JP2014080348A - Method of manufacturing glass laminate and method of manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a glass laminate which has a resin layer excellent in flatness and in which formation of a gap between the resin layer and a glass substrate is suppressed.SOLUTION: The method of manufacturing a glass laminate comprises: a composition layer 12 forming step of forming a curable resin composition containing an organopolysiloxane, a platinum group metal-based catalyst, a reaction inhibitor, and a solvent on a support substrate 10; a removal step of removing the reaction inhibitor and the solvent from a curable resin composition layer 12 to obtain the support substrate with a resin layer 14; and a lamination step of peelably laminating a glass substrate on the resin layer 14 to obtain a glass laminate having the glass substrate. In the removal step, the support substrate having the uncured curable resin composition layer 12 on its surface is arranged on a setter 54 placed on the top of a plurality of support pins 52, and the reaction inhibitor and the solvent are removed.

Description

  The present invention relates to a method for producing a glass laminate having a glass substrate, and a method for producing an electronic device using the glass laminate produced from the method for producing a glass laminate.

  In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

  Therefore, conventionally, a method of forming a device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used. However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials.

  In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

Recently, in order to cope with the above-mentioned problems, a glass laminate in which a glass substrate and a reinforcing plate are laminated is prepared. After forming a member for an electronic device such as a display device on the glass substrate of the glass laminate, the glass laminate is formed. A method of obtaining an electronic device by separating a reinforcing plate from a body has been proposed (see, for example, Patent Document 1 and Patent Document 2). The reinforcing plate has a support substrate and a resin layer fixed on the support substrate, and the resin layer and the glass substrate are in close contact with each other in a peelable manner. The reinforcing plate separated from the glass substrate after the interface between the resin layer of the glass laminate and the glass substrate is peeled off can be laminated with a new glass substrate and reused as a glass laminate.
In particular, in the example of Patent Document 2, a predetermined polyorganosiloxane, a platinum catalyst, a reaction inhibitor (HC≡C—C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ ), a solvent ( It is disclosed that a resin layer is formed using a composition containing n-heptane).

International Publication No. 07/018028 JP 2011-46174 A

On the other hand, conventionally, a method is known in which a support substrate having a coating film disposed on the surface thereof is placed on top of a plurality of support pins and dried by heating.
According to the method described in Patent Documents 1 and 2, the present inventor performed heat drying on the top of the plurality of support pins to produce a glass laminate, and the resin layer and the glass substrate positioned above the support pins. In some cases, many bubbles (voids) were included between the two. The inventor further investigated the cause, and found out that it was mainly caused by unevenness on the surface of the resin layer.

In recent years, with the demand for higher performance of electronic devices, further miniaturization of electronic device members has progressed, and the steps performed have become more complicated. Even under such circumstances, it is required to manufacture an electronic device having excellent performance with high productivity.
When an electronic device is manufactured using the glass laminate described in Patent Documents 1 and 2, a functional layer such as a conductive layer is formed on the exposed surface of the glass substrate in the glass laminate. In that case, various solutions such as a resist solution are used. However, if there are many voids between the resin layer and the glass substrate, the voids expand as the conveyance and heat treatment are repeated. Solution enters by capillary action. The material that has entered the voids is difficult to remove even by washing, and tends to remain as foreign matter after drying. Since the foreign matter becomes a contamination source that contaminates the electronic device member by heat treatment or the like, the performance of the electronic device may be reduced, or the yield may be reduced.

This invention is made in view of the said subject, Comprising: Generation | occurrence | production of the space | gap between a resin layer and a glass substrate was provided, and the manufacturing method of the glass laminated body which has the resin layer excellent in flatness is provided. The purpose is to do.
Another object of the present invention is to provide a method for producing an electronic device using a glass laminate produced by the method for producing a glass laminate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that an uncured curable resin composition layer is disposed when removing the reaction inhibitor and the solvent contained in the composition. It has been found that the above problem can be solved by interposing a setter between the substrate and the support pin.

  That is, in order to achieve the above object, the first aspect of the present invention is a reaction between an organopolysiloxane having an alkenyl group, an organopolysiloxane having a hydrogen atom bonded to a silicon atom, a platinum group metal catalyst, A composition layer forming step of applying a curable resin composition containing an inhibitor and a solvent on a support substrate to form an uncured curable resin composition layer on the support substrate, and the curable property Removing the reaction inhibitor and the solvent from the resin composition layer, curing the curable resin composition layer to obtain a support substrate with a resin layer, and peeling the glass substrate on the resin layer The uncured curable resin composition layer on a setter placed on top of a plurality of support pins in the removing step. The table Provided by arranging the support substrate, the reaction inhibitor and the removal of the solvent, a method of manufacturing a glass laminate.

In the first aspect, the maximum cross-sectional height (W _t ) of the waviness curve on the surface of the resin layer is preferably 0.30 μm or less.

  According to a second aspect of the present invention, a member is formed by forming a member for an electronic device on the surface of the glass substrate of the glass laminate produced by the production method of the first aspect, and obtaining a laminate with the member for an electronic device. And a separation step of removing the support substrate with a resin layer from the laminate with the electronic device member and obtaining an electronic device having the glass substrate and the electronic device member. is there.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the glass laminated body which has the resin layer excellent in flatness by which generation | occurrence | production of the space | gap between a resin layer and a glass substrate was suppressed can be provided.
Moreover, according to this invention, the manufacturing method of an electronic device can also be provided using the glass laminated body manufactured from the manufacturing method of this glass laminated body.

It is a flowchart which shows the manufacturing process of the suitable embodiment of the manufacturing method of the electronic device of this invention. It is typical sectional drawing which shows the suitable embodiment of the manufacturing method of the electronic device of this invention to process order. (A) It is the schematic which shows the aspect by which the support substrate in which the curable resin composition layer was formed in the surface was mounted in the top part of the support pin. (B) It is the schematic which shows the aspect by which the removal process was implemented and the resin layer was formed on the support substrate. (A) It is the schematic which shows the aspect by which the support substrate in which the curable resin composition layer was formed on the surface was mounted on the setter mounted in the top part of the support pin. (B) It is the schematic which shows the aspect by which the removal process was implemented and the resin layer was formed on the support substrate.

Hereinafter, preferred 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 can be made to the following embodiments without departing from the scope of the present invention. Variations and substitutions can be added.
In the present invention, the resin layer and the glass substrate are in close contact with each other so that the peel strength at the interface between the support substrate layer and the resin layer is higher than the peel strength at the interface between the resin layer and the glass substrate. The support substrate and the resin layer are fixed.

The present inventor may place the glass substrate directly on the top of the support pin as a cause of unevenness on the surface of the resin layer in the glass laminate used in the prior art (the inventions of Patent Documents 1 and 2). I found it relevant. More specifically, in the process of removing the reaction inhibitor and the solvent from the uncured curable resin composition layer (for example, heat drying), a predetermined position of the glass substrate is supported throughout the process of the coating film. If the pin is supported, the coating film may be unevenly dried due to a temperature difference between the glass substrate and the periphery of the support pin. Specifically, as shown in FIG. 3A, the support substrate 10 on which the curable resin composition layer 12 on the tops of the plurality of support pins 52 disposed on the support base 50 is placed is placed. When the removal process of the reaction inhibitor and the solvent is performed, minute irregularities may be generated on the surface of the resin layer 14 located near the upper portion of the support pin 52 as shown in FIG.
Therefore, the present inventor has found that the unevenness on the surface of the resin layer can be further suppressed by providing a setter between the support pin and the support substrate instead of placing the support substrate directly on the top of the support pin. Yes. Specifically, as shown in FIG. 4A, a setter 54 is placed on top of a plurality of support pins 52 arranged on a support base 50, and a curable resin composition is further placed on the setter 54. When the support substrate 10 on which the layer 12 is placed is placed and the reaction inhibitor and the solvent are removed, as shown in FIG. 4B, the influence of the support pins 52 is further suppressed and the resin formed. The surface unevenness of the layer 14 is further suppressed.
Below, the manufacturing method of a glass laminated body and an electronic device is demonstrated in order of each process.

FIG. 1 is a flowchart showing manufacturing steps in a preferred embodiment of the method for manufacturing an electronic device of the present invention. As shown in FIG. 1, the electronic device manufacturing method includes a composition layer forming step S102, a removing step S104, a laminating step S106, a member forming step S108, and a separation step S110. In addition, the manufacturing method of the glass laminated body of this invention is equipped with the said composition layer formation process S102, removal process S104, and lamination process S106.
Below, the material used in each process and its procedure are explained in full detail. First, the composition layer forming step S102 will be described in detail.

<Composition layer formation step>
The composition layer forming step S102 includes a linear organopolysiloxane having an alkenyl group, an organopolysiloxane having a hydrogen atom bonded to a silicon atom, a platinum group metal catalyst, a reaction inhibitor, and a solvent. In this step, the curable resin composition to be applied is applied onto a support substrate to form an uncured curable resin composition layer on the support substrate. By performing this step S102, the curable resin composition layer 12 is formed on the support substrate 10 as shown in FIG.

  Hereinafter, first, the materials (support substrate, curable resin composition) used in this step S102 will be described in detail, and then the procedure of step S102 will be described in detail.

[Support substrate]
The support substrate 10 cooperates with a resin layer 14 described later to support and reinforce a glass substrate 18 described later, and manufactures an electronic device member in a member forming step S108 (electronic device member manufacturing process) described later. In this case, the glass substrate 18 is prevented from being deformed, scratched or broken. In addition, when a glass substrate having a thickness smaller than that of a conventional glass substrate is used, a glass laminated body having the same thickness as that of the conventional glass substrate is used, so that in the member forming step S108, the manufacturing suitable for the conventional glass substrate is performed. One of the purposes of using the support substrate 10 is to enable technology and manufacturing equipment.

  As the support substrate 10, for example, a metal plate such as a glass plate, a plastic plate, a SUS plate, or a ceramic plate is used. When the member forming step S108 involves heat treatment, the support substrate 10 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 18, and more preferably formed of the same material as the glass substrate 18. The support substrate 10 is preferably a glass plate. In particular, the support substrate 10 is preferably a glass plate made of the same glass material as the glass substrate 18.

  The thickness of the support substrate 10 may be thicker or thinner than the glass substrate 18. Preferably, the thickness of the support substrate 10 is selected based on the thickness of the glass substrate 18, the thickness of the resin layer 14, and the thickness of the glass laminate. For example, when the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the glass substrate 18 and the thickness of the resin layer 14 is 0.1 mm, the support is provided. The thickness of the substrate 10 is 0.4 mm. In general, the thickness of the support substrate 10 is preferably 0.2 to 5.0 mm.

  In the case where the support substrate 10 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient at 25 to 300 ° C. between the support substrate 10 and the glass substrate 18 (hereinafter simply referred to as “average linear expansion coefficient”) is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably It is 300 × 10 ⁻⁷ / ° C. or less, more preferably 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate may be warped severely during heating and cooling in the member forming step S108, or the glass substrate 18 and the support substrate 16 with a resin layer described later may be peeled off. When the material of the glass substrate 18 and the material of the support substrate 10 are the same, it can suppress that such a problem arises.

[Curable resin composition]
The curable resin composition contains an organopolysiloxane having an alkenyl group, an organopolysiloxane having a hydrogen atom bonded to a silicon atom, a platinum group metal catalyst, a reaction inhibitor, and a solvent. The curable resin composition is cured through a removal step S104 described later to become a cured silicone resin.
Below, the material contained in this composition is explained in full detail.

(Organopolysiloxane)
In the composition, an organopolysiloxane having an alkenyl group (hereinafter also referred to as polysiloxane (a)) and an organopolysiloxane having a hydrogen atom bonded to a silicon atom (hereinafter also referred to as polysiloxane (b)). And are included. The composition corresponds to a so-called addition-reaction type silicone resin composition, and in the presence of a platinum group metal catalyst described later, an alkenyl group and a hydrosilyl group react to cause a crosslinking reaction, and a resin containing a silicone resin. Layer 14 is formed. The resin layer 14 (silicone resin layer) is excellent in heat resistance and peelability. That is, the resin layer 14 is in close contact with the surface of the glass substrate 18 and the free surface thereof has excellent easy peelability.

The polysiloxane (a) has an alkenyl group bonded to a silicon atom, and the bonding position is not particularly limited, and examples thereof include a molecular end or a side chain.
Although the kind of alkenyl group is not particularly limited, usually, those having 2 to 8 carbon atoms are preferred, and those having 2 to 4 carbon atoms are more preferred. For example, a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group, a heptenyl group, and the like can be given. Among them, a vinyl group is preferable because of excellent heat resistance.
The number of alkenyl groups contained in the polysiloxane (a) is not particularly limited, but it is preferable that the resin layer 14 has at least two alkenyl groups in one molecule in terms of more excellent heat resistance. More preferably.
Although the content of the alkenyl group contained in the polysiloxane (a) is not particularly limited, it is 0 with respect to all silicon atom-bonded organic groups in the polysiloxane (a) in that the heat resistance of the resin layer 14 is more excellent. 0.001 to 10 mol% is preferable, and 0.01 to 5 mol% is more preferable.

  The polysiloxane (a) may have an organic group bonded to a silicon atom other than an alkenyl group (hereinafter, also referred to as “silicon atom-bonded organic group”), and does not have an aliphatic unsaturated bond. If it does not specifically limit, For example, an unsubstituted or substituted monovalent | monohydric hydrocarbon group (The number of carbon atoms is 1-12 are preferable, and 1-10 are more preferable.). Examples of the unsubstituted or substituted monovalent hydrocarbon 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, and a heptyl group; a cycloalkyl group such as a cyclohexyl group; Aryl groups such as a group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; some or all of hydrogen atoms of these groups are halogen atoms such as a chlorine atom, a fluorine atom and a bromine atom Substituted halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. are mentioned, preferably alkyl group and aryl group, more preferably methyl group , A phenyl group.

The polysiloxane (b) has a hydrogen atom bonded to a silicon atom, and the bonding position is not particularly limited, and examples thereof include a molecular end or a side chain.
The number of hydrogen atoms contained in the polysiloxane (b) is not particularly limited, but it is preferable to have at least two and more preferably at least three in one molecule in terms of more excellent heat resistance of the resin layer 14. preferable. Although an upper limit in particular is not restrict | limited, Usually, 500 or less are preferable and 200 or less are more preferable.

The polysiloxane (b) may have an organic group bonded to a silicon atom other than a hydrogen atom, and examples thereof include the silicon atom-bonded organic group described above.
The content of hydrogen atoms bonded to silicon atoms in the polysiloxane (b) is not particularly limited, but all the silicon atom-bonded organic groups and all the groups in the polysiloxane (b) are superior in that the heat resistance of the resin layer 14 is more excellent. 0.1-60 mol% is preferable with respect to the sum total with a silicon atom bond hydrogen atom, and 1-50 mol% is more preferable.

  The molecular structure of polysiloxane (a) and polysiloxane (b) is not particularly limited, and examples thereof include linear, cyclic, and branched chains.

  The viscosity of the polysiloxane (a) and the polysiloxane (b) is not particularly limited, and the viscosity at 25 ° C. is 0.1 to 5,000 cP (centipoise) because the film-forming property of the curable resin composition layer 12 is more excellent. ), More preferably 0.5 to 1,000 cP, and even more preferably 5 to 500 cP.

  The content ratio of the polysiloxane (a) and the polysiloxane (b) in the composition is not particularly limited, but the hydrogen atom bonded to the silicon atom in the polysiloxane (b) and the total alkenyl in the polysiloxane (a) It is preferable to adjust the molar ratio of groups (hydrogen atom / alkenyl group) to be 0.7 to 1.05. Especially, it is preferable to adjust a content ratio so that it may become 0.8-1.0. If it is in the said range, while raising the peeling force left to stand for a long time will be suppressed, it is excellent by chemical resistance.

  Examples of the polysiloxanes (a) and (b) include a combination of vinyl silicone “8500” (Arakawa Chemical Industries) and methyl hydrogen polysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11364”. ”(Arakawa Chemical Industries, Ltd.) and methylhydrogenpolysiloxane“ 12031 ”(Arakawa Chemical Industries, Ltd.), vinyl silicone“ 11365 ”(Arakawa Chemical Industries) and methylhydrogenpolysiloxane“ 12031 ”( Combination with Arakawa Chemical Industries).

(Platinum group metal catalyst)
The platinum group metal catalyst (platinum group metal catalyst for hydrosilylation) is used to promote and accelerate the hydrosilylation reaction between the alkenyl group in the polysiloxane (a) and the hydrogen atom in the polysiloxane (b). It is a catalyst.
Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity. A known catalyst can be used as the platinum-based catalyst. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
The content of the platinum group metal catalyst in the composition is not particularly limited, but is preferably 2 to 400 ppm, more preferably 5 to 300 ppm in terms of mass ratio to the total mass of polysiloxane (a) and polysiloxane (b). 8 to 200 ppm is particularly preferable.

(Reaction inhibitor)
The reaction inhibitor (reaction inhibitor for hydrosilylation) is a so-called pot life extender (retarding agent) that suppresses the catalytic activity of the platinum group metal catalyst at room temperature and lengthens the pot life of the composition of the present invention. Also called).
Examples of the reaction inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds. In particular, acetylene compounds (for example, acetylene alcohols and silylated products of acetylene alcohols) are suitable.
More specifically, as reaction inhibitors, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 2-ethynylisopropanol, 2 -Acetylene alcohols such as ethynylbutan-2-ol and 3,5-dimethyl-1-hexyn-3-ol; trimethyl (3,5-dimethyl-1-hexyne-3-oxy) silane, methylvinylbis ( Silylated acetylenic alcohols such as 3-methyl-1-butyne-3-oxy) silane and ((1,1-dimethyl-2-propynyl) oxy) trimethylsilane; diallyl malate, dimethyl malate, diethyl fumarate , Unsaturated carboxylic acid esters such as diallyl fumarate and bis (methoxyisopropyl) malate; 2-isobutyl- -Buten-3-yne, 3,5-dimethyl-3-hexen-1-yne, 3-methyl-3-penten-1-yne, 3-methyl-3-hexen-1-yne, 1-ethynylcyclohexene, Conjugated ene-ynes such as 3-ethyl-3-buten-1-yne and 3-phenyl-3-buten-1-yne; 1,3,5,7-tetramethyl-1,3,5,7- Examples include vinylcyclotetrasiloxanes such as tetravinylcyclotetrasiloxane.

  The boiling point of the reaction inhibitor is not particularly limited, but is preferably 250 ° C. or less, and preferably 200 ° C. or less from the viewpoint that it is easy to remove and the deterioration of the resin layer 14 can be further prevented when the reaction inhibitor is removed by heating. More preferred. Although a minimum in particular is not restrict | limited, From the point which is more excellent in the storage stability of a composition, 50 degreeC or more is preferable and 80 degreeC or more is more preferable.

  Although content in particular of the reaction inhibitor in a composition is not restrict | limited, It is in the range of 0.00001-5 mass parts with respect to the total 100 mass parts of the said polysiloxane (a) and polysiloxane (b). preferable.

(solvent)
The solvent is contained in the composition until it is removed in the removing step S104 described later, and improves the handleability (film forming property, etc.) of the composition.
The boiling point of the solvent contained in the composition is preferably higher than the boiling point of the reaction inhibitor. When the boiling point of the solvent is higher than the boiling point of the reaction inhibitor, the reaction inhibitor can be removed preferentially in the removal step S104. Thereby, the curing reaction can proceed in the curable resin composition layer in a state where the solvent remains, and when the solvent is volatilized, unevenness caused by the volatilization of the solvent on the surface of the composition layer or the like can be caused. Generation | occurrence | production etc. can be suppressed.

  Although the boiling point of the solvent is not particularly limited, it is preferably 270 ° C. or lower, more preferably 250 ° C. or lower, more preferably 230 ° C. or lower, because it is easy to remove and the deterioration of the resin layer 14 can be further prevented when the solvent is removed by heating. More preferably, it is not higher than ° C. Although a minimum in particular is not restrict | limited, From the point which is more excellent in the storage stability of a composition, 50 degreeC or more is preferable and 80 degreeC or more is more preferable.

  Further, the difference between the boiling point of the solvent and the boiling point of the reaction inhibitor is not particularly limited, but is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher, in that the unevenness on the surface of the resin layer 14 can be further suppressed. The upper limit is not particularly limited, but is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, in that the heating temperature can be lowered when the solvent is removed by heating.

  The type of the solvent is not particularly limited. For example, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,4,5-tetra Aromatic hydrocarbon compounds such as methylbenzene, n-dodecylbenzene and cyclohexylbenzene; chain or cyclic such as n-decane, i-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane and cyclooctane A paraffinic mixed solvent or an isoparaffinic mixed solvent comprising an aliphatic hydrocarbon compound or a mixture of two or more thereof; an ester compound such as ethyl benzoate and diethyl phthalate; an ether compound such as dibutyl ether, anisole, and phenetole; and The mixture of 2 or more types of these organic solvents is illustrated.

  The content ratio of the solvent and the reaction inhibitor in the composition is not particularly limited, but the mass ratio (the mass of the solvent / the mass of the reaction inhibitor) is 40 to 400 in that the unevenness of the resin layer 14 can be further suppressed. Is preferable, and 60 to 150 is preferable.

  Although the content of the solvent in the composition is not particularly limited, it is preferably 20 to 70% by mass, preferably 30 to 60% by mass with respect to the total amount of the composition in terms of more excellent film formability of the curable resin composition layer. % Is more preferable.

(Other additives)
The present composition may contain other optional components as necessary. As optional components, inorganic fillers such as dry silica, wet silica, calcined silica, crystalline silica, titanium oxide, alumina, calcium carbonate, carbon black; fine organic resin powders such as epoxy resin and fluororesin; silver, copper Examples thereof include conductive metal powders such as dyes and pigments.

  The viscosity of the composition containing the above components is not particularly limited, and the viscosity at 25 ° C. is preferably 0.5 to 100 cP (centipoise) from the viewpoint that the film forming property of the curable resin composition layer 12 is more excellent. 5 to 50 cP is more preferable.

[Procedure of Step S102]
The method in particular of apply | coating the said curable resin composition on the surface of the support substrate 10 is not restrict | limited, A well-known method can be employ | adopted. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of curable resin composition.

Moreover, it is not applied amount particularly limited curable resin composition, from the viewpoint that a suitable thickness of the resin layer 14 is obtained, it is preferably from 1 to 100 g / m ^2, is 5 to 20 g / m ² Is more preferable.

In addition, after forming the curable resin composition layer 12 that becomes the resin layer 14 on the surface of the support substrate 10, the support substrate 10 including the curable resin composition layer 12 is statically fixed before the removal step S <b> 104 described later. It is preferable to place them. By standing for a predetermined time, the flatness of the surface of the curable resin composition layer 12 is improved, and the surface of the resin layer 14 can be further prevented from being roughened during curing.
The temperature at the time of leaving still is not restrict | limited, What is necessary is just to leave still at the temperature lower than the temperature of the boiling point of a reaction inhibitor, It is preferable that it is 0-100 degreeC, and 0-room temperature (about 25 degreeC) is more. preferable.
The standing time is not particularly limited, and is preferably 30 seconds to 1 hour, more preferably 1 minute to 10 minutes, in that the balance between the flatness and productivity of the resin layer 14 is more excellent.

<Removal process>
In the removal step S104, after the composition layer forming step S102, the reaction inhibitor and the solvent are removed from the curable resin composition layer 12, the curable resin composition layer is cured, and the support substrate with the resin layer is formed. It is a process to obtain. By performing the step S104, as shown in FIG. 2B, the reaction inhibitor and the solvent are removed from the curable resin composition layer 12, and the polysiloxane (a ) And the polysiloxane (b) further progress, and the composition layer 12 is cured to form the resin layer 14.
In step S104, a support substrate provided with an uncured curable resin composition layer on the surface thereof is placed on a setter (holding plate) placed on top of a plurality of support pins, and a reaction inhibitor. And removal of the solvent.
First, members (support pins, setters) used in this step S104 will be described in detail, and the procedure of step S104 will be described in detail.

(Support pin)
A plurality of support pins 52 shown in FIG. 4 are spaced apart from each other on the support base 50 and support the lower surface of the setter 54 on the tip (top) thereof.
The number of support pins 52 is three in FIG. 4, but the number is not particularly limited, and may be ten or more. Further, the arrangement position of the support pins 52 is not particularly limited, and may be arranged at a predetermined interval or randomly.

(Setter)
The setter 54 is a plate in which the first main surface 54a is in contact with the top of the support pin 52 and the support substrate 10 is supported by the second main surface 54b.
The maximum cross-sectional height (W _t ) of the waviness curve on the surface of the second main surface 54b of the setter 54 is preferably 0.300 μm or less. If the surface waviness of the second main surface 54b of the setter 54 is within the above range, the contact area between the setter 54 and the support substrate 10 is increased, and as a result, the surface of the curable resin composition layer 12 in the removing step S104 is removed. Temperature unevenness is reduced, and surface irregularities of the resin layer 14 are further suppressed. In particular, the maximum cross-sectional height (W _t ) of the waviness curve is preferably 0.200 μm or less, and more preferably 0.100 μm or less, in terms of further suppressing the surface unevenness of the resin layer 14. The lower limit is not particularly limited, but is preferably 0.010 μm or more from the viewpoint that the manufacturing process of the setter 54 becomes easier.
The “surface waviness” is a value obtained by measuring the maximum cross-sectional height (W _t ) of a waviness curve described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. In the present invention, the cutoff value of the filtered waviness curve is 0.8 mm, and the measurement length is 40 mm.
As a method for reducing the surface waviness on the surface of the setter 54, a known polishing method (for example, a known physical polishing or chemical polishing, more specifically, CMP or the like) can be used.

The material of the setter 54 is not particularly limited, and examples thereof include metals, ceramics, and glass.
The thickness of the setter 54 is not particularly limited, and is preferably 500 to 5000 μm, more preferably 1000 to 3000 μm, from the viewpoint that surface unevenness of the resin layer 14 is further suppressed.

[Process procedure]
Hereinafter, the procedure of the removal step S104 will be described in detail.
The procedure in this step S104 is not particularly limited, and any method may be performed as long as the reaction inhibitor and the solvent can be removed. For example, the reaction inhibitor may be obtained by a method of heating the curable resin composition layer 12 at a temperature equal to or higher than the boiling point of the reaction inhibitor and the solvent, or by a decompression treatment in which the reaction inhibitor and the solvent in the curable resin composition layer 12 are volatilized. And a method of removing the solvent from the curable resin composition layer 12. The above heating method is preferable from the viewpoint of further progress of the crosslinking of the formed resin layer 14.
Below, the method to heat is mainly explained in full detail.

  The heating temperature in the step S104 is not particularly limited as long as the reaction inhibitor and the solvent can be removed, and is preferably 50 to 300 ° C, more preferably 80 to 270 ° C, in that the surface unevenness of the resin layer 14 is further suppressed. .

  The heating time is appropriately selected depending on the type of the reaction inhibitor and the solvent used, but is preferably 30 seconds to 2 hours in terms of excellent productivity and further suppression of surface irregularities of the resin layer 14. 1 minute to 1 hour is more preferable.

The heating method is not particularly limited, and a known heating device such as an oven can be used.
Note that when heating is performed, heat treatment may be performed stepwise at different temperatures.

(Preferred embodiment 1)
As a suitable aspect of process S104, the 1st removal process which removes the reaction inhibitor contained in curable resin composition layer using the solvent which has a boiling point higher than the boiling point of reaction inhibitor, and curable resin It is preferable to carry out in a stepwise manner the second removal step of removing the solvent remaining in the composition layer.
By dividing the removal of the reaction inhibitor and the solvent in the curable resin composition layer into the above two stages, respectively, first, the reaction inhibitor is removed in the first removal stage, and in the curable resin composition layer. The curing reaction begins to progress. As a result, even when a crosslinked structure of the resin is formed and then the solvent is removed, a change in the shape of the layer is further suppressed, and a resin layer with less surface unevenness can be obtained. The procedure is described in more detail below.

The first removal step is a step of removing the reaction inhibitor from the curable resin composition layer 12 after the composition layer forming step S102. By carrying out this step, the reaction inhibitor is removed from the curable resin composition layer 12, and the addition reaction between the polysiloxane (a) and the polysiloxane (b) in the curable resin composition layer 12. Begins to progress further, and the curable resin composition layer 12 becomes semi-cured.
The procedure of the first removal step is not particularly limited, and any method may be performed as long as the reaction inhibitor can be removed. For example, a method of heating the curable resin composition layer 12 at a temperature not lower than the boiling point of the reaction inhibitor and lower than the boiling point of the solvent (first heating step), or a solvent in the curable resin composition layer 12 A method of removing the reaction inhibitor from the curable resin composition layer 12 by a reduced pressure treatment in which the reaction inhibitor volatilizes without being volatilized may be mentioned. The first heating step is preferable because the reaction inhibitor can be more selectively removed.
Below, the 1st heating process is mainly explained in full detail.

The heating temperature in this step may be a temperature not lower than the boiling point of the reaction inhibitor and lower than the boiling point of the solvent. Especially, it is more preferable that it is 10 degreeC or more temperature higher than the boiling point of a reaction inhibitor by the point by which the surface asperity of the resin layer 14 is suppressed more.
Moreover, it is preferable that it is 20 degreeC or more lower than the boiling point of a solvent at the point by which the surface unevenness | corrugation of the resin layer 14 is suppressed more, and it is more preferable that it is 10 degreeC or more lower temperature.

The heating time is appropriately selected depending on the type of the reaction inhibitor and the solvent to be used. However, 30 seconds to 1 hour is preferable because the productivity is excellent and the surface unevenness of the resin layer 14 is further suppressed. 1 minute-30 minutes are more preferable.
In this step, the solvent in the curable resin composition layer 12 may partially volatilize within a range that does not impair the effects of the present invention.

  The second removal step is a step of removing the solvent remaining in the curable resin composition layer after the first removal step and curing the curable resin composition layer to obtain a resin layer. is there. The solvent in the curable resin composition layer 12 is volatilized, the addition reaction (curing reaction) in the composition layer 12 further proceeds, and the resin layer 14 is formed on the support substrate 10.

The procedure in this step is not particularly limited, and any method may be performed as long as the solvent can be removed. For example, the solvent is removed from the curable resin composition layer 12 by a method of heating the curable resin composition layer 12 at a temperature equal to or higher than the boiling point of the solvent (second heating step) or a decompression process in which the solvent volatilizes. The method of doing is mentioned.
Especially, the said 2nd heating process is preferable at the point which the addition reaction (curing reaction) in this composition layer 12 advances more.
Hereinafter, mainly the second heating step will be described in detail.

The heating temperature in this process should just be the temperature more than the boiling point of the said solvent. Especially, it is more preferable that it is 10 degreeC or more temperature higher than the boiling point of a solvent at the point by which the surface asperity of the resin layer 14 is suppressed more.
The heating time is appropriately selected according to the type of solvent used, but it is preferably 5 minutes to 2 hours in terms of excellent productivity and more suppressed surface irregularities of the resin layer 14. One hour is more preferable.

[Resin layer]
The resin layer 14 formed through the step S104 is fixed on at least one surface of the support substrate 10 and is in close contact with a glass substrate 18 to be described later in a peelable manner. The resin layer 14 prevents the positional displacement of the glass substrate 18 until the operation of separating the glass substrate 18 and the support substrate 10 is performed, and is easily separated from the glass substrate 18 by the separation operation, so that the glass substrate 18 and the like are separated. Prevent damage by operation. In addition, the resin layer 14 is fixed to the support substrate 10, and the resin layer 14 and the support substrate 10 do not peel in the separation operation, and the support substrate 16 with the resin layer is obtained by the separation operation. In order to facilitate the separation of the interface between the resin layer 14 and the glass substrate 18 by the separation operation, it is preferable to perform separation by providing a separation starting point at the interface.
The surface 14a of the resin layer 14 that is in contact with the glass substrate 18 is in close contact with the first main surface 18a of the glass substrate 18 in a peelable manner. In this invention, the property which can peel this resin layer surface 14a easily is called easy peelability (peelability).

In the present invention, the above-mentioned fixing and (separable) adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the adhesion. Further, the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling of the fixed surface. Specifically, in the glass laminate of the present invention, when the operation of separating the glass substrate 18 and the support substrate 10 is performed, it means that the glass substrate 18 is peeled off at the closely contacted surface and is not peeled off at the fixed surface. Therefore, when the operation of separating the glass laminate into the glass substrate 18 and the support substrate 10 is performed, the glass laminate is separated into two, the glass substrate 18 and the support substrate 16 with a resin layer.
That is, the bonding force of the resin layer 14 to the surface of the support substrate 10 is relatively higher than the bonding force of the resin layer 14 to the first main surface 18a of the glass substrate 18. For this reason, the peel strength between the resin layer 14 and the support substrate 10 is higher than the peel strength between the resin layer 14 and the glass substrate 18.

The resin layer 14 is preferably fixed to the surface of the support substrate 10 with a strong bonding force such as an adhesive force or an adhesive force. Usually, the resin layer 14 adheres to the surface of the support substrate 10 by reaction curing of the curable resin composition on the surface of the support substrate 10. In addition, the bonding force between the surface of the support substrate 10 and the resin layer 14 can be increased by applying a treatment (for example, treatment using a coupling agent) that generates a strong bonding force between the surface of the support substrate 10 and the resin layer 14. .
On the other hand, the resin layer 14 is preferably bonded to the first main surface of the glass substrate 18 with a weak bonding force, for example, bonded with a bonding force resulting from van der Waals force between solid molecules. The resin layer surface 14a before coming into contact with the glass substrate 18 is an easily peelable surface, and by bringing the easily peelable resin layer surface 14a into contact with the first main surface 18a of the glass substrate 18, both surfaces are brought into contact with each other. It can be combined with a weak binding force.

  Although the thickness of the resin layer 14 is not specifically limited, It is preferable that it is 1-100 micrometers, It is more preferable that it is 5-30 micrometers, It is further more preferable that it is 7-20 micrometers. This is because if the thickness of the resin layer 14 is within such a range, the resin layer 14 and the glass substrate 18 described later are sufficiently adhered. Moreover, even if a foreign substance may be present between the resin layer 14 and the glass substrate 18, the occurrence of a distortion defect in the glass substrate 18 can be further suppressed. In addition, if the thickness of the resin layer 14 is too thick, it takes time and materials to form the resin layer 14 and is not economical.

The surface of the resin layer 14 is preferably flat. In particular, the maximum cross-sectional height (W _t ) of the surface waviness curve is preferably 0.300 μm or less. If the surface waviness of the resin layer 14 is within the above range, the generation of bubbles between the resin layer 14 and the glass substrate 18 is further suppressed. In particular, the maximum cross-sectional height (W _t ) of the undulation curve is preferably 0.200 μm or less, and more preferably 0.100 μm or less. The lower limit is not particularly limited, but is often 0.010 μm or more.
The “surface waviness” is a value obtained by measuring the maximum cross-sectional height (W _t ) of a waviness curve described in JIS B-0610 (1987) using a known stylus type surface shape measuring device. In the present invention, the cutoff value of the filtered waviness curve is 0.8 mm, and the measurement length is 40 mm.

<Lamination process>
Lamination process S106 is a process of laminating | stacking a glass substrate so that peeling is possible on the resin layer 14 surface (14a) of the support substrate 16 with a resin layer obtained by the said removal process S104. More specifically, as shown in FIG. 2C, in this step S106, a glass substrate 20 is obtained by laminating a glass substrate 18 on the surface of the resin layer 14 of the support substrate 16 with a resin layer.
In addition, when the external force for peeling the support substrate 16 with a resin layer is applied to the laminated body with the member for electronic devices mentioned later, the exfoliation is possible at the interface between the support substrate 10 and the resin layer 14 and inside the resin layer 14. It means the property of peeling at the interface between the glass substrate 18 and the resin layer 14 without peeling.

  First, the glass substrate 18 used at this process S106 is explained in full detail, and the procedure of subsequent process S106 is explained in full detail.

[Glass substrate]
As for the glass substrate 18, the 1st main surface 18a adheres to the resin layer 14, and the member for electronic devices mentioned later is provided in the 2nd main surface 18b on the opposite side to the resin layer 14 side.
The kind of the glass substrate 18 may be a common one, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 18 is excellent in chemical resistance and moisture permeability and has a low thermal shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  When the linear expansion coefficient of the glass substrate 18 is large, the member forming step S108 is often accompanied by heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 18, if the glass substrate 18 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 18.

  The glass substrate 18 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. Further, the glass substrate 18 having a particularly small thickness can be obtained by heating the glass once formed into a plate shape to a moldable temperature, and stretching it by means of stretching or the like to make it thin (redraw method).

  The glass of the glass substrate 18 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

  As the glass of the glass substrate 18, glass suitable for the type of electronic device member and its manufacturing process is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 18 is 0.3 mm or less, more preferably 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 18. In the case of more than 0.3 mm, the glass substrate 18 cannot satisfy the demand for thickness reduction and / or weight reduction. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 18. In the case of 0.15 mm or less, the glass substrate 18 can be wound into a roll.
The thickness of the glass substrate 18 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 18 and easy handling of the glass substrate 18.

  The glass substrate 18 may be composed of two or more layers. In this case, the material forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate 18” means the total thickness of all the layers.

[Procedure of Step S106]
In this step S106, the support substrate 16 with the resin layer and the glass substrate 18 described above are prepared, and both the resin layer surface 14a of the support substrate 16 with the resin layer and the first main surface 18a of the glass substrate 18 are laminated surfaces. Are stuck together. The laminated surface 14a of the resin layer 14 is easily peelable based on the properties of the silicone resin that is a material constituting the layer, and can be easily peeled and adhered by normal overlapping and pressing. .

The method in particular of laminating | stacking the glass substrate 18 on the resin layer 14 is not restrict | limited, A well-known method is employable.
For example, after the glass substrate 18 is stacked on the surface 14a of the easily peelable resin layer 14 under a normal pressure environment, the resin layer 14 and the glass substrate 18 may be pressure-bonded using a roll or a press. It is preferable because the resin layer 14 and the glass substrate 18 are more closely adhered by pressure bonding with a roll or a press. Further, it is preferable because air bubbles mixed between the resin layer 14 and the glass substrate 18 are relatively easily removed by pressure bonding with a roll or a press.

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause distortion defects of the glass substrate 18.

  When the resin layer 14 is detachably adhered to the first main surface 18a of the glass substrate 18, the surfaces of the resin layer 14 and the glass substrate 18 that are in contact with each other are sufficiently washed and laminated in a clean environment. It is preferable to do. Even if a foreign substance is mixed between the resin layer 14 and the glass substrate 18, the resin layer 14 is deformed and thus does not affect the flatness of the surface of the glass substrate 18. Is preferable because it becomes favorable.

[Glass laminate]
The glass laminate 20 of the present invention can be used for various applications. For example, it manufactures electronic parts such as display panel, PV, thin film secondary battery, and semiconductor wafer having a circuit formed on the surface. The use to do is mentioned. In this application, the glass laminate 20 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 300 ° C. or higher).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

<Member formation process>
Member formation process S108 is a process of forming the member for electronic devices on the surface of the glass substrate in the glass laminated body obtained in the said lamination process S106.
More specifically, as shown in FIG. 2D, in this step S108, the electronic device member 22 is formed on the second main surface 18b of the glass substrate 18, and the electronic device member-attached laminate 24 is formed. obtain.

  First, the electronic device member 22 used in this step S108 will be described in detail, and then the procedure of step S108 will be described in detail.

(Electronic device components (functional elements))
The electronic device member 22 is a member that is formed on the second main surface 18b of the glass substrate 18 in the glass laminate 20 and constitutes at least a part of the electronic device. More specifically, the electronic device member 22 includes a member 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 the surface thereof. . Examples of the display device panel include an organic EL panel, a plasma display panel, a field emission panel, and the like.

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

(Process procedure)
The manufacturing method of the laminated body 24 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 18 of the glass laminated body 20 is used. An electronic device member 22 is formed on the surface 18b.
The electronic device member 22 is not all of the members finally formed on the second main surface 18b of the glass substrate 18 (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the resin layer 14 can be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed on the peeling surface (first main surface) of the glass substrate with all members peeled from the resin layer 14. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 16 with a resin layer from the laminate with all members. Furthermore, an electronic device can also be manufactured by assembling an electronic device using two laminates with all members, and then peeling the two support substrates 16 with a resin layer from the laminate with all members.

  For example, taking the case of manufacturing an OLED as an example, an organic EL structure on the surface of the glass laminate 20 opposite to the resin layer 14 side of the glass substrate 18 (corresponding to the second main surface 18b of the glass substrate). Forming a transparent electrode, depositing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed, forming a back electrode, sealing plate Various layer formation and processing, such as sealing using, are performed. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

  Further, for example, the TFT-LCD manufacturing method is formed on the second main surface 18b of the glass substrate 18 of the glass laminate 20 by a general film forming method such as a CVD method and a sputtering method using a resist solution. Forming a thin film transistor (TFT) by patterning a metal film and a metal oxide film to be formed, and patterning a resist solution on the second main surface 18b of the glass substrate 18 of another glass laminate 20 The CF forming step for forming a color filter (CF) and the laminate with TFT obtained in the TFT forming step and the laminate with CF obtained in the CF forming step are arranged so that the TFT and CF face each other. It has various processes, such as a bonding process of laminating through a seal.

In the TFT forming process and the CF forming process, the TFT and CF are formed on the second main surface of the glass substrate by using a well-known photolithography technique or etching technique. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, you may wash | clean the 2nd main surface of a glass substrate before forming TFT and CF as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the bonding step, for example, a liquid crystal material is injected and laminated between the laminated body with TFT and the laminated body with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

[Separation process]
Separation process S110 is a process of removing the support substrate with a resin layer from the laminate 24 with an electronic device member obtained in the member forming process S108 to obtain an electronic device having a glass substrate and an electronic device member. .
More specifically, as shown in FIG. 2 (E), the support substrate 16 with a resin layer is separated and removed from the laminate 24 with a member for electronic devices by the step S110, and the glass substrate 18 and the electronic device are separated. The electronic device 26 including the working member 22 is obtained.

When the member for electronic devices on the glass substrate at the time of peeling is a part of formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate after separation.
Hereinafter, the procedure of this process S110 is explained in full detail.

  The method of peeling the 1st main surface 18a of the glass substrate 18 and the surface 14a of the resin layer 14 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 18 and the resin layer 14 to provide a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed to peel off the film. can do. Preferably, the electronic device member-attached laminate 24 is placed on the surface plate so that the support substrate 10 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 side is vacuum-adsorbed on the surface plate. (In the case where support substrates are laminated on both sides, the steps are sequentially performed). In this state, first, the blade is inserted into the glass substrate 18-resin layer 14 interface. Then, the support substrate 10 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed at the interface between the resin layer 14 and the glass substrate 18, and the air layer spreads over the entire interface, and the support substrate 10 can be easily peeled off.

  Moreover, when removing the glass substrate 16 with a resin layer from the laminated body 24 with a member for electronic devices, the static electricity which may affect the electronic device 26 is suppressed by controlling the spraying and humidity by an ionizer. it can. Alternatively, a circuit that consumes static electricity may be incorporated into the electronic device 26, or a sacrificial circuit may be incorporated to conduct electricity from the terminal portion to the outside of the laminate.

  The electronic device 26 obtained by the step S110 is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

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

<Example 1-1>
Prepare a glass substrate (“AN100”, linear expansion coefficient 38 × 10 ⁻⁷ / ° C. non-alkali glass plate: manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.5 mm as a support substrate and washed with pure water The substrate was cleaned by UV cleaning to obtain a support substrate with a cleaned surface.
Next, as a component (A), linear vinylmethylpolysiloxane (“VDT-127”, viscosity at 25 ° C. 700-800 cP (centipoise): manufactured by Azumax, mol% of vinyl group in 1 mol of organopolysiloxane: 0.325 ) And linear methylhydropolysiloxane (“HMS-301” as component (B), viscosity 25-35 cP (centipoise) at 25 ° C .: manufactured by Asmax, the number of hydrogen atoms bonded to silicon atoms in one molecule: 8) are mixed so that the molar ratio of all vinyl groups to hydrogen atoms bonded to all silicon atoms (hydrogen atoms / vinyl groups) is 0.9, with respect to 100 parts by weight of this siloxane mixture, 1 part by mass of a silicon compound having an acetylenically unsaturated group represented by the following formula (1) as the component (C) (boiling point: 120 ° C.) Mixed.
HC≡C—C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ Formula (1)
Next, a platinum-based catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) such that the platinum metal concentration is 100 ppm in terms of platinum with respect to the total amount of component (A), component (B), and component (C). ) Was added to obtain a mixed liquid of the organopolysiloxane composition. Furthermore, 150 parts by weight of heptane (boiling point: 98 ° C., manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts by weight of the obtained mixed liquid to obtain a mixed solution.

Next, while discharging the mixed solution from the die coater onto the support substrate (speed 40 mm / s, GAP 100 μm, discharge pressure 50 kPa), moving the die coater from one end side to the other end side of the support substrate, A curable resin composition layer was formed thereon.
Then, the support substrate was mounted on the setter supported by the top part of a some support pin as shown in FIG.
The setter was an aluminum substrate having a thickness of 1 mm, and the filtered center line waviness (W _CA ) of the surface on which the support substrate was placed was 0.100 μm.

Then, after carrying out a heat curing treatment (first removal step) at 180 ° C. for 10 minutes in the atmosphere, a heat curing treatment (second removal step) at 270 ° C. for 30 minutes in the atmosphere, A cured silicone resin layer (length 350 mm × width 300 mm × thickness 15 μm) was formed on the support substrate to obtain a support substrate A with a resin layer.
In the above step, in the first removal step, hexane as a solvent and a silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by formula (1) as a reaction inhibitor are removed. It was.

On the other hand, a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm (“AN100”, an alkali-free glass plate having a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C .: manufactured by Asahi Glass Co., Ltd.) is washed with pure water and UV washed. The surface of the glass substrate was cleaned.
Then, after aligning the said support substrate A and a glass substrate, peeling of the cured silicone resin layer of the 1st main surface of a glass substrate and the support substrate A with a resin layer at room temperature using a vacuum press apparatus. A glass laminate was obtained by bringing the surface into close contact.

<Example 1-2>
A glass was prepared according to the same procedure as in Example 1-1 except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Example 2-1>
A glass laminate was produced according to the same procedure as in Example 1 except that the heating temperature in the first removal step was changed from 180 ° C to 120 ° C.
In this example, in the first removal step, hexane as a solvent and silicon compound having an acetylenically unsaturated group represented by formula (1) as a reaction inhibitor (boiling point: 120 ° C.) are removed. It had been.

<Example 2-2>
A glass was prepared according to the same procedure as in Example 2-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Example 3-1>
A glass laminate was produced according to the same procedure as in Example 1 except that the conditions of the first removal step were changed from a heat curing treatment at 180 ° C. for 10 minutes in the air to a vacuum drying treatment at room temperature. .
In this example, in the first removal step, hexane as a solvent and silicon compound having an acetylenically unsaturated group represented by formula (1) as a reaction inhibitor (boiling point: 120 ° C.) are removed. It had been.

<Example 3-2>
A glass was prepared according to the same procedure as in Example 3-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Example 4-1>
A glass laminate was produced according to the same procedure as in Example 1-1 except that the first removal step was not performed.

<Example 4-2>
A glass was prepared according to the same procedure as in Example 4-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Example 5-1>
A glass laminate was produced in the same manner as in Example 1-1 except that IP solvent 2028 (boiling point: 213 to 262 ° C., manufactured by Idemitsu Kosan Co., Ltd.) was used instead of heptane.
In this example, in the first removal step, the silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by the formula (1) as the reaction inhibitor is removed, and the IP solvent remains. The IP solvent was removed in the second removal step.

<Example 5-2>
A glass was prepared according to the same procedure as in Example 5-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Example 6-1>
A glass laminate was produced according to the same procedure as in Example 2-1, except that IP solvent 2028 (boiling point: 213 to 262 ° C., manufactured by Idemitsu Kosan Co., Ltd.) was used instead of heptane.
In this example, in the first removal step, the silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by the formula (1) as the reaction inhibitor is removed, and the IP solvent remains. The IP solvent was removed in the second removal step.

<Example 6-2>
According to the same procedure as in Example 6-1 except that a glass substrate having a length of 350 mm, a width of 300 mm, and a plate thickness of 0.2 mm was used instead of a glass substrate having a length of 350 mm, a width of 300 mm, and a plate thickness of 0.1 mm. A laminate was produced.

<Example 7-1>
A glass laminate was produced according to the same procedure as in Example 3-1, except that IP solvent 2028 (boiling point: 213 to 262 ° C., manufactured by Idemitsu Kosan Co., Ltd.) was used instead of heptane.
In this example, in the first removal step, the silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by the formula (1) as the reaction inhibitor is removed, and the IP solvent remains. The IP solvent was removed in the second removal step.

<Example 7-2>
A glass was prepared according to the same procedure as in Example 7-1 except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Comparative Example 1-1>
Instead of placing the support substrate on the setter, a glass laminate was produced according to the same procedure as in Example 1-1 except that the setter was not used and the support substrate was placed directly on top of the support pins. .

<Comparative Example 1-2>
Glass was used in accordance with the same procedure as Comparative Example 1-1 except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Comparative Example 2-1>
Instead of placing the support substrate on the setter, a glass laminate was produced according to the same procedure as in Example 2-1, except that the setter was not used and the support substrate was placed directly on top of the support pins. .

<Comparative Example 2-2>
Glass was used in accordance with the same procedure as Comparative Example 2-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Comparative Example 3-1>
Instead of placing the support substrate on the setter, a glass laminate was produced according to the same procedure as in Example 3-1, except that the setter was not used and the support substrate was placed directly on top of the support pins. .

<Comparative Example 3-2>
Glass was used in accordance with the same procedure as Comparative Example 3-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Comparative Example 4-1>
Instead of placing the support substrate on the setter, a glass laminate was produced according to the same procedure as in Example 4-1, except that the setter was not used and the support substrate was placed directly on top of the support pins. .

<Comparative Example 4-2>
Glass was used in accordance with the same procedure as Comparative Example 4-1, except that a glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.2 mm was used instead of the glass substrate having a length of 350 mm, a width of 300 mm, and a thickness of 0.1 mm. A laminate was produced.

<Evaluation 1>
Bubbles generated between the cured silicone resin layers of the laminates obtained in the above Examples and Comparative Examples and the glass substrate were visually confirmed and evaluated according to the following criteria. The results are summarized in Table 1.
In practice, it is desirable that the value is not “x”.
“◯”: No bubbles are visually observed “Δ”: A very small amount of bubbles (bubbles having a diameter of 2 mm or less) are observed, but there is no practical problem. “×”: Bubbles (bubbles having a diameter of more than 2 mm) are confirmed. When heated, there is a possibility that bubbles will expand and there is a practical problem

<Evaluation 2>
The resin layer surface of the support substrate with a resin layer obtained in the above Examples and Comparative Examples was measured by Surfcom (Tokyo Seimitsu Co., Ltd .: 1400D-12), and the maximum of the swell curve described in JIS B-0610 (1987) The cross-sectional height (W _t ) was measured.

In Table 1, the “Setter use / non-use” column indicates “○” when the setter is used, and “X” when the setter is not used.
In the “removal step” column, “A” indicates that the solvent is removed in the first removal step, and “solvent is removed in the second removal step when the solvent is not removed in the first removal step. B ”.
The “Evaluation 1” column shows the result of the evaluation 1.

As shown in Table 1 above, in the method for producing a glass laminate of the present invention, a glass having a resin layer excellent in flatness in which generation of bubbles (voids) between the resin layer and the glass substrate is suppressed. A laminate is obtained.
As can be seen from the comparison between Examples 1-1 and 1-2, when a thinner glass substrate (a glass substrate having a thickness of 0.1 mm) is used, the rigidity of the substrate is reduced, and the surface of the resin layer is reduced. It is presumed that the followability increased, and as a result, the generation of bubbles was further suppressed.
In particular, as can be seen from the comparison between Example 1-2 and Example 5-2, a thicker glass substrate is used by removing the reaction inhibitor and the solvent stepwise using a high boiling point solvent. Even in this case, it was confirmed that the generation of bubbles can be further suppressed.
On the other hand, as shown in Comparative Examples 1-1 to 4-2, when the setter was not used, the generation of bubbles could not be suppressed.

<Example 8>
In this example, an OLED was produced using the glass laminate produced in Example 1-1.
More specifically, a molybdenum film was formed by a sputtering method on the second main surface of the glass substrate subjected to the polishing treatment in the glass laminate, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide is formed by sputtering and photolithography is used. A pixel electrode was formed by etching.
Subsequently, on the second main surface side of the glass substrate, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then formed on the second main surface side of the glass substrate by sputtering. Aluminum was deposited, and a counter electrode was formed by etching using a photolithography method.Next, ultraviolet light was formed on the second main surface of the glass substrate on which the counter electrode was formed. Another glass substrate was bonded and sealed through a chemical adhesive layer, and the glass laminate having the organic EL structure on the glass substrate obtained by the above procedure was laminated with an electronic device member. Applies to the body.
Subsequently, after the sealed body side of the obtained glass laminate is vacuum-adsorbed to a surface plate, a 0.1 mm thick stainless steel product is formed at the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate. A blade was inserted, and the support substrate with a resin layer was separated from the glass laminate to obtain an OLED panel (corresponding to an electronic device, hereinafter referred to as panel A). When an IC driver was connected to the manufactured panel A and driven under normal temperature and normal pressure, display unevenness was not observed in the driving region. Further, even when driven in a high temperature and high humidity environment (80 ° C., 80% RH), display unevenness was not recognized.

<Example 9>
In this example, an LCD was produced using the glass laminate produced in Example 1-1.
Two glass laminates are prepared. First, a molybdenum film is formed by sputtering on the second main surface of a glass substrate that has been subjected to polishing treatment in one glass laminate, and etching is performed using a photolithography method. A gate electrode was formed. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD, indium tin oxide was formed by sputtering and photolithography was used. A pixel electrode was formed by etching. Next, a polyimide resin liquid was applied on the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminated body is called glass laminated body A1.
Next, a chromium film was formed by sputtering on the second main surface of the glass substrate on which the other glass laminate had been subjected to polishing treatment, and a light-shielding layer was formed by etching using photolithography. Next, a color resist was further applied by a die coating method to the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second main surface side of the glass substrate by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid was applied to the second main surface of the glass substrate provided with the counter electrode by a die coating method, and columnar spacers were formed by a photolithography method and heat curing. Next, a polyimide resin solution was applied on the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. Next, after the sealing resin liquid is drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal is dropped in the frame by the dispenser method, the above-described glass laminate A1 is used. The 2nd main surface side of the glass substrate of a sheet of glass laminated body was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained. Hereinafter, the laminate having the LCD panel is referred to as a laminate B2 with a panel.
Next, LCD panel B (corresponding to an electronic device) composed of a substrate on which a TFT array is formed and a substrate on which a color filter is formed is peeled off from both sides of the laminated body B2 with a panel in the same manner as in Example 1. Got.
When an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region. Further, even when driven in a high temperature and high humidity environment (80 ° C., 80% RH), display unevenness was not recognized.

DESCRIPTION OF SYMBOLS 10 Support substrate 12, 12a, 12b Curable resin composition layer 14 Resin layer 16 Support substrate 18 with resin layer Glass substrate 20 Glass laminate 22 Electronic device member 24 Electronic device member laminate 26 Electronic device 50 Support base 52 Support pin 54 Setter

Claims (3)

A curable resin composition containing an organopolysiloxane having an alkenyl group, an organopolysiloxane having a hydrogen atom bonded to a silicon atom, a platinum group metal catalyst, a reaction inhibitor, and a solvent on a supporting substrate. Applying a composition layer forming step of forming an uncured curable resin composition layer on the support substrate; and
Removing the reaction inhibitor and the solvent from the curable resin composition layer, curing the curable resin composition layer, and obtaining a support substrate with a resin layer; and
Laminating a glass substrate on the resin layer in a peelable manner to obtain a glass laminate having a glass substrate,
In the removing step, the support substrate provided with the uncured curable resin composition layer on the surface thereof is placed on a setter placed on top of a plurality of support pins, and the reaction inhibitor and the solvent The manufacturing method of the glass laminated body which removes. The maximum section height of the waviness curve of the resin layer surface (W _t) is less than 0.30 .mu.m, method of manufacturing a glass laminate according to claim 1. A member forming step of forming a member for an electronic device on the surface of the glass substrate of the glass laminate produced by the production method according to claim 1 or 2 to obtain a laminate with a member for an electronic device;
A separation step of removing the support substrate with a resin layer from the laminate with the member for electronic devices and obtaining an electronic device having the glass substrate and the member for electronic devices.