a filter having a pore size of 0.45 μm to obtain a curable composition 3.

(Preparation of laminate)
Using the prepared curable composition 3, a laminate was prepared in the same manner as in Example 1. The thickness of the silicone resin layer was 10 μm.
It was confirmed by microinfrared spectroscopic analysis that no hydroxy group was present 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 prepared in the same manner as in Example 8 except that a silicon wafer was used as the supporting base material, and the peel strength and the like were evaluated. The silicon wafer used was one in which the laminated surface was corona-treated after being washed with pure water.

The above evaluation results are summarized in Table 1 below.

In the "peeling interface" of Table 1 above, the "supporting base material" means that the silicone resin layer and the supporting substrate were peeled off cleanly, and the "base material" was peeled off cleanly at the interface between the substrate and the silicone resin layer. Means that. Further, "decomposition" means that the silicone resin layer has been decomposed.

As is clear from the results shown in Table 1 above, in Examples 1 to 7, after the heat treatment at 220 ° C. and 450 ° C., the substrate and the silicone resin layer were cleanly peeled off at the interface, and the silicone resin layer adhered to the substrate. I was able to suppress that. 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. Therefore, no distortion defect due to foreign matter was observed on the substrate.
On the other hand, in Examples 8 to 9, after the heat treatment at 220 ° C. and 450 ° C., the silicone resin layer was peeled off at the interface between the supporting base material, and the adhesion of the silicone resin layer to the substrate could not be suppressed.

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

In order to measure the peel strength between the silicone resin layer and the substrate in the laminate that has not been heat-treated, a treatment that intentionally increases the peel strength between the supporting base material and the silicone resin layer in the process of manufacturing the laminate. Was done.
That is, the laminate prepared in the same manner as in Example 1 was peeled off without heat treatment, except that the silicone resin layer was corona-treated and then the supporting base material (glass substrate “AN100”) was attached. As a result of evaluation, it was peeled off cleanly at the interface between the substrate and the silicone resin layer, and the peeling strength was 0.20 N / 25 mm.
Similarly, the laminates prepared in the same manner as in Examples 2 to 9 were evaluated for peeling without heat treatment, except that the silicone resin layer was corona-treated and then the supporting base material was bonded. , It peeled off cleanly at the interface between the substrate and the silicone resin layer. The peel strength of each was as follows, and all were 0.3 N / 25 mm or less.
Example 2: 0.10N / 25mm, Example 3: 0.20N / 25mm, Example 4: 0.25N / 25mm, Example 5: 0.25N / 25mm, Example 6: 0.20N / 25mm, Example 7: 0. 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 No. 2018-005558 filed on January 17, 2018, the contents of which are incorporated herein by reference.

10 Laminated body 12 Support base material 14 Silicone resin layer 14a Silicone resin layer surface 16 Substrate 16a First main surface of the substrate 16b Second main surface of the substrate 18 Support base material with silicone resin layer 20 Electronic device member 22 For electronic devices Laminated body with members 24 Substrate with members (electronic device)

Claims (17)

A supporting base material having a hydroxy group on the surface, a silicone resin layer having a hydroxy group, and a substrate are provided in this order.
The substrate is a polyimide resin substrate or a laminated substrate having at least one layer each of a polyimide resin substrate and a gas barrier film.
A laminate in which the peel strength between the silicone resin layer and the substrate is greater than the peel strength between the supporting base material and the silicone resin layer. The laminate according to claim 1, wherein the supporting base material is a glass plate or a silicon wafer. The substrate is the laminated substrate,
The laminate according to claim 1 or 2, wherein the gas barrier film in the laminated substrate is a gas barrier film made of an inorganic material. The laminate according to any one of claims 1 to 3, wherein the plurality of substrates and the silicone resin layer are arranged on one of the supporting substrates. The laminate according to any one of claims 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. The laminate according to any one of claims 1 to 5, wherein the thickness of the silicone resin layer is more than 1 μm and 100 μm or less. The laminate according to any one of claims 1 to 6, wherein the peel strength between the silicone resin layer and the 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 ratio of the trifunctional organosiloxy units is 20 mol% or more and 90 mol% or less with respect to all 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 surface roughness Ra of the surface of the silicone resin layer on the substrate side is 0.1 to 20 nm. The laminated substrate having at least one layer each of the polyimide resin substrate and the gas barrier film is a polyimide resin substrate / gas barrier film from the side closer to the silicone resin layer.
The laminate according to any one of claims 1 to 9, wherein the gas barrier film / polyimide resin substrate or the gas barrier film / polyimide resin substrate / gas barrier film is laminated in this order. The 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 method for producing a laminated body, comprising a laminating step of obtaining the laminated body by laminating the supporting base material 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 if necessary, and a coating film is formed in the coating film. The method for producing a laminate according to claim 11, further comprising a step of curing the curable silicone of the above to form a silicone resin layer. The method for producing a laminate according to claim 12, wherein the curable silicone is a mixture of an organoalkenyl polysiloxane and an organohydrogen polysiloxane. The method for producing a laminate according to claim 12, wherein the curable silicone is a partially hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable organosilane compound or a hydrolyzable organosilane compound. 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 10 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 the substrate and the electronic device having the member for the electronic device. A method of manufacturing an electronic device to be provided. The method for manufacturing an electronic device according to claim 15, wherein the member forming step is a step including a heat treatment. The method for manufacturing an electronic device according to claim 15 or 16, 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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