WO2014050834A1 - Organopolysiloxane, procédé de fabrication d'organopolysiloxane, organopolysiloxane réticulé, et composition de revêtement - Google Patents

Organopolysiloxane, procédé de fabrication d'organopolysiloxane, organopolysiloxane réticulé, et composition de revêtement Download PDF

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WO2014050834A1
WO2014050834A1 PCT/JP2013/075766 JP2013075766W WO2014050834A1 WO 2014050834 A1 WO2014050834 A1 WO 2014050834A1 JP 2013075766 W JP2013075766 W JP 2013075766W WO 2014050834 A1 WO2014050834 A1 WO 2014050834A1
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organopolysiloxane
glass substrate
siloxane unit
formula
group
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Japanese (ja)
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絢 松井
庚薫 閔
大輔 内田
純一 角田
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C08G77/52—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to an organopolysiloxane, a method for producing organopolysiloxane, a crosslinked organopolysiloxane that is a crosslinked product of organopolysiloxane, and a coating composition containing the organopolysiloxane.
  • 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.
  • PV solar cells
  • LCD liquid crystal panels
  • OLED organic EL panels
  • a method of forming a device member for example, a thin film transistor
  • a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
  • 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.
  • 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.
  • 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.
  • the present invention has been made in view of the above points.
  • 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.
  • 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).
  • siloxane units is an alkyl group (B-1), and none of R 5 and R 6 consists of siloxane units is an alkyl group having 4 or less carbon atoms, respectively (B-2),
  • the ratio of [siloxane unit (B-1)] ⁇ 100 / [siloxane unit (B-1) + siloxane unit (B-2)], which is the ratio of the siloxane unit (B-1) to the siloxane unit (B), is 25.
  • Organopolysiloxane which is ⁇ 90 mol%.
  • R 1 to R 4 each independently represents an alkyl group having 4 or less carbon atoms
  • Ar represents a phenylene group which may have a substituent.
  • 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 silane compound represented is a silane compound 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, and , Each of R 5 and R 6 is composed of a silane compound that is an alkyl group having 4 or less carbon atoms.
  • R 1 ⁇ R 4 and Ar have the same meanings as R 1 ⁇ R 4 and Ar in Formula (1), in the formula (4), R 5 and R 6 has the formula (2) It is synonymous with R 5 and R 6 in the formula, and in formula (3) and formula (4), X and Y each independently represent a hydrogen atom, a hydroxy 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) above and a solvent.
  • an organopolysiloxane that, when a crosslinked product is used, has adhesion to a laminated glass substrate and suppresses decomposition under high-temperature treatment conditions.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a glass laminate.
  • 2A to 2D are schematic cross-sectional views showing an embodiment of a method for producing a glass substrate with members in the order of steps.
  • 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 a silicon atom, and is called D unit as shown below. Bifunctional siloxane unit with two organic groups bonded, called T unit, trifunctional siloxane unit with one organic group bonded, monofunctional siloxane called M unit with three organic groups bonded It consists of a unit and a tetrafunctional siloxane unit called Q unit which has 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.
  • R represents a monovalent organic group represented by a methyl group or a phenyl group.
  • 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 1 ⁇ 2, O 1/2 is expressed.
  • one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit.
  • the formula is -O 1/2 -R 2 Si-O 1/ 2- . Since there are two O 1/2 s , the D unit is usually expressed as R 2 SiO 2/2 .
  • an O 1/2 expression is used for each oxygen atom to express the M unit, the D unit, the T unit, and the Q unit as follows.
  • the atoms other than the silicon atom bonded to the O 1/2 of the terminal unit are 1 ⁇ 2 oxygen atoms, and one in total And represents an oxygen atom in a hydroxyl group or an alkoxy group.
  • 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).
  • a siloxane unit (A) represented by the formula (1)
  • a siloxane unit (B) represented by the formula (2).
  • each of two silicon atoms is bonded to an oxygen atom, and each oxygen atom is bonded to a silicon atom outside the unit, and therefore, expressed as O 1/2 in the formula.
  • 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 each independently represents an alkyl group having 4 or less carbon atoms
  • 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 preferable, a methyl group is more preferable, 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.
  • 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.
  • 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.
  • 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 above all, the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed. For reasons, vinyl groups are preferred.
  • the silane compound represented by the formula (2) is a silane compound in which one of R 5 and R 6 is an alkenyl group having 3 or less carbon atoms and the other is an alkyl group having 4 or less carbon atoms, R 5 and R 6 Both are composed of a silane compound having an alkenyl group having 3 or less carbon atoms and a silane compound in which each of R 5 and R 6 is an alkyl group having 4 or less carbon atoms.
  • 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 From the reason that the adhesion to the glass substrate and the releasability are also good, it is 30 to 60 mol%, preferably 35 to 55 mol%, more preferably 45 to 55 mol%.
  • the organopolysiloxane of the present invention may contain other siloxane units such as M units, T units, and Q units.
  • siloxane units (A) and siloxane units (B) with respect to all siloxane units The total ratio is 90 to 100% by mole, and is preferably 95 to 100% by mole, more preferably 97 to 100% by mole because the adhesion and release properties of the crosslinked product to the glass substrate become better. .
  • 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.
  • the alkyl group having 4 or less carbon atoms is preferably a methyl group or an ethyl group
  • the alkenyl group having 3 or less carbon atoms is preferably a vinyl group.
  • the ratio of the M unit to the total 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.
  • the organopolysiloxane of the present invention contains a T unit (its organic group is preferably an alkyl group having 4 or less carbon atoms) or a Q unit, the total ratio of these units to all siloxane units is 5 mol% or less. Preferably, 3 mol% or less is more preferable. Since there exists a possibility that the softness
  • 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.
  • the M unit contained in the organopolysiloxane of the present invention is not particularly limited, and examples thereof include a siloxane unit represented by the following formula (S).
  • R 7 each independently represents a hydrocarbon group having 6 or less carbon atoms.
  • the hydrocarbon group represented by R 7 include an alkyl group, an aryl group, and an alkenyl group.
  • 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
  • specific examples of the alkenyl group include a vinyl group.
  • the siloxane unit (B-1), which is an alkyl group having 4 or less, and the siloxane unit (B-2), each of R 5 and R 6 are each an alkyl group 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.
  • Preferable embodiments of the siloxane unit (B-2) include an embodiment in which both R 5 and R 6 are methyl groups.
  • [siloxane unit (B-1)] ⁇ 100 / [siloxane unit (B-1) + siloxane unit (B), which is the ratio of siloxane unit (B-1) to all siloxane units (B). -2)] is 25 to 90 mol%.
  • the above ratio is preferably 25 to 75 mol% because the decomposition of the cross-linked product under high-temperature treatment conditions is further suppressed and the adhesion and peelability of the cross-linked product to the glass substrate are also improved. 45 to 55 mol% is more preferable.
  • 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.
  • 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).
  • 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% with respect to the total of the above three types of bonds. .
  • 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.
  • the analysis method of alternating copolymerization see, for example, Journal of Applied Polymer Science, Vol. 106, 1007-1013 (2007).
  • 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.
  • the method for producing the organopolysiloxane of the present invention is not particularly limited. For example, Macromolecules 1998, 31, 850-856, Journal of Applied Polymer Science, Vol. 106, 1007, 2007, and other publicly known methods can be employed.
  • 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.
  • 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).
  • one of X and Y is a hydroxy group and the other is a primary to tertiary amino group such as an amino group, monoalkylamino group, dialkylamino group or the like.
  • 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.
  • 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.
  • Examples of the method for producing an alternating copolymer in the present invention include, for example, Macromolecules 1998, 31, 850-856, Journal of Applied Polymer Science, Vol. 106, 1007, 2007, and other publicly known methods can be employed.
  • 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.
  • 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 a silane compound is simultaneously added to a solvent and allowed to react for 1 to 2 hours.
  • 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 mol of the silane compound represented by the following formula (4). It is preferably a mol%.
  • a reaction catalyst can also be used.
  • R 1 ⁇ R 4 and Ar have the same meanings as R 1 ⁇ R 4 and Ar in Formula (1)
  • R 5 and R 6 has the formula (2) Synonymous with R 5 and R 6 in the middle.
  • X and Y each independently represent a hydrogen atom, a hydroxy group or a hydrolyzable group.
  • 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.
  • the silane compound represented by the formula (4) is a silane compound in which one of R 5 and R 6 is an alkenyl group having 3 or less carbon atoms and the other is an alkyl group having 4 or less carbon atoms, R 5 and R 6 Both are composed of a silane compound having an alkenyl group having 3 or less carbon atoms and a silane compound in which each of R 5 and R 6 is an alkyl group having 4 or less carbon atoms.
  • a silane represented by the following formula (S ′) is further used from the viewpoint of molecular weight control and the like. You may mix
  • R 7 has the same meaning as R 7 in the formula (S), Z represents a polymerizable reactive group.
  • 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;
  • Equation (5) in, R 1 ⁇ R 4 and Ar have the same meanings as R 1 ⁇ R 4 and Ar in Formula (1), R 5 and R 6 in the formula (6) the formula (2) Synonymous with R 5 and R 6 in the middle.
  • “—OH” in the formula (5) may be provided by hydrolysis of a hydrolyzable group such as a halogen group or an alkoxy group.
  • 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 ).
  • organopolysiloxane of the present invention which is an alternating copolymer.
  • organic borane specifically, “—H” in formula (7) and “—OR” in formula (8) react to give “RH (eg, CH 4 )” as a by-product.
  • RH eg, CH 4
  • R 1 ⁇ R 4 and Ar have the same meanings as R 1 ⁇ R 4 and Ar in Formula (1), R 5 and R 6 in the formula (8), equation (2) Synonymous with R 5 and R 6 in the middle.
  • R represents an alkyl group having 1 to 5 carbon atoms such as a methyl group (—CH 3 ) or an ethyl group (—C 2 H 5 ).
  • the conditions for this reaction are not particularly limited. For example, it is preferable to carry out the reaction for 3 to 5 hours in a temperature range of 25 to 40 ° C.
  • 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).
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the crosslinked organopolysiloxane can be used even under high temperature conditions (about 400 ° C. or higher) such as a TFT array production process.
  • 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 rate of temperature increase of 15 ° C./min. The temperature at which the weight is reduced by 5%.
  • 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 that contributes 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. Further, the crosslinked organopolysiloxane of the present invention can be 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 of the range of the present invention described above. The situation where it cannot be avoided is avoided, and the peelability is also excellent.
  • 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.
  • toluene, xylene, tetrahydrofuran (THF) , Chloroform and the like are examples of toluene, xylene, tetrahydrofuran (THF) , Chloroform and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 laminate 10 is used up to a member forming process described later. That is, the glass 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
  • 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.
  • the peel strength (x) is higher than the peel strength (y).
  • 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 separated. 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. .
  • 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.
  • 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.
  • each layer (glass substrate 16, support base material 12, silicone resin layer 14) constituting the glass laminate 10 will be described in detail.
  • 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 preferably 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.
  • the member forming process often involves heat treatment, and various inconveniences are likely to occur.
  • 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.
  • 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 containing silicon oxide are preferable.
  • the oxide glass is preferably a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide.
  • glass suitable for the type of electronic device member and the manufacturing process thereof is employed.
  • 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) Components are preferably included).
  • 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.
  • the material forming each layer may be the same material or a different material.
  • the thickness of the glass substrate 16 means the total thickness of all the layers.
  • 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 , is preferably made of SnO 2, Sb 2 O 3, ZnO and oxide inorganic oxides such as glass, it is preferably an oxide glass.
  • oxide glass what was described as oxide glass of the glass substrate 16 is mentioned.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 between the support base 12 and the glass substrate 16 at 25 to 300 ° C. is preferably 500 ⁇ 10 ⁇ 7 / ° C. or less, and more preferably Is not more than 300 ⁇ 10 ⁇ 7 / ° C., more preferably not more than 200 ⁇ 10 ⁇ 7 / ° C. 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.
  • 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 (first main surface) 14 a that contacts the glass substrate 16 of the silicone resin layer 14 is in close contact with the first main surface 16 a of the glass substrate 16 so as to be peelable.
  • 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.
  • 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.
  • peelability the property which can peel this silicone resin layer 14 surface easily is called peelability.
  • the 1st main surface of the support base material 12 and the silicone resin layer 14 are couple
  • 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).
  • the silicone resin layer 14 and the glass substrate 16 are bonded to each other with a weak adhesive force or a bonding force resulting from van der Waals force.
  • the surface 14a 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.
  • 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.
  • a strong bonding force such as an adhesive force or an adhesive force.
  • a high bonding strength can be obtained by crosslinking the organopolysiloxane of the present invention on the surface of the support substrate 12.
  • the process for example, process using a coupling agent
  • the bond strength between the support base material 12 surface and the silicone resin layer 14 is given.
  • 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.
  • the thickness of the silicone resin layer 14 is not particularly limited, but is preferably 2 to 100 ⁇ m, more preferably 4 to 50 ⁇ m, and even more preferably 5 to 20 ⁇ m. 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.
  • 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.
  • 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.
  • the organopolysiloxane of this invention is bridge
  • 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).
  • the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 to produce the glass laminate 10.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermal crosslinking is explained in full detail.
  • the temperature conditions for the 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 to 450 ° C. is more preferable.
  • the heating time is usually preferably from 30 to 300 minutes, more preferably from 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.
  • 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.
  • stacking the glass substrate 16 on the silicone resin layer 14 is not restrict
  • a well-known method is employable.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a chemical method 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
  • a surface such as a sandblast treatment
  • a mechanical processing method increase the catch by increasing the roughness of the material.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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).
  • 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.
  • 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.
  • various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
  • 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.
  • 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.
  • 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. Alternatively, an electronic device can be manufactured by assembling a laminate with all members and then peeling the substrate 18 with a silicone resin layer from the laminate with all members. Furthermore, the laminate with all members is assembled using two sheets, and then the two substrates 18 with a silicone resin layer are peeled from the laminate with all members to produce a glass substrate with a member having two glass substrates. You can also
  • 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).
  • 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.
  • 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.
  • 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.
  • a cleaning method known dry cleaning or wet cleaning can be used.
  • the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other, and are bonded using a sealant (for example, an ultraviolet curable sealant for cell formation).
  • a sealant for example, an ultraviolet curable sealant for cell formation.
  • a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF.
  • the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 can be easily peeled off. can do.
  • the support base material 12 can be laminated
  • the above-described method for manufacturing the glass substrate with member 24 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.
  • the present invention can be applied to both passive drive type and active drive type display devices.
  • 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.
  • the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.
  • reaction solution was 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 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 in toluene (40 parts by mass).
  • toluene 40 parts by mass
  • 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 (S3).
  • the obtained organopolysiloxane (S3) had a number average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) of 1.2 ⁇ 10 4 .
  • GPC gel permeation chromatography
  • organopolysiloxane (S3) (30 parts by mass) was dissolved in xylene (70 parts by mass) to prepare a coating composition containing the organopolysiloxane (S3).
  • 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 as a supporting base material.
  • a glass plate (240 mm long, 240 mm wide, 0.4 mm thick, linear expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C., product name “AN100” manufactured by Asahi Glass Co., Ltd., which is 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, the coating composition containing the organopolysiloxane (S3) was applied on the first main surface of the supporting substrate with a spin coater (coating amount 120 g / m 2 ). Next, this was heat-cured (thermal crosslinking) in the atmosphere at 375 ° C. for 30 minutes to form a silicone resin layer having a thickness of 6 ⁇ m on the first main surface of the support substrate.
  • S3 organopolysiloxane
  • 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.
  • 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.
  • 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. Then, a glass substrate is formed while inserting a stainless steel blade having a thickness of 0.1 mm into the interface between the glass substrate and the silicone resin layer at one corner of the four positions of the glass laminate A to form a notch for peeling.
  • the vacuum suction pad was adsorbed on the surface of each of the support substrate and the support substrate, and the glass substrate and the support substrate were separated from each other without damaging them by applying an external force in the direction in which the glass substrate and the support substrate were separated from each other.
  • 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.
  • 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 ⁇ m-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.
  • the glass laminated body B was isolate
  • the silicone resin layer is separated from the glass substrate together with the support base material. From the results, the peel strength (x) at the interface between the support base material layer and the silicone resin layer is determined as the peel strength at the interface between the silicone resin layer and the glass substrate (y ) Was confirmed.
  • ⁇ Comparative example 1> In the same manner as in Example 1, a 6 ⁇ m-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 ⁇ m 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.
  • 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.
  • 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.
  • the glass substrate was partially separated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un organopolysiloxane qui comprend un motif siloxane (A) représenté par la formule développée (1) et un motif siloxane (B) représenté par la formule développée (2), le rapport du motif siloxane (A) par rapport au total des motifs siloxane (A) et des motifs siloxane (B) étant de 30 à 60 % en mole, et le rapport du total des motifs siloxane (A) et des motifs siloxane (B) par rapport à tous les motifs siloxane étant de 90 à 100 % en mole. Le motif siloxane (B) comprend un motif siloxane prescrit (B-1) et un motif siloxane prescrit (B-2), et [motif siloxane (B-1)]×100/[motif siloxane (B-1)]+[motif siloxane (B-2)] est de 25 à 90 % en mole.
PCT/JP2013/075766 2012-09-27 2013-09-24 Organopolysiloxane, procédé de fabrication d'organopolysiloxane, organopolysiloxane réticulé, et composition de revêtement WO2014050834A1 (fr)

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CN113336945B (zh) * 2021-06-28 2023-08-29 中国科学院长春应用化学研究所 一种主链含亚苯基(苯撑)的硅氧烷聚合物及其制备方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015156395A1 (fr) * 2014-04-10 2015-10-15 旭硝子株式会社 Stratifié de verre, son procédé de fabrication et procédé de fabrication de dispositif électronique
JPWO2015156395A1 (ja) * 2014-04-10 2017-04-13 旭硝子株式会社 ガラス積層体およびその製造方法、電子デバイスの製造方法
WO2018105716A1 (fr) * 2016-12-09 2018-06-14 ダイキン工業株式会社 Polymère, composition et article moulé
JPWO2018105716A1 (ja) * 2016-12-09 2019-08-08 ダイキン工業株式会社 ポリマー、組成物及び成形品

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