JP2015232053A - Organopolysiloxane, crosslinked organopolysiloxane and composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organopolysiloxane having adhesiveness to a glass substrate and having suppressed decomposition under high temperature treatment condition when made to be a crosslinked article.SOLUTION: There is provided an organopolysiloxane containing a siloxane unit (A) represented by the formula (1) and a siloxane unit (B) represented by the formula (2), where a percentage of the siloxane unit (A) is 30 to 60 mol%, the total percentage of the siloxane unit (A) and the siloxane unit (B) based on the total siloxane unit is 90b to 100 mol% and the siloxane unit (B) contains alkenyl having 3 or less carbon atoms.

Description

  The present invention relates to an organopolysiloxane, a crosslinked organopolysiloxane which is a crosslinked product thereof, and a coating composition containing the organopolysiloxane.

  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 problems, after preparing a glass laminate in which a thin glass substrate and a reinforcing plate are laminated and forming a member for an electronic device such as a display device on the thin glass substrate of the glass laminate, A method for separating a support plate from a thin glass substrate has been proposed (see, for example, Patent Document 1). The reinforcing plate has a support plate and a silicone resin layer made of a crosslinked organopolysiloxane fixed on the support plate, and the silicone resin layer and the thin glass substrate are in close contact with each other so as to be peeled off.
The interface between the silicone resin layer of the glass laminate and the thin glass substrate is peeled off, and the reinforcing plate separated from the thin glass substrate is laminated with a new thin glass substrate and can be reused as a glass laminate. .

International Publication No. 07/018028 Pamphlet

In recent years, higher heat resistance has been required for the glass laminate described in Patent Document 1. As the electronic device members formed on the glass substrate of the glass laminate become more functional and complex, the temperature at which the electronic device members are formed becomes even higher, and the time exposed to the high temperatures also increases. It often takes a long time.
The glass laminate described in Patent Document 1 can withstand treatment at 300 ° C. for 1 hour in the air. However, according to the study by the present inventors, the crosslinked product of organopolysiloxane constituting the silicone resin layer in the glass laminate described in Patent Document 1 is decomposed in a short time at 400 ° C. Outgassing occurs. Generation | occurrence | production of such an outgas contaminates the member for electronic devices formed on a glass substrate, and becomes a cause of reducing the productivity of an electronic device as a result.

  The present invention has been made in view of the above points. When a crosslinked product is formed, the present invention adheres detachably to a laminated glass substrate and suppresses decomposition under high-temperature treatment conditions. An object is to provide an organopolysiloxane.

As a result of intensive studies to achieve the above object, the inventors of the present invention have a crosslinked organopolysiloxane having a specific structure, while exhibiting good adhesion to the laminated glass substrate, The present invention has been completed by finding that it can be easily peeled off and further that decomposition under high temperature treatment conditions is suppressed.
That is, the present invention provides the following (i) to (x).

(I) including the siloxane unit (A) represented by the formula (1) and the siloxane unit (B) represented by the formula (2), and the total of the siloxane unit (A) and the siloxane unit (B) The ratio of the siloxane unit (A) to 30 to 60 mol% with respect to the total, and the total proportion of the siloxane unit (A) and the siloxane unit (B) to the total siloxane units is 90 to 100 mol% Polysiloxane, in which at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms and R ⁵ and R ⁶ other than the alkenyl group are 4 or less carbon atoms. siloxane units is an alkyl group (B-1), and none of R ⁵ and R ⁶ consists of siloxane units (B-2) is an alkyl group having 4 or less carbon atoms, the total the siloxane [Siloxane unit (B-1)] / [siloxane unit (B-1) + siloxane unit (B-2)], which is a ratio of the siloxane unit (B-1) to the position (B), is 25 to 90 mol%. An organopolysiloxane characterized by being:

In formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 4 or less carbon atoms, and Ar represents a phenylene group which may have a substituent.

In formula (2), R ⁵ and R ⁶ each independently represents an alkyl group having 4 or less carbon atoms or an alkenyl group having 3 or less carbon atoms.

(Ii) The organopolysiloxane according to (i), wherein the organopolysiloxane is an alternating copolymer of the siloxane unit (A) and the siloxane unit (B).
(Iii) The organopolysiloxane according to (i) or (ii) above, wherein each of R ^{1 to} R ⁴ is a methyl group.
(Iv) The organopolysiloxane according to any one of (i) to (iii), wherein R ⁵ and R ⁶ are each independently a methyl group or a vinyl group.
(V) The organopolysiloxane according to any one of (i) to (iv) above, wherein the siloxane unit (B-1) is a siloxane unit having a methyl group and a vinyl group.
(Vi) The organopolysiloxane according to any one of (i) to (v) above, having a number average molecular weight of 5,000 to 30,000.

  (Vii) The organosilane obtained by reacting the silane compound represented by the formula (3) and the silane compound represented by the formula (4) so that the reaction ratios are 30 to 60 mol% and 70 to 40 mol%, respectively. A method for producing polysiloxane, wherein the method drops a solution containing a silane compound represented by the formula (3) and a solution containing a silane compound represented by the formula (4) onto one of them. A method for producing an organopolysiloxane, which is a method for reacting or a method in which a silane compound represented by formula (3) and a silane compound represented by formula (4) are simultaneously added to a solvent and reacted.

In the formula (3), R ¹ to R ⁴ are the same as R ¹ to R ⁴ in the formula (1), in the formula (4), R ⁵ and R ^6, R ⁵ in formula (2) and R ⁶ in the above formula, in the formula (3) and (4), X and Y each independently represent a hydrogen atom, a hydroxyl group or a hydrolyzable group.

(Viii) A crosslinked organopolysiloxane which is a crosslinked product obtained by crosslinking the organopolysiloxane according to any one of (i) to (vi) above.
(Ix) The crosslinked organopolysiloxane according to (viii) above, wherein the crosslinking is thermal crosslinking.
(X) A coating composition comprising the organopolysiloxane according to any one of (i) to (vi) and a solvent.

  ADVANTAGE OF THE INVENTION According to this invention, when it is set as a crosslinked material, organopolysiloxane which has adhesiveness with respect to the glass substrate laminated | stacked and can suppress decomposition | disassembly under high temperature processing conditions can be provided.

It is a typical sectional view showing one embodiment of a glass layered product. It is typical sectional drawing which shows one Embodiment of the manufacturing method of the glass substrate with a member in order of a process.

[Organopolysiloxane]
In describing the organopolysiloxane of the present invention, first, general organopolysiloxane will be described. Usually, the basic structural unit of organopolysiloxane is classified according to how many monovalent organic groups represented by methyl group and phenyl group are bonded to silicon atoms. The organic group called D unit shown below is 2 Bifunctional siloxane unit with one bond, trifunctional siloxane unit with one organic group called T unit, monofunctional siloxane unit with three organic groups called M unit, called Q unit It consists of a tetrafunctional siloxane unit having no organic group. 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 a siloxane unit in the present invention. In the following formulae, R represents a monovalent organic group represented by a methyl group or a phenyl group.
In the siloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, so that the oxygen atom per silicon atom in the siloxane bond is regarded as ½, Expressed as O _1/2 . More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit. its formula _{-O 1/2 -R 2 Si-O 1/2} - and becomes. Since there are two O _{1/2 s} , the D unit is usually expressed as R ₂ SiO _2/2 . However, in the present invention, in accordance with the expression of the A unit described later, the expression of O _1/2 is used for each oxygen atom to express the M unit, D unit, T unit, and Q unit as follows.
In addition, when the terminal unit of the polymer chain is a unit other than the M unit, atoms other than silicon atoms bonded to O _1/2 of the terminal unit are ½ oxygen atoms, and one in total And represents an oxygen atom in a hydroxyl group or an alkoxy group. When expressed in the same manner as the expression of the following siloxane unit, for example, the hydroxyl group bonded to the silicon atom of the terminal unit is —O _1/2 —H.

The organopolysiloxane of the present invention is roughly an organopolysiloxane containing a siloxane unit (A) represented by the formula (1) and a siloxane unit (B) represented by the formula (2).
In siloxane units (A), each of the two silicon atoms is bonded to an oxygen atom, for each of the oxygen atoms attached to a silicon atom in the outside unit, wherein is expressed as O _1/2. The same applies to the siloxane unit (B). Since the siloxane unit (A) and the siloxane unit (B) are bifunctional, they can be regarded as D units. Hereinafter, in the present invention, the siloxane unit (A) is regarded as one type of D unit, and the organopolysiloxane of the present invention will be described.

R ^{1 to} R ⁴ in the formula (1) each independently represent an alkyl group having 4 or less carbon atoms, and Ar represents a phenylene group which may have a substituent. The two bonds of Ar are bonds of carbon atoms constituting the aromatic ring.
Examples of the alkyl group having 4 or less carbon atoms represented by R ^{1 to} R ^{4 in the} formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. A methyl group and an ethyl group are preferred, a methyl group is more preferred, and R ^{1 to} R ⁴ are all preferably methyl groups because the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed.
The substituent that the phenylene group represented by Ar in formula (1) may have is not particularly limited, and examples thereof include a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, and an arylalkyl. Group, aryloxy group, heterocyclic group, amino group, nitro group, cyano group and the like, and the phenylene group represented by Ar is preferably an unsubstituted phenylene group.

In formula (2), R ⁵ and R ⁶ each independently represents an alkyl group having 4 or less carbon atoms or an alkenyl group having 3 or less carbon atoms.
In formula (2), examples of the alkyl group having 4 or less carbon atoms represented by R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. A methyl group and an ethyl group are preferable, and a methyl group is more preferable because decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed.
In formula (2), examples of the alkenyl group having 3 or less carbon atoms represented by R ⁵ and R ⁶ include a vinyl group and an allyl group, and among them, the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed. For reasons, vinyl groups are preferred.

  In the organopolysiloxane of the present invention, the ratio of the siloxane unit (A) to the total of the siloxane unit (A) and the siloxane unit (B) is such that the decomposition of the cross-linked product under high-temperature treatment conditions is suppressed, and the cross-linked product 30 to 60 mol%, preferably 35 to 55 mol%, more preferably 45 to 55 mol%, because the adhesion and releasability to the glass substrate are improved.

  The organopolysiloxane of the present invention may contain other siloxane units such as M units, T units, and Q units. For example, siloxane units (A) and siloxane units (B) with respect to all siloxane units The ratio of the total is 90 to 100 mol%, and 95 to 100 mol% is preferable, and 97 to 100 mol% is more preferable because the adhesiveness and peelability of the crosslinked product to the glass substrate become better. .

When the organopolysiloxane of the present invention contains other siloxane units, the units are preferably M units. The M unit is a unit in which all three organic groups bonded to the silicon atom are alkyl groups having 4 or less carbon atoms, or one organic group bonded to the silicon atom is an alkenyl group having 3 or less carbon atoms. A unit in which two organic groups are alkyl groups having 4 or less carbon atoms is preferred. Here, the alkyl group having 4 or less carbon atoms is preferably a methyl group or an ethyl group, and the alkenyl group having 3 or less carbon atoms is preferably a vinyl group. When M units are included, the ratio of M units to all siloxane units is preferably 1 to 10 mol%, and more preferably 2 to 7 mol%. When it has M units in this range, the molecular weight can be easily adjusted. Moreover, since the cleavage from the terminal of organopolysiloxane will be suppressed when M unit is included, heat resistance improves.
When the organopolysiloxane of the present invention contains a T unit (the organic group is preferably an alkyl group having a prime number of 4 or less) or a Q unit, the total ratio of these units to the total siloxane units is preferably 5 mol% or less. 3 mol% or less is more preferable. Since there exists a possibility that the softness | flexibility of crosslinked organopolysiloxane may fall when T unit and Q unit exist, it is especially preferable that the organopolysiloxane of this invention does not contain T unit or Q unit.

  In addition, when the organopolysiloxane of the present invention contains T units and / or Q units, the heat resistance of the cured product is improved, but the flexibility is lowered and the adhesion is inferior, and the peelability is also lowered. In some cases, from the viewpoint of adhesion and peelability, it is preferable not to include T units and Q units.

  Although it does not specifically limit as M unit which the organopolysiloxane of this invention contains, For example, the siloxane unit represented by a following formula (S) is mentioned.

In the formula (S), R ⁷ each independently represents a hydrocarbon group having 4 or less carbon atoms. Examples of the hydrocarbon group represented by R ⁷ include an alkyl group, an aryl group, and an alkenyl group. Here, specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Among them, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. . Specific examples of the aryl group include a phenyl group, and specific examples of the alkenyl group include a vinyl group.

Then, the organopolysiloxane of the present invention, the siloxane unit (B), R ⁵ and at least one of the R ⁵ and R ⁶ in the case other than the alkenyl group is an alkenyl group having 3 or less carbon atoms number of carbon atoms in R ⁶ It consists of a siloxane unit (B-1) which is an alkyl group having 4 or less, and a siloxane unit (B-2) in which all of R ⁵ and R ⁶ are alkyl groups having 4 or less carbon atoms.

A preferred embodiment of the siloxane unit (B-1) is an embodiment in which one of R ^{5 and} R ⁶ is a methyl group and the other is a vinyl group because the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed. Is mentioned.
A preferred embodiment of the siloxane unit (B-2) includes an embodiment in which both R ⁵ and R ⁶ are methyl groups.

  Further, in the present invention, [siloxane unit (B-1)] / [siloxane unit (B-1) + siloxane unit (B-2) which is the ratio of siloxane unit (B-1) to all siloxane units (B). )] Is 25 to 90 mol%, and the reason is that the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed, and the adhesiveness and peelability of the cross-linked product to the glass substrate are also improved. It is preferable that it is -75 mol%, and it is more preferable that it is 45-55 mol%.

  The bonding mode of the siloxane unit (A) and the siloxane unit (B) in the organopolysiloxane of the present invention is not particularly limited, and examples thereof include a random copolymer, a block copolymer, and an alternating copolymer. Among these, an alternating copolymer is preferable because the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed.

In the present invention, the alternating copolymer of the siloxane unit (A) and the siloxane unit (B) means that the bond between the siloxane unit (A) and the siloxane unit (B) is a combination of the siloxane unit (A) and the siloxane unit (A). ) And the sum of the bonds of the siloxane unit (B) and the siloxane unit (B).
These three types of bonds can be distinguished by, for example, ¹ H NMR measurement and ²⁹ Si NMR measurement, and the relative number ratio of these bonds can be calculated by the measurement.
The alternating copolymer of the siloxane unit (A) and the siloxane unit (B) in the present invention may contain a small number of random bond portions or block bond portions.
The ratio of the bond between the siloxane unit (A) and the siloxane unit (B) in the alternating copolymer is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, based on the total of the three types of bonds. .
In addition, although it does not distinguish whether it is an alternating copolymer, when the polysiloxane of this invention is an alternating copolymer, the siloxane unit (A) in the alternating copolymer and a siloxane unit (B) The ratio of the siloxane unit (A) to the total of 50 ± 5 mol% is preferable.
For the analysis method of alternating copolymerization, for example, Journal of Applied Polymer Science, Vol. 106, 1007-1013 (2007) can be referred to.

Although the number average molecular weight of the organopolysiloxane of the present invention is not particularly limited, it is excellent in handleability, excellent in film formability, and is more resistant to decomposition of a cross-linked product under high temperature processing conditions. The number average molecular weight in terms of polystyrene as measured by permeation chromatography) is preferably from 5,000 to 30,000, more preferably from 10,000 to 18,000.
The number average molecular weight of the organopolysiloxane of the present invention can be adjusted by controlling the reaction conditions. For example, by adjusting the amount of the solvent in producing the organopolysiloxane of the present invention and increasing the monomer concentration, a high molecular weight product is obtained, and when the concentration is lowered, a low molecular weight product is obtained.

[Method for producing organopolysiloxane]
The method for producing the organopolysiloxane of the present invention is not particularly limited. For example, the method described in known literature such as Macromolecules 1998, 31, 850-856, Journal of Applied Polymer Science, Vol. 106, 1007, 2007, etc. Can be adopted.

When the organopolysiloxane of the present invention is an alternating copolymer of the siloxane unit (A) and the siloxane unit (B) (hereinafter also simply referred to as “alternating copolymer”), the alternating copolymer is reactive. Can be obtained by polymerizing two different monomers.
For example, X which is a polymerization reactive group which the silane compound represented by the following formula (3) which becomes the siloxane unit (A) has, and the silane compound represented by the following formula (4) which becomes the siloxane unit (B). By selecting a compound having a mutual reactivity with Y, which is a polymerization reactive group, higher than the reactivity between X and the reactivity between Y, substantially the same of the above two kinds of silane compounds, etc. By reacting the molar amount, an alternating copolymer can be produced. By setting the reactivity between X and Y to be higher than both the reactivity between X and the reactivity between Y, an alternating copolymer having less random bond portions and block bond portions can be obtained.
When producing an alternating copolymer, it is preferable that one of X and Y is a hydroxy group and the other is a primary to tertiary amino group such as an amino group, a monoalkylamino group, or a dialkylamino group. In particular, one is preferably a hydroxy group and the other is a dialkylamino group, more preferably X is a hydroxy group and Y is a dialkylamino group. In addition, as an alkyl group in a monoalkylamino group or a dialkylamino group, an alkyl group having 4 or less carbon atoms is preferable, and a methyl group is particularly preferable.
As the method for producing the alternating copolymer in the present invention, for example, a method described in a known document such as Macromolecules 1998, 31, 850-856, Journal of Applied Polymer Science, Vol. 106, 1007, 2007 is employed. it can.

More specifically, for example, there is a method in which a silane compound represented by the following formula (3) and a silane compound represented by the following formula (4) are heated in a solvent such as toluene while stirring. Specifically, for example, a silane compound represented by the following formula (3) is added to a solvent and a silane compound represented by the following formula (4) is added to a solvent separately. A method in which one is dropped into the other over 5 to 10 minutes and then reacted for 1 to 1.5 hours; a silane compound represented by the following formula (3) and a following formula (4) Examples include a method in which a silane compound is simultaneously added to a solvent and reacted for 1 to 2 hours.
Here, the ratio of each silane compound to be reacted is preferably 30 to 60 mol% of the silane compound represented by the following formula (3), and 70 to 40 silane compound represented by the following formula (4). It is preferably a mol%.
Moreover, it is preferable to heat in the temperature range of 80-110 degreeC at this time, and it is more preferable to heat in the temperature range of 90-110 degreeC. If necessary, a reaction catalyst can also be used.

In the formula (3), R ¹ to R ⁴ are the same as R ¹ to R ⁴ in the formula (1), in the formula (4), R ⁵ and R ^6, R ⁵ in formula (2) And R ⁶ is synonymous. Moreover, in Formula (3) and Formula (4), X and Y each independently represent a hydrogen atom, a hydroxy group or a hydrolyzable group. Here, examples of the hydrolyzable group include a chlorine atom, an alkoxy group, an acyl group, an amino group, a secondary amino group, a tertiary amino group, and an isocyanate group.
The alkoxy group which is the hydrolyzable group is preferably an alkoxy group having 4 or less carbon atoms, more preferably a methoxy group or an ethoxy group. The acyl group is preferably an acyl group having 5 or less carbon atoms. The secondary amino group is preferably a monoalkylamino group, the tertiary amino group is preferably a dialkylamino group, and the alkyl group in each is preferably an alkyl group having 4 or less carbon atoms.

  When reacting the silane compound represented by the formula (3) with the silane compound represented by the formula (4), a silane represented by the following formula (S ′) is further used from the viewpoint of molecular weight control and the like. You may mix | blend a compound.

In the formula (S ′), R ⁷ has the same meaning as R in the formula (S), and Z represents a polymerizable reactive group. Examples of the polymerizable reactive group represented by Z include a hydroxy group; a primary to tertiary amino group such as an amino group, a monoalkylamino group, and a dialkylamino group;

An embodiment of the method for producing an organopolysiloxane of the present invention as described above will be described. For example, a polycondensation reaction between a disilanol compound represented by formula (5) and a diaminosilane compound represented by formula (6) And obtaining the organopolysiloxane of the present invention.
Specifically, in this polycondensation reaction, “—OH” in the formula (5) and “—N (CH ₃ ) ₂ ” in the formula (6) react to form “( CH ₃ ) ₂ NH ”is provided to produce the alternating copolymer of the present invention as the main product.

In the formula (5), R ¹ to R ⁴ are the same as R ¹ to R ⁴ in the formula (1), R ⁵ and R ⁶ in the formula (6) is, R ⁵ in formula (2) And R ⁶ is synonymous. In addition, “—OH” in the formula (5) may be provided by hydrolysis of a hydrolyzable group such as a halogen group or an alkoxy group.

Further, the organopolysiloxane of the present invention which is an alternating copolymer includes a dihydrosilane compound represented by formula (7) in which X in formula (3) is a hydrogen atom, and Y in formula (4) is alkoxy. It can also be produced from a dialkoxysilane compound represented by the formula (8) which is a group. Specifically, for example, a dihydrosilane compound represented by formula (7) and a dialkoxysilane compound represented by formula (8) are mixed with tris (pentafluorophenyl) borane (B (C ₆ F ₅ ). _{And 3} )) in the presence of an organic borane to obtain an organopolysiloxane of the present invention which is an alternating copolymer.
In this reaction, specifically, “—H” in formula (7) and “—OR” in formula (8) react to give “RH (eg, CH ₄ )” as a by-product. Thus, the organopolysiloxane of the present invention is produced as a main product.

In the formula (7), R ¹ to R ⁴ are the same as R ¹ to R ⁴ in the formula (1), R ⁵ and R ⁶ in the formula (8) is, R ⁵ in formula (2) And R ⁶ is synonymous. Incidentally, R in the formula (8) is a methyl group (-CH _3), an alkyl group having 1 to 5 carbon atoms such as ethyl group (-C ₂ H _5).

  The reaction conditions and the like are not particularly limited. For example, the reaction is preferably performed in a temperature range of 25 to 40 ° C. for 3 to 5 hours.

[Crosslinked organopolysiloxane (crosslinked product of organopolysiloxane)]
The crosslinked organopolysiloxane of the present invention is a crosslinked product obtained by crosslinking the above-described organopolysiloxane of the present invention. That is, the organopolysiloxane of the present invention is crosslinked and cured through a predetermined crosslinking reaction to form a crosslinked product (cured product).
Hereinafter, the crosslinking and curing of the organopolysiloxane of the present invention to form a crosslinked product is also simply referred to as curing of the organopolysiloxane of the present invention.

The form of crosslinking is not particularly limited, and a known form can be appropriately employed depending on the kind of the crosslinkable group contained in the organopolysiloxane of the present invention, and examples thereof include hydrosilylation reaction, condensation reaction, radical reaction and the like. .
However, since the organopolysiloxane of the present invention containing the siloxane unit (B) represented by the formula (2) has an alkenyl group which is a radical reactive group, in principle, a form through radical reaction is adopted. The
In addition, examples of the radical reaction employed here include a reaction by heat treatment, a reaction by high energy ray treatment, a reaction by a radical polymerization initiator, and the like. Preferably there is.
Hereinafter, crosslinking via a radical reaction by heat treatment is also referred to as “thermal crosslinking”. The crosslinked organopolysiloxane of the present invention is preferably a crosslinked product obtained by thermally crosslinking the above-described organopolysiloxane of the present invention.
The preferred conditions for thermal crosslinking will be described in the “resin layer forming step” described later.

  Such a crosslinked organopolysiloxane of the present invention is inhibited from being decomposed under high temperature treatment conditions. The reason is that the phenylene group is contained in the organopolysiloxane of the present invention. By including this phenylene group, the bond energy of the organopolysiloxane of the present invention (crosslinked organopolysiloxane of the present invention) is improved, the mobility is lowered, and the cleavage of the siloxane bond is difficult to proceed. As a result, generation of a cyclic compound of siloxane generated along with cleavage is suppressed, and generation of outgas, displacement of the glass substrate, and the like are further suppressed.

The crosslinked organopolysiloxane of the present invention has excellent heat resistance. Specifically, the 5% weight loss temperature of the crosslinked organopolysiloxane of the present invention is preferably 450 ° C. or higher, more preferably 500 ° C. or higher. The upper limit is not particularly limited, but is usually 600 ° C. or lower in many cases. Within the above range, for example, in the above-mentioned glass laminate using the crosslinked organopolysiloxane of the present invention as a resin layer, the crosslinked organopolysiloxane can be used even under high temperature conditions (about 400 ° C. or higher) such as a TFT array production process. Decomposition is suppressed, and foaming and the like are further suppressed.
The 5% weight loss temperature is determined when the sample is heated from room temperature to 700 ° C. under a nitrogen atmosphere (100 mL / min) using a thermogravimetric analyzer at a heating rate of 15 ° C./min. The temperature at which the weight is reduced by 5%.

Moreover, the crosslinked organopolysiloxane of the present invention is excellent in adhesion to a glass substrate. This is because the ratio of the siloxane unit (B-1) having an alkenyl group contributing to crosslinking is not more than the upper limit of the range of the present invention described above, so that the crosslinked organopolysiloxane of the present invention is not too hard and flexible. This is considered to be because of having adhesiveness.
Moreover, the crosslinked organopolysiloxane of the present invention is easily peeled off from the glass substrate without being hardened in the form of a viscous liquid because the ratio of the siloxane unit (B-1) is not less than the lower limit value of the above-described range of the present invention. The situation where it cannot be avoided is avoided, and the peelability is also excellent.

[Coating composition]
The coating composition of the present invention is a composition containing the organopolysiloxane of the present invention described above and a solvent.
As described later, the organopolysiloxane layer of the present invention is formed on the surface of a predetermined substrate, and the organopolysiloxane of the present invention is crosslinked on this surface to form the crosslinked organopolysiloxane layer of the present invention. In this case, it is preferable to use the coating composition of the present invention.
Specifically, using the coating composition of the present invention, this composition is applied onto a supporting substrate to form a solution layer, and then the solvent is removed to form the organopolysiloxane layer of the present invention. It is preferable to do. The thickness of the layer can be controlled by adjusting the concentration of the organopolysiloxane of the present invention in the composition.
The solvent is not particularly limited as long as it can easily dissolve the organopolysiloxane of the present invention in a working environment and can be easily removed by volatilization. For example, toluene, xylene, tetrahydrofuran (THF) , Chloroform and the like.

[Method for Producing Substrate Having Crosslinked Organopolysiloxane Layer]
Here, it describes about the method of manufacturing the base material which has the layer of the bridge | crosslinking organopolysiloxane of this invention mentioned above. In the following, for convenience, the crosslinked organopolysiloxane layer of the present invention is also referred to as a “silicone resin layer”, and a substrate having a silicone resin layer is also referred to as a “substrate with a silicone resin layer”, with a silicone resin layer. The method for producing a substrate is also referred to as “the method for producing a substrate with a resin layer of the present invention”.
The method for producing a substrate with a resin layer according to the present invention generally includes applying the above-described coating composition of the present invention to a substrate, removing the solvent, and applying the organopolysiloxane of the present invention onto the substrate. A layer is formed, and then the organopolysiloxane of the present invention is crosslinked to form a crosslinked organopolysiloxane layer (silicone resin layer) to obtain a substrate with a silicone resin layer. Constitutes a resin layer forming step (described later). Therefore, please refer to the description about a resin layer formation process for explanation of a manufacturing method of a substrate with a resin layer of the present invention.

[Glass laminate]
Next, a glass laminated body is demonstrated also serving as the description of the manufacturing method of the base material with a resin layer of this invention, and the base material with a silicone resin layer. The glass laminate has a silicone resin layer between a base material (hereinafter also referred to as “support base material”) layer and a glass substrate layer.
In the glass laminate, the silicone resin layer is a layer of the above-described crosslinked organopolysiloxane of the present invention, so that it exhibits excellent adhesion to the glass substrate and decomposes the silicone resin layer under high temperature treatment conditions. Is suppressed. As a result, generation of outgas, displacement of the glass substrate, and the like are further suppressed.

FIG. 1 is a cross-sectional view schematically showing an example of a glass laminate.
As shown in FIG. 1, in the glass laminated body 10, the layer of the support base material 12, the layer of the glass substrate 16, and the silicone resin layer 14 exist among them. One side of the silicone resin layer 14 is in contact with the layer of the support base 12, and the other side is in contact with the first main surface 16 a of the glass substrate 16. In other words, the silicone resin layer 14 is in contact with the first major surface 16 a of the glass substrate 16.
The two-layer portion including the layer of the support base 12 and the silicone resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel. And the two-layer part which consists of the layer of the support base material 12 manufactured beforehand for manufacture of the glass laminated body 10, and the silicone resin layer 14 is the "base material 18 with a silicone resin layer."

  The glass laminated body 10 is used until the member formation process mentioned later. That is, the laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Then, the laminated body in which the member for electronic devices was formed is isolate | separated into the support base material 12 and the glass substrate with a member, and the base material 18 with a silicone resin layer does not become a part which comprises an electronic device. The base material 18 with the silicone resin layer is laminated with a new glass substrate 16 and can be reused as a new glass laminate 10.

The interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the silicone resin layer 14. And the interface of the support base material 12 and the silicone resin layer 14 peels. The interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y), and when a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, The interface between the silicone resin 14 layer and the glass substrate 16 peels off.
In the glass laminate 10 (which also means a laminate with an electronic device member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when a stress is applied to the glass laminate 10 in the direction in which the support base 12 and the glass substrate 16 are peeled off, the glass substrate 10 is peeled off at the interface between the silicone resin layer 14 and the glass substrate 16, and the glass substrate 16 and the silicone resin layer are peeled off. Separated into the attached substrate 18.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
In order to increase the adhesion of the silicone resin layer 14 to the support substrate 12, it is preferable to form the silicone resin layer 14 by curing the organopolysiloxane of the present invention on the support substrate 12. The silicone resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of curing.
On the other hand, the bonding strength of the crosslinked product of the organopolysiloxane of the present invention (crosslinked organopolysiloxane of the present invention) after curing to the glass substrate 16 is usually lower than the bonding strength generated during the curing. Therefore, the organopolysiloxane of the present invention is cured on the support substrate 12 to form the silicone resin layer 14, and then the glass substrate 16 is laminated on the surface of the silicone resin layer 14 to produce the glass laminate 10. Is preferred.

  Below, first, each layer (the glass substrate 16, the support base material 12, and the silicone resin layer 14) which comprises the glass laminated body 10 is explained in full detail.

[Glass substrate]
As for the glass substrate 16, the 1st main surface 16a touches the silicone resin layer 14, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the silicone resin layer 14 side.
The glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat 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 16 is large, the member forming process often involves a heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.

  The glass substrate 16 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. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

  The glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide glasses mainly composed of silicon oxide are preferable. As oxide glass, the glass whose content of silicon oxide by oxide conversion is 40-90 mass% is preferable.

  As the glass of the glass substrate 16, 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 16 is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 16 is preferably 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 16. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

  The glass substrate 16 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or different materials. In this case, “the thickness of the glass substrate 16” means the total thickness of all the layers.

[Base material (support base material)]
The support base material 12 supports and reinforces the glass substrate 16, and the glass substrate 16 is deformed and scratched when the electronic device member is manufactured in a member forming step (step of manufacturing an electronic device member) described later. Prevent damage.

The material of the support substrate 12 is not particularly limited, but at least the surface (first main surface) on which the organopolysiloxane layer of the present invention is formed is Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , It is preferably made of an inorganic oxide such as SnO ₂ , Sb ₂ O ₃ , ZnO or oxide glass, and is preferably oxide glass. In addition, as oxide glass, what was described as oxide glass of the glass substrate 16 is mentioned.

  However, since the member forming process described later usually involves heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16 and is formed of the same material as the glass substrate 16. More preferably. In particular, the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

  The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicone resin layer 14, and the thickness of the glass laminate 10. 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 16 and the thickness of the silicone resin layer 14 is 0.1 mm, The thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 5.0 mm.

  In addition, when the support base material 12 is a glass plate, it is preferable that the thickness of a glass plate is 0.08 mm or more from the reason of being easy to handle and being hard 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 (hereinafter simply referred to as “average linear expansion coefficient”) at 25 to 300 ° C. between the support base 12 and the glass substrate 16 is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably. Is 300 × 10 ⁻⁷ / ° C. or less, more preferably 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 10 may be severely warped or the support substrate 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

[Silicone resin layer]
The silicone resin layer 14 is a layer made of the above-mentioned crosslinked product of the organopolysiloxane of the present invention (crosslinked organopolysiloxane of the present invention).
The silicone resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support base 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation. The surface 14a of the silicone resin layer 14 that is in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16 in a peelable manner. The silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peeling strength (y) at the interface is the peeling at the interface between the silicone resin layer 14 and the support base 12. Lower than strength (x).
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first main surface 16 a of the glass substrate 16 and the silicone resin layer 14, and the support base material 12 and the silicone resin layer 14 are separated. It is difficult to peel off at the interface. For this reason, the silicone resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In this invention, the property which can peel this silicone resin layer 14 surface easily is called peelability. On the other hand, the 1st main surface of the support base material 12 and the silicone resin layer 14 are couple | bonded by the bonding force which cannot be peeled relatively.
The bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may change before and after the electronic device member is formed on the surface (second main surface 16b) of the glass substrate 16 of the glass laminate 10. (That is, the peel strength (y) may change). However, even after the electronic device member is formed, the peel strength (y) is lower than the peel strength (x).

  It is considered that the silicone resin layer 14 and the glass substrate 16 are bonded to each other with a bonding force resulting from weak adhesive force or van der Waals force. In some cases, the surface of the silicone resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination can be laminated by performing a treatment for weakening the bonding force between them. By performing non-adhesive treatment or the like on the surface to be laminated and then laminating, the bonding strength at the interface between the silicone resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.

The silicone resin layer 14 is bonded to the surface of the support base 12 with a strong bonding force such as an adhesive force or an adhesive force. As described above, a high bonding strength can be obtained by crosslinking the organopolysiloxane of the present invention on the surface of the support substrate 12. Moreover, the process (for example, process using a coupling agent) which produces strong bond strength between the support base material 12 surface and the silicone resin layer 14 is given, and the bond strength between the support base material 12 surface and the silicone resin layer 14 is given. Can be increased.
The fact that the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peel strength (x) at the interface between them is high.

Although the thickness of the silicone resin layer 14 is not specifically limited, It is preferable that it is 2-100 micrometers, It is more preferable that it is 4-50 micrometers, It is further more preferable that it is 5-20 micrometers. When the thickness of the silicone resin layer 14 is within such a range, even if air bubbles or foreign matter may be present between the silicone resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 is suppressed. can do. Moreover, when the thickness of the silicone resin layer 14 is too thick, it takes time and materials to form, and this is not economical.
The silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the layers.
When the silicone resin layer 14 is composed of two or more layers, the crosslinked product forming each layer is a crosslinked product of the organopolysiloxane of the present invention (crosslinked organopolysiloxane of the present invention). It may consist of different cross-linked products.

  Since the silicone resin layer 14 made of the crosslinked organopolysiloxane of the present invention has excellent heat resistance, decomposition is suppressed even under high temperature conditions (about 400 ° C. or higher) such as a TFT array manufacturing process, and the glass laminate 10 The occurrence of foaming inside is further suppressed.

[Method for producing glass laminate]
As a manufacturing method of the glass laminated body 10, in order to obtain the glass laminated body 10 whose peeling strength (x) is higher than peeling strength (y), the organopolysiloxane of this invention is bridge | crosslinked on the support base material 12 surface. A method of forming the silicone resin layer 14 is preferable. That is, a layer of the organopolysiloxane of the present invention is formed on the surface of the support substrate 12, and the organopolysiloxane of the present invention is crosslinked on the surface of the support substrate 12 to form a silicone resin layer 14 (crosslinked organopolysiloxane of the present invention). And then the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 to produce the glass laminate 10.
When the organopolysiloxane of the present invention is crosslinked (cured) on the surface of the support substrate 12, it adheres due to the interaction with the surface of the support substrate 12 during the reaction, and the peel strength between the crosslinked product and the surface of the support substrate 12 is It is thought to be higher. Therefore, even if the glass substrate 16 and the support base 12 are made of the same material, a difference can be provided in the peel strength between the silicone resin layer 14 and the both.
Hereinafter, the step of forming the organopolysiloxane layer of the present invention on the surface of the support substrate 12 and crosslinking the organopolysiloxane of the present invention on the surface of the support substrate 12 to form the silicone resin layer 14 is referred to as “resin layer”. The process called “formation process” and the process of laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14 to form the glass laminate 10 is called “lamination process”, and the procedure of each process will be described in detail.

<Resin layer forming process>
First, the resin layer forming step will be described. The description of this step also serves as the description of the above-described method for producing the substrate with a resin layer of the present invention.
In the resin layer forming step, the layer of the organopolysiloxane of the present invention is formed on the surface of the support substrate 12, the organopolysiloxane of the present invention is crosslinked on the surface of the support substrate 12, and the crosslinked organopolysiloxane of the present invention. A silicone resin layer 14 is formed.
At this time, in order to form the organopolysiloxane layer of the present invention on the support substrate 12, the above-described coating composition of the present invention is used, and this composition is applied onto the support substrate 12. A solution layer is formed, and then the solvent is removed to form the organopolysiloxane layer of the present invention.

  The method for applying the coating composition of the present invention on the surface of the supporting substrate 12 is not particularly limited, and a known method can be used, for example, spray coating method, die coating method, spin coating method, dip coating method. , Roll coating method, bar coating method, screen printing method, gravure coating method and the like.

Next, the organopolysiloxane of the present invention on the support substrate 12 is crosslinked to form the silicone resin layer 14. More specifically, as shown in FIG. 2A, in this step, a silicone resin layer 14 is formed on the surface of at least one side of the support base 12.
The crosslinking mode is preferably thermal crosslinking because the crosslinked organopolysiloxane of the present invention having excellent adhesion to the glass substrate 16 and heat resistance can be obtained. Hereinafter, the aspect of thermal crosslinking is explained in full detail.

  The temperature conditions for thermal crosslinking are not particularly limited as long as the heat resistance of the silicone resin layer 14 is improved and the peel strength (y) after lamination with the glass substrate 16 can be controlled as described above, but is 300 to 475 ° C. Is preferable, and 350-450 degreeC is more preferable. The heating time is usually preferably 30 to 300 minutes, more preferably 30 to 120 minutes. When the temperature is too low, the heat resistance and the flatness of the silicone resin layer 14 are lowered. On the other hand, when the temperature is too high, the peel strength (y) is too low. Sexuality may be weakened.

<Lamination process>
In the laminating step, the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the layer of the supporting base 12, the silicone resin layer 14, and the glass substrate 16 are laminated. This is a step of obtaining the glass laminate 10 provided in this order. More specifically, as shown in FIG. 2 (B), a glass substrate having a surface 14a opposite to the support base 12 side of the silicone resin layer 14, and a first main surface 16a and a second main surface 16b. The silicone resin layer 14 and the glass substrate 16 are laminated by using the first principal surface 16a of 16 as a lamination surface, and the glass laminate 10 is obtained.

The method in particular of laminating | stacking the glass substrate 16 on the silicone resin layer 14 is not restrict | limited, A well-known method is employable.
For example, a method of stacking the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned. If necessary, after the glass substrate 16 is overlaid on the surface of the silicone resin layer 14, the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 using a roll or a press. Air bubbles mixed between the silicone resin layer 14 and the glass substrate 16 can be removed relatively easily by pressure bonding using a roll or a press, which is preferable.

  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 not likely to lead to a distortion defect of the glass substrate 16.

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

In addition, formation of the silicone resin layer 14 which provided the difference in the peeling strength with respect to the 1st main surface of the glass substrate 16 and the peeling strength with respect to the 1st main surface of the support base material 12 is not restricted to the said method.
For example, when the support base material 12 having a higher adhesion to the surface of the crosslinked organopolysiloxane of the present invention than the glass substrate 16 is used, the organopolysiloxane of the present invention is crosslinked (cured) on some peelable surface. Thus, a crosslinked product film can be produced, and this film can be interposed between the glass substrate 16 and the supporting substrate 12 and laminated simultaneously.
Further, when the adhesion due to the crosslinking (curing) of the organopolysiloxane of the present invention is sufficiently low with respect to the glass substrate 16 and the adhesion is sufficiently high with respect to the support base 12, the glass substrate 16 and the support base 12 are included. The silicone resin layer 14 can be formed by crosslinking (curing) the organopolysiloxane of the present invention.
Furthermore, even when the support base 12 is made of the same glass material as that of the glass substrate 16, it is possible to increase the peel strength with respect to the silicone resin layer 14 by performing a process for improving the adhesion of the support base 12 surface. For example, a chemical method (primer treatment) that improves the fixing force chemically such as a silane coupling agent, a physical method that increases surface active groups such as a flame (flame) treatment, or a surface such as a sandblast treatment Examples of such a mechanical processing method increase the catch by increasing the roughness of the material.

[Use of glass laminate]
The glass laminate 10 can be used for various applications, for example, a display device panel, PV, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed on its surface. Is mentioned. In this application, the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 400 ° 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.

[Glass substrate with member and method for producing the same]
A glass substrate with a member (a glass substrate with a member for electronic devices) including a glass substrate and a member for electronic devices is manufactured using the glass laminate described above.
Although the manufacturing method of the glass substrate with a member is not specifically limited, From the point which is excellent in the productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the glass laminated body mentioned above, and the laminated body with a member for electronic devices is used. A method of separating the manufactured and obtained laminated body with a member for electronic devices into a glass substrate with a member and a base material with a silicone resin layer by using the glass substrate side interface of the silicone resin layer as a release surface is preferable.
Hereinafter, the process of forming a member for an electronic device on a glass substrate in the glass laminate and producing a laminate with the member for an electronic device is referred to as a “member forming step”, and the silicone resin layer is formed from the laminate with the member for an electronic device. The step of separating the glass substrate side interface of the glass substrate with the member into the glass substrate with the member and the base material with the silicone resin layer is referred to as a “separation step”.
The materials and procedures used in each process are described in detail below.

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

(Electronic device components (functional elements))
The electronic device member 20 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 20, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

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 circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body 22 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 16 of the glass laminated body 10 is used. The electronic device member 20 is formed on the surface 16b.
The electronic device member 20 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member. The glass substrate with a partial member peeled from the silicone resin layer 14 can be used as a glass substrate with an all member (corresponding to an electronic device described later) in the subsequent steps.
Moreover, the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the silicone resin layer 14. FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.

  For example, when an OLED is manufactured as an example, an organic EL is formed on the surface of the glass laminate 10 opposite to the silicone resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form a structure, a transparent electrode is formed, and 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 sealing is performed. Various layers are formed and processed, such as sealing with a plate. 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, when manufacturing a TFT-LCD, a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 16b of the glass substrate 16 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

  In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other using a sealing agent (for example, an ultraviolet curable sealing agent for cell formation). Thereafter, a liquid crystal material is injected into a 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 drop injection method.

<Separation process>
As shown in FIG. 2 (D), the separation step is performed by using the electronic device member-attached laminate 22 obtained in the above-described member formation step, with the interface between the silicone resin layer 14 and the glass substrate 16 as a release surface. This is a step of separating the glass substrate 16 (glass substrate with a member) on which the device member 20 is laminated and the supporting base material 12 to obtain the glass substrate 24 with a member including the electronic device member 20 and the glass substrate 16.
When the electronic device member 20 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

The method of peeling the glass substrate 16 and the support base material 12 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off. Preferably, the electronic device member-attached laminate 22 is placed on the surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuumed on the surface plate. In this state, the blade is first allowed to enter the interface between the glass substrate 16 and the silicone resin layer 14. Then, the support substrate 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. As a result, an air layer is formed on the interface between the silicone resin layer 14 and the glass substrate 16 and on the cohesive failure surface of the silicone resin layer 14, and the air layer spreads over the entire interface and cohesive failure surface, so that the supporting substrate 12 is easily peeled off. can do.
Moreover, the support base material 12 can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.

  When separating the glass substrate 24 with a member from the glass laminate 10, it is more likely that the fragments of the silicone resin layer 14 are electrostatically adsorbed to the glass substrate 24 with a member by controlling the spraying and humidity with an ionizer. Can be suppressed.

  The manufacturing method of the glass substrate 24 with a member mentioned above is suitable for manufacture of the small display apparatus used for mobile terminals, such as a mobile telephone and 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.

  As the glass substrate 24 with a member manufactured by the manufacturing method described above, a display device panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, a glass substrate and a thin film secondary material. Examples include a thin-film secondary battery having a battery member and an electronic component having a glass substrate and an electronic device member. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Production Example 1> Production of organopolysiloxane (S3) 1,4-bis (hydroxydimethylsilyl) benzene (35 parts by mass) as a compound represented by formula (5) to be siloxane unit (A) in a nitrogen atmosphere , Manufactured by Gelest Co.) was added to toluene (90 parts by mass). Next, the reaction solution is heated to 110 ° C., and bis (dimethylamino) methylvinylsilane (11 parts by mass, manufactured by Gerest) as a compound represented by the formula (6) to be a siloxane unit (B-1) A toluene (40 parts by mass) solution in which bis (dimethylamino) dimethylsilane (12 parts by mass, manufactured by Gelest Co.) as a compound represented by the formula (6) to be a siloxane unit (B-2) is dissolved. The solution was added dropwise to the reaction solution over about 5 minutes. Thereafter, the reaction solution was stirred at 110 ° C. for 1 hour. After completion of the stirring, the reaction solution was naturally cooled to room temperature, and the reaction solution was added to methanol (3250 parts by mass) for reprecipitation treatment. Next, the precipitate was collected and vacuum-dried to obtain a colorless and transparent organopolysiloxane (S1).
The obtained organopolysiloxane (S3) had a number average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) of 1.2 × 10 ⁴ . Further, by using a thermogravimetric analyzer (manufactured by TA Instruments Inc.), the temperature is increased from room temperature to 700 ° C. in a nitrogen atmosphere (100 ml / min) at a rate of temperature increase of 15 ° C./min. It was 535 degreeC when the 5% weight reduction | decrease temperature of polysiloxane (S1) was measured. Furthermore, the structure of organopolysiloxane (S1) was identified by ¹ H NMR measurement and ²⁹ Si NMR measurement. ^For assignment of spectra in ¹ H NMR measurement and ²⁹ Si NMR measurement, Journal of Applied Polymer Science, 2007, 106, 1007-1013 was referred.

¹ H NMR ²⁹ Si NMR, measuring apparatus: ECA600 manufactured by JEOL RESONANCE
¹ H NMR measurement method: CDCL ₃ was added to a sample to prepare a sample concentration of 10% by mass. Tetramethylsilane was used as a standard.
²⁹ Si NMR measurement method: CDCL ₃ was added to a sample to prepare a sample concentration of 30% by mass. Moreover, acetylacetone chromium salt was added as a relaxation reagent, and it prepared so that it might become 0.1 mass% with respect to a sample. Tetramethylsilane was used as a standard.
The composition of the copolymer is determined from ¹ H NMR measurement. Each assignment of the spectrum obtained from ¹ H NMR measurement was determined by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013. As a result, 7.55 ppm derived from the phenylene group of the siloxane unit (A), 0.337 ppm and 0.142 ppm derived from the methyl group of the siloxane unit (B-1) and the siloxane unit (B-2), and siloxane 5.9 ppm derived from the vinyl group of the unit (B-2) was confirmed.
²⁹ Si NMR measurements give information about the bonds.
Each assignment was determined for the spectrum obtained from ²⁹ Si NMR measurement by the method described in Journal of Applied Polymer Science, 2007, 106, 1007-1013.
In the formulas represented by the following formulas (α) to (δ), spectra of −19.5 ppm, −33.4 ppm, −2.5 ppm, and −1.6 ppm, which are attributions of Si , were confirmed. Moreover, the spectrum of the silicon atom to which the same siloxane unit was connected was not observed, or even when observed, the concentration was extremely low. It was confirmed that the siloxane unit (A) and the siloxane unit (B) were alternating copolymers in which the siloxane units (B) were alternately arranged. Moreover, from the integral value of the spectrum of -19.5 ppm and -33.4 ppm, it was confirmed that the coupling | bonding of a siloxane unit (A) and a siloxane unit (B) is 90 mol%.

  Next, the obtained organopolysiloxane (S3) (30 parts by mass) was dissolved in xylene (70 parts by mass) to prepare a coating composition containing the organopolysiloxane (S3).

<Production Examples 2 to 4> Production of organopolysiloxanes (S1), (S2) and (S4) Table 1 shows organopolysiloxanes (S1), (S2) and (S4) in the same manner as in Production Example 1. It manufactured with the composition ratio shown. Next, in the same manner as in Production Example 1, a coating composition containing the obtained organopolysiloxane (S1), (S2) and (S4) was produced.

In the following Examples and Comparative Examples, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.3 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., manufactured by Asahi Glass Co., Ltd.) The name “AN100”) was used. Further, as the supporting base material, a glass plate (240 mm long, 240 mm wide, 0.4 mm thick, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd., also made of non-alkali borosilicate glass. )It was used.

<Example 1>
First, a support substrate having a thickness of 0.4 mm was cleaned with pure water, and further cleaned with UV.
Next, a coating composition containing an organopolysiloxane (S3) was applied onto the first main surface of the support substrate with a spin coater (coating amount 120 g / m ² ).
Next, this was heat-cured at 375 ° C. for 30 minutes in the air to form a 6 μm-thick silicone resin layer on the first main surface of the support substrate.

Then, the glass substrate A and the silicone resin layer surface of the supporting substrate were bonded together by vacuum pressing at room temperature to obtain a glass laminate A.
In the obtained glass laminate A, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.

Next, the glass laminate A was heated at 450 ° C. for 60 minutes in the air and cooled to room temperature. As a result, the glass substrate A was separated from the support substrate and the glass substrate, and the silicone resin layer was foamed and whitened. The above change was not observed.
And while forming the notch part of peeling by inserting the stainless steel cutting tool of thickness 0.1mm in the interface of the glass substrate and support silicone resin layer in the corner part of one place among four places of the glass laminated body A, glass A vacuum suction pad was adsorbed on the surface of each of the substrate and the supporting substrate that were not peeled surfaces, and an external force was applied in the direction in which the glass substrate and the supporting substrate were separated from each other, thereby separating the glass substrate and the supporting substrate without damaging them. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Specifically, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap.
In addition, the silicone resin layer is separated from the glass substrate together with the supporting base material. From the result, the peeling strength (x) at the interface between the supporting base material layer and the silicone resin layer is determined as the peeling strength at the interface between the silicone resin layer and the glass substrate. It was confirmed that it was higher than (y).

<Example 2>
In the same manner as in Example 1, a 6 μm-thick silicone resin layer made of a crosslinked product of organopolysiloxane (S2) was formed on the first main surface of the support substrate.
Subsequently, a glass laminate B was obtained in the same manner as in Example 1.
In the obtained glass laminate B, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate B was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate B and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And the glass laminated body B was isolate | separated by the method similar to Example 1, without damaging a glass substrate and a support base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate layer and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.

<Comparative example 1>
In the same manner as in Example 1, a 6 μm-thick silicone resin layer made of a crosslinked product of organopolysiloxane (S1) was formed on the first main surface of the support substrate.
Subsequently, a glass laminate O was obtained in the same manner as in Example 1. However, although the silicone resin layer is in close contact with the supporting base material and the glass substrate, the silicone resin layer remains in a viscous liquid state and does not harden, and is extremely difficult to peel off from the glass substrate.
Moreover, when the heat processing similar to Example 1 were performed, foaming of the silicone resin layer was recognized.

<Comparative example 2>
In the same manner as in Example 1, a 6 μm thick silicone resin layer made of a crosslinked product of organopolysiloxane (S4) was formed on the first main surface of the support substrate.
Subsequently, a glass laminate P was obtained in the same manner as in Example 1. However, when an external force was applied to the obtained glass laminate P, the glass substrate was peeled from the silicone resin layer. Thereby, it turned out that the adhesiveness with respect to the glass substrate of a silicone resin layer is inadequate.
Further, when the same heat treatment as in Example 1 was performed, no change in appearance such as foaming or whitening of the silicone resin layer was observed, but when an external force was applied to the obtained glass laminate P, silicone was obtained. The glass substrate peeled from the resin layer. Thereby, even after heat processing, it turned out that the adhesiveness with respect to the glass substrate of a silicone resin layer is inadequate.

<Comparative Example 3>
After cleaning the support substrate with pure water cleaning, UV cleaning, etc., the solvent-free addition reaction type release paper silicone containing no group represented by the formula (1) on the support substrate (Shin-Etsu Silicone Co., Ltd.) KNS-320A) 100 parts by mass and a platinum catalyst (CAT-PL-56 manufactured by Shin-Etsu Silicone Co., Ltd.) 2 parts by mass were coated with a spin coater (coating amount 10 g / m ² ) at 180 ° C. It was cured by heating in the air for 30 minutes to obtain a silicone resin layer having a film thickness of 16 μm.
After cleaning the surface of the glass substrate that contacts the silicone resin layer with pure water cleaning, UV cleaning, etc., the silicone resin layer forming surface of the support substrate and the glass substrate are bonded together by a vacuum press at room temperature. A glass laminate Q having an addition polymerization type silicone resin layer was obtained.
Next, when the glass laminate Q was subjected to the same heat treatment as in Example 1, changes in appearance such as foaming of the silicone resin layer and whitening were confirmed. In the glass laminate Q, the glass substrate was partially separated.

10 Glass laminate 12 Support base material (base material)
DESCRIPTION OF SYMBOLS 14 Silicone resin layer 14a 1st main surface of silicone resin layer 16 Glass substrate 16a 1st main surface of glass substrate 16b 2nd main surface of glass substrate 18 Base material with silicone resin layer 20 Member for electronic devices 22 With member for electronic devices Laminated body 24 Glass substrate with members

Claims (10)

The siloxane containing the siloxane unit (A) represented by the formula (1) and the siloxane unit (B) represented by the formula (2), and the total of the siloxane unit (A) and the siloxane unit (B) An organopolysiloxane in which the proportion of the unit (A) is 30 to 60 mol%, and the total proportion of the siloxane unit (A) and the siloxane unit (B) with respect to all siloxane units is 90 to 100 mol%. There,
The siloxane unit (B) is a siloxane unit in which at least one of R ⁵ and R ⁶ is an alkenyl group having 3 or less carbon atoms and R ⁵ and R ⁶ other than the alkenyl group are alkyl groups having 4 or less carbon atoms. (B-1), and R ⁵ and R ⁶ are both composed of a siloxane unit (B-2) that is an alkyl group having 4 or less carbon atoms,
[Siloxane unit (B-1)] / [siloxane unit (B-1) + siloxane unit (B-2)], which is the ratio of the siloxane unit (B-1) to the total siloxane unit (B), is 25 to 25. Organopolysiloxane characterized by being 90 mol%.
(In formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 4 or less carbon atoms, and Ar represents a phenylene group which may have a substituent.)
(In formula (2), R ⁵ and R ⁶ each independently represents an alkyl group having 4 or less carbon atoms or an alkenyl group having 3 or less carbon atoms.)   The organopolysiloxane according to claim 1, wherein the organopolysiloxane is an alternating copolymer of the siloxane unit (A) and the siloxane unit (B). The organopolysiloxane according to claim 1 or 2, wherein all of R ^{1 to} R ⁴ are methyl groups. The organopolysiloxane according to any one of claims 1 to 3, wherein R ⁵ and R ⁶ are each independently a methyl group or a vinyl group.   The organopolysiloxane according to any one of claims 1 to 4, wherein the siloxane unit (B-1) is a siloxane unit having a methyl group and a vinyl group.   The organopolysiloxane according to any one of claims 1 to 5, having a number average molecular weight of 5,000 to 30,000. The silane compound represented by the formula (3) and the silane compound represented by the formula (4) are reacted so that the reaction ratios are 30 to 60 mol% and 70 to 40 mol%, respectively, to thereby form the organopolysiloxane. A method of manufacturing comprising:
The method is a method of reacting a solution containing a silane compound represented by formula (3) and a solution containing a silane compound represented by formula (4) while dropping one on the other, or formula (3) A method for producing an organopolysiloxane, which is a method in which a silane compound represented by formula (4) and a silane compound represented by formula (4) are simultaneously added and reacted in a solvent.

(In the formula (3), R ¹ to R ⁴ are the same as R ¹ to R ⁴ in the formula (1), in the formula (4), R ⁵ and R ^6, R in the formula (2) ⁵ and R ⁶ have the same meaning, and in Formula (3) and Formula (4), X and Y each independently represent a hydrogen atom, a hydroxy group or a hydrolyzable group.   Crosslinked organopolysiloxane, which is a crosslinked product obtained by crosslinking the organopolysiloxane according to any one of claims 1 to 6.   The crosslinked organopolysiloxane according to claim 8, wherein the crosslinking is thermal crosslinking.   The coating composition containing the organopolysiloxane as described in any one of Claims 1-6, and a solvent.