WO2015182766A1 - Composition adhésive, corps support et procédé de production associé, et stratifié en verre - Google Patents

Composition adhésive, corps support et procédé de production associé, et stratifié en verre Download PDF

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Publication number
WO2015182766A1
WO2015182766A1 PCT/JP2015/065644 JP2015065644W WO2015182766A1 WO 2015182766 A1 WO2015182766 A1 WO 2015182766A1 JP 2015065644 W JP2015065644 W JP 2015065644W WO 2015182766 A1 WO2015182766 A1 WO 2015182766A1
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Prior art keywords
silicone compound
support
resin layer
glass substrate
bonded
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PCT/JP2015/065644
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English (en)
Japanese (ja)
Inventor
隆俊 八百板
大輔 内田
庚薫 閔
祥孝 松山
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旭硝子株式会社
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Publication of WO2015182766A1 publication Critical patent/WO2015182766A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • 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 adhesive composition, a support, a method for producing the same, and a glass laminate.
  • a glass laminate is prepared by laminating a glass substrate and a reinforcing plate, and after forming an electronic device member such as a display device on the glass substrate, the glass substrate and A method of separating the reinforcing plate has been proposed (see, for example, Patent Document 1).
  • the temperature at which the electronic device members are formed becomes even higher, and the time of exposure to the high temperatures may take a long time. is there. As a result, high heat resistance is required for the glass laminate.
  • the glass laminate described in Patent Document 1 can withstand processing conditions of 300 ° C. for 1 hour in the atmosphere, but decomposition may occur within a short time in high-temperature heat treatment (450 ° C.).
  • the present invention has been made in view of the above points, and is a pressure-sensitive adhesive composition for a resin layer in which decomposition is suppressed even after high-temperature heat treatment, a support including the resin layer, a method for producing the support, and glass It aims at providing a laminated body.
  • the pressure-sensitive adhesive composition of the present invention is A linear silicone compound (a) having an alkenyl group bonded to a silicon atom; A silicone compound (b) having at least three hydrogen atoms bonded to silicon atoms per molecule; A cyclic silicone compound (c1) having an alkenyl group bonded to a silicon atom; It is characterized by including.
  • the support of the present invention comprises It has a support base material and a resin layer provided on the support base material, and is a support for laminating a glass substrate on the resin layer,
  • the resin layer is A linear silicone compound (a) having an alkenyl group bonded to a silicon atom;
  • the method for producing the support of the present invention comprises: Preparing a support substrate; A linear silicone compound (a) having an alkenyl group bonded to a silicon atom, a silicone compound (b) having at least three hydrogen atoms bonded to a silicon atom per molecule, and a ring having an alkenyl group bonded to a silicon atom Preparing a pressure-sensitive adhesive composition comprising a silicone compound (c1); Applying the pressure-sensitive adhesive composition on the support substrate and curing to form a resin layer; It is characterized by including.
  • the glass laminated body of this invention contains a support body and the glass substrate which contact
  • an adhesive composition for a resin layer in which decomposition is suppressed even after high-temperature heat treatment a support containing the resin layer, a method for producing the support, and a glass laminate.
  • the pressure-sensitive adhesive composition of the present invention that is, the curable silicone resin composition
  • the support the method for producing the support
  • the glass laminate including the support of the present invention the display panel with the support
  • the display device panel will be described in detail based on a preferred embodiment shown in the drawings.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a display device-equipped panel according to the present invention.
  • a panel 10 for a display device with a support shown in FIG. 1 includes a support 20 according to the present invention, and includes a support base 12, a resin layer 14, a glass substrate 16, and a component 18 of the display device panel. Are stacked in this order.
  • the thickness of each layer is not limited by FIG.
  • the support base material 12 and the resin layer 14 comprise the support body 20 of this invention
  • the support body 20 and the glass substrate 16 comprise the glass laminated body 30, and the structural member of the glass substrate 16 and the panel for display apparatuses. 18 constitutes a display device panel 40 (without the support 20).
  • each layer which comprises the support body 20, the glass laminated body 30, the display apparatus panel 40, and the display apparatus panel 10 with a support body of this invention is demonstrated.
  • the support substrate 12 used in the present invention is not particularly limited as long as it supports the glass substrate 16 through the resin layer 14 and reinforces the strength of the glass substrate 16. Although it does not restrict
  • the composition thereof is, for example, a silicate glass (such as soda lime glass) containing an alkali metal oxide, or an alkali-free silicate glass (alkali metal oxide).
  • a silicate glass such as soda lime glass
  • an alkali-free silicate glass alkali metal oxide
  • Glass of various compositions, such as borosilicate glass substantially free of Of these, alkali-free silicate glass is preferred because of its low thermal shrinkage.
  • substantially not containing means that inclusion of impurities from the material is not excluded.
  • the difference in coefficient of linear expansion between the glass substrate 16 and the glass used for the support base 12 is preferably 150 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 100 ⁇ 10 ⁇ 7 / ° C. or less, and 50 ⁇ 10 ⁇ 7 / ° C.
  • the glass of the glass substrate 16 and the glass of the support base 12 may be the same material. In this case, the difference between the linear expansion coefficients of both glasses is zero.
  • the type is not particularly limited.
  • polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyethersulfone resin examples thereof include polyether ketone resins, polyether ether ketone resins, polyethylene naphthalate resins, polyacrylic resins, various liquid crystal polymer resins, and silicone resins.
  • the type thereof is not particularly limited, and examples thereof include stainless steel and copper.
  • the heat resistance of the support substrate 12 is not particularly limited, but when the glass substrate 16 is laminated on the support substrate 12 and a TFT array of a display device member is formed, the heat resistance is preferably high.
  • the heat resistance is defined as a 5% weight loss by heating when the support base 12 is heated in the presence of air.
  • the 5% heating weight loss temperature refers to a temperature at which a weight loss of more than 5% has occurred in the heating process, based on the weight of the support substrate 12 before heating.
  • the heating weight loss temperature is preferably 300 ° C. or more, and more preferably 350 ° C. or more. In this case, any of the above-mentioned glasses is applicable in terms of heat resistance.
  • Examples of preferable plastics from the viewpoint of heat resistance include polyimide resins, fluororesins, polyamide resins, polyaramid resins, polyethersulfone resins, polyetherketone resins, polyetheretherketone resins, polyethylene naphthalate resins, and various liquid crystal polymer resins. Is done.
  • the thickness of the support substrate 12 is not particularly limited, but is preferably 0.3 to 1.1 mm, and more preferably 0.4 to 0.8 mm. More preferably, the thickness is 0.5 to 0.7 mm. When the thickness of the support base 12 is 0.3 mm or more, the strength to reinforce the glass substrate 16 tends to be insufficient, and breakage hardly occurs.
  • the thickness of the glass substrate 16 is not particularly limited, but is preferably 0.05 to 0.4 mm, and more preferably 0.05 to 0.2 mm. More preferably, the thickness is 0.5 to 0.1 mm. When the thickness of the glass substrate 16 is 0.05 mm or more, the strength of the glass tends to be insufficient, and breakage hardly occurs. It is assumed that the thickness of the glass substrate 16 is thinner than the thickness of the support base 12.
  • the surface of the support substrate 12 composed of the various materials described above may be a polished surface that has been subjected to a polishing process, or a non-etched surface that is not subjected to the polishing process (fabric surface). It may be. From the viewpoint of productivity and cost, a non-etched surface (fabric surface) is preferable.
  • the support base 12 has a first main surface and a second main surface, and the shape is not limited, but a rectangle is preferable.
  • the rectangle is substantially a rectangle and includes a shape obtained by cutting off the corners of the peripheral portion (corner cut).
  • the first main surface 12A of the support substrate 12 is a surface on which the resin layer 14 is formed, and the second main surface 12B is the opposite surface.
  • the size of the support substrate 12 is not limited, but for example, in the case of a rectangle, it may be 100 to 2000 mm ⁇ 100 to 2000 mm, and preferably 500 to 1000 mm ⁇ 500 to 1000 mm.
  • the resin layer 14 in the present invention is fixed on the first main surface 12A of the support base 12 described above, and the glass laminate 30 in which the glass substrate 16 is laminated has a first main surface and a second main surface.
  • the glass substrate 16 is in close contact with the first main surface.
  • the first main surface 16A of the glass substrate 16 is a surface in contact with the resin layer 14, and the second main surface 16B is the opposite surface.
  • “Fixed” in this specification refers to a bond between the resin layer 14 and the support base 12, and “adhesion” in this specification refers to a bond between the glass substrate 16 and the resin layer 14.
  • the bond (so-called fixing) between the resin layer 14 and the support base 12 means a stronger bonding force than the bond (so-called close contact) between the glass substrate 16 and the resin layer 14.
  • the resin layer 14 and the glass substrate 16 are bonded by a very weak force. For example, forces represented by intermolecular forces and van der Waals forces. More specific description will be given below.
  • the peel strength between the first main surface 16A of the glass substrate 16 and the resin layer 14 needs to be lower than the peel strength between the first main surface 12A of the support base 12 and the resin layer 14.
  • the glass substrate 16 and the support base 12 are separated, the glass substrate 16 is peeled off at the interface between the first main surface 16A of the glass substrate 16 and the resin layer 14, and the first main surface 12A of the support base 12 and the resin are separated. It must be difficult to peel off at the interface with the layer 14. For this reason, the 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 resin layer 14 is bonded to the first main surface 16 ⁇ / b> A of the glass substrate 16 with a certain bonding force to prevent the glass substrate 16 from being displaced.
  • the resin layer 14 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16.
  • the easily peelable property of the resin layer 14 is called peelability.
  • the bonding force between the first main surface 12A of the support base 12 and the resin layer 14 is a bonding force that is less likely to peel than the bonding force between the first main surface 16A of the glass substrate 16 and the resin layer 14.
  • An agent composition (hereinafter, the adhesive composition is also referred to as a curable silicone resin composition) is cured on the first main surface 12A of the support base 12 to form a resin layer 14 made of a cured silicone resin, and then It is preferable that the glass substrate 16 is laminated and adhered to the resin layer 14 made of a cured silicone resin. Even if the cured silicone resin in the present invention is in close contact with the glass substrate 16, the peel strength is low.
  • the curable silicone resin composition to be a cured silicone resin is cured on the surface of the support substrate 12, it adheres by interaction with the surface of the support substrate during the curing reaction, and the cured silicone resin after curing and the support substrate
  • the peel strength from the surface is considered to be high. 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 resin layer and the peel strength between them.
  • the formation of the resin layer 14 having a difference between the peel strength with respect to the first main surface 16A of the glass substrate 16 and the peel strength with respect to the first main surface 12A of the support base 12 is not limited to the above method.
  • the glass substrate 16 and the support base material 12 are laminated simultaneously with a cured silicone resin film interposed. Can do.
  • a curable silicone resin composition is used for the support base material 12.
  • a glass substrate 16 is laminated on the curable silicone resin composition, and the curable silicone resin composition is cured between the glass substrate 16 and the support base 12.
  • the resin layer 14 can be formed. 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 resin layer 14 by performing a process for increasing the adhesion of the surface of the support base 12. For example, it is possible to increase the bonding strength with the resin layer 14 by performing a treatment for increasing the concentration of silanol groups on the surface of the support substrate 12 made of a glass material.
  • An addition reaction type curable silicone resin composition (that is, a pressure-sensitive adhesive composition) includes a linear silicone compound having an alkenyl group bonded to a silicon atom, a silicone compound having a hydrogen atom bonded to a silicon atom, and a silicon atom.
  • a curable pressure-sensitive adhesive composition comprising an alkenyl group bonded to a linear silicone compound having an alkenyl group bonded to a silicon atom, and a hydrogen atom bonded to a silicon atom.
  • a curable composition comprising a linear silicone compound having a cyclic silicone compound having an alkenyl group bonded to a silicon atom, and an additive such as a catalyst, and cured by heating to form a cured silicone resin.
  • the resin layer 14 in the present invention generally includes at least 3 linear silicone compounds (a), which are linear silicone compounds having an alkenyl group bonded to a silicon atom, and at least 3 hydrogen atoms bonded to a silicon atom per molecule.
  • An addition reaction type curable silicone resin composition containing a linear silicone compound (b) having a linear silicone compound and a cyclic silicone compound (c1) having an alkenyl group bonded to a silicon atom; It is a layer of a cured silicone resin.
  • the curable silicone resin composition may contain a cyclic silicone compound (c2) having a hydrogen atom bonded to a silicon atom.
  • the cured product of the addition reaction type curable silicone resin composition in the present invention has optimized the molar ratio of Si—H groups to vinyl groups in the composition, unreacted hydrogen atoms (silicon atoms after curing) The residual amount of hydrogen atoms bonded to is small. For this reason, the change in peel strength with time is small, and the heat resistance is excellent.
  • the pressure-sensitive adhesive composition used for forming the resin layer 14, that is, the curable silicone resin composition will be described in detail below.
  • the linear silicone compound (a) contained in the curable silicone resin composition in the present invention is preferably a linear silicone compound having at least two alkenyl groups per molecule.
  • the alkenyl group is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group, and the like. Groups are preferred.
  • the alkenyl group concentration is preferably 0.1 to 20.4 mmol / g, and more preferably 0.5 to 11.6 mmol / g.
  • monofunctional units at both ends of the linear silicone compound (a) are referred to as M units, and difunctional units other than both ends are referred to as D units, and a line having n D units.
  • the structure of the silicone compound (a) is represented by M (D) n M.
  • M (D) n M when expressing the average composition of each unit, it may be represented by M 2 (D) n .
  • the alkenyl group is present in the M unit or D unit, and may be present in both the M unit and D unit. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.
  • the linear silicone compound (a) having an alkenyl group only in the M unit has a lower heat resistance because the higher the molecular weight, the lower the alkenyl group concentration per molecule and the lower the crosslinking density of the cured silicone resin. It is preferable to have an alkenyl group in part of the D unit as well as the M unit.
  • the number of alkenyl groups per molecule of the linear silicone compound (a) is preferably 2 to 120, more preferably 2 to 100, from the viewpoint of heat resistance of the cured product.
  • a linear organopolysiloxane having an average composition represented by the following formula (1) is preferable.
  • M 1 is an M unit having neither an alkenyl group nor a hydrogen atom bonded to a silicon atom
  • M 2 is an M unit having an alkenyl group bonded to a silicon atom
  • D 1 is a hydrogen bonded to an alkenyl group and a silicon atom.
  • D unit having no atom, and D 2 represents a D unit having an alkenyl group bonded to a silicon atom
  • a is a number from 0 to 2
  • b is a number from 0 to 2
  • a + b 2
  • c is 0
  • d is a number of 0 or more
  • c + d n (where b + d is 2 or more).
  • a is a number of 0 or more and less than 1
  • b is a number of 1 or more and 2 or less
  • c is a number of 1 or more
  • d is a number of 1 or more. It is.
  • the M 2 unit may have two or three alkenyl groups bonded to a silicon atom, but preferably has one.
  • the D 2 unit may have two alkenyl groups bonded to a silicon atom, but preferably has one.
  • the alkenyl group is preferably a vinyl group.
  • the M 1 unit, D 1 unit, preferred M 2 unit, and preferred D 2 unit are preferably those represented by the following formulae.
  • R 1 to R 5 each independently represents an alkyl group having 4 or less carbon atoms, a fluoroalkyl group, or a phenyl group, as described above.
  • R 1 to R 5 are preferably all methyl groups.
  • the above formula (1) represents the composition of the linear silicone compound (a) for each unit, and represents an average composition.
  • the linear silicone compound (a) may be a mixture with another linear silicone compound having an alkenyl group bonded to a silicon atom, but usually only the linear silicone compound (a) is used.
  • the linear silicone compound having an alkenyl group bonded to a silicon atom may be a mixture of two or more linear silicone compounds having an alkenyl group bonded to a silicon atom.
  • the sequence of D 1 and D 2 may be a random copolymer chain structure. It may be a block copolymer chain structure.
  • the linear silicone compound (a) described in International Publication No. 2007/018028 can be used.
  • the number average molecular weight (Mn) of the linear silicone compound (a) is preferably 500 to 3,000,000, more preferably 1,000 to 2,000,000, and further preferably 1500 to 500,000. By setting Mn within this range, volatilization during heat curing is suppressed, and workability is improved without becoming too viscous.
  • the viscosity of the linear silicone compound (a) at 25 ° C. is preferably 100 to 1000 mPas, more preferably 300 to 700 mPas.
  • the linear silicone compound (b) contained in the curable silicone resin composition in the present invention is preferably a linear silicone compound (b) having at least 3 hydrogen atoms per molecule.
  • the concentration of hydrogen atoms bonded to silicon atoms (Si—H groups) is preferably 0.90 to 43.5 mmol / g, more preferably 3.0 to 16.7 mmol / g. .
  • a hydrogen atom bonded to a silicon atom is preferably present in at least one of the two M units.
  • a more preferable linear silicone compound (b) has a hydrogen atom bonded to a silicon atom in each of two M units, and a part of the D units of n D units also bonded to a silicon atom. It is a linear silicone compound in which hydrogen atoms are present.
  • the linear silicone compound (b) can also be used in combination with other linear silicone compounds having a hydrogen atom bonded to a silicon atom.
  • linear silicone compound having a hydrogen atom bonded to a silicon atom for example, there is no hydrogen atom bonded to a silicon atom in the M unit, and a hydrogen atom bonded to a silicon atom is only part of the D unit.
  • Examples include existing linear silicone compounds.
  • Examples of the linear silicone compound (b) or a mixture of the linear silicone compound (b) and another linear silicone compound having a hydrogen atom bonded to a silicon atom are represented by the following formula (2).
  • a linear silicone compound having a hydrogen atom bonded to a silicon atom having an average composition is preferably mentioned.
  • M 1 is an M unit in which neither a hydrogen atom bonded to a silicon atom nor an alkenyl group exists (the same as the M 1 unit in the above formula (1))
  • M 3 is an M unit in which a hydrogen atom bonded to a silicon atom is present.
  • ⁇ is a number of 0 or more and less than 1, ⁇ is a number of 1 or more and 2 or less, ⁇ is a number of 1 or more, and ⁇ is a number of 1 or more.
  • the M 3 unit may have two or three hydrogen atoms bonded to a silicon atom, but preferably has one.
  • the D 3 unit may have two hydrogen atoms bonded to a silicon atom, but preferably has one.
  • the M 1 unit, D 1 unit, preferred M 3 unit, and preferred D 3 unit are preferably those represented by the following formulae.
  • R 1 to R 5 each independently represents an alkyl group having 4 or less carbon atoms, a fluoroalkyl group, or a phenyl group.
  • R 1 to R 5 are preferably all methyl groups.
  • ⁇ / ⁇ which is the abundance ratio between D 1 and D 3
  • the abundance ratio ( ⁇ / ⁇ ) is preferably 0.2 to 30, and particularly preferably 0.5 to 20. If this abundance ratio is too small, the residual amount of unreacted hydrogen atoms (hydrogen atoms bonded to silicon atoms) in the cured silicone resin will increase, and the change in peel strength of the cured silicone resin with respect to the glass substrate over time May increase, and heat resistance may be reduced. On the other hand, if the abundance ratio is too large, the crosslink density of the cured silicone resin decreases, which may cause a decrease in heat resistance.
  • ⁇ / ⁇ representing the abundance ratio of M 3 units to D 3 units is preferably 15 ⁇ ( ⁇ / ⁇ ) ⁇ 1000 ⁇ 1500. More preferably, 15 ⁇ ( ⁇ / ⁇ ) ⁇ 1000 ⁇ 1000, and particularly preferably 15 ⁇ ( ⁇ / ⁇ ) ⁇ 1000 ⁇ 500.
  • ( ⁇ / ⁇ ) ⁇ 1000 is less than 15, the molecular weight increases, or the steric hindrance of the functional group increases and the reactivity decreases, so that the change in the peel strength of the cured silicone resin with respect to the glass substrate with time is changed. May grow.
  • ( ⁇ / ⁇ ) ⁇ 1000 is larger than 1500, the crosslink density becomes small, so that a cured silicone resin having sufficient physical properties such as strength may not be obtained.
  • the above formula (2) represents the composition of the linear silicone compound (b) for each unit, and represents an average composition.
  • a more preferable linear silicone compound (b) is a compound in which ⁇ is a number of 0 or more and less than 1, ⁇ is a number of 1 or more and 2 or less, ⁇ is a number of 1 or more, and ⁇ is a number of 1 or more.
  • (beta) + (epsilon) is 3 or more because the linear silicone compound (b) has 3 or more hydrogen atoms couple
  • the number of hydrogen atoms bonded to silicon atoms per molecule of the linear silicone compound (b) is 2, high heat resistance cannot be achieved by crosslinking. Therefore, the number of hydrogen atoms bonded to silicon atoms per molecule of the linear silicone compound (b) is preferably 3 to 120 in terms of heat resistance of the cured product, and more preferably 3 to 100. preferable.
  • Examples of the linear silicone compound having a hydrogen atom bonded to a silicon atom other than the linear silicone compound (b) include silicon in which ⁇ is 2, ⁇ is 0, ⁇ is an integer of 0 or more, and ⁇ is an integer of 1 or more.
  • the sequence of the D 1 and D 3 may be a block copolymer chain structure may be a random copolymer chain structure.
  • a copolymer chain is formed by ring-opening polymerization of a cyclic siloxane, so that it is considered that the ring-opened cyclic siloxane block has a random copolymerized structure.
  • the linear silicone compound having a hydrogen atom bonded to a silicon atom not only the linear silicone compound whose individual molecule is the linear silicone compound (b), but also the linear silicone compound (b) and silicon. It may be a mixture of other linear silicone compounds having a hydrogen atom bonded to an atom (the average composition of which is represented by the formula (2)). In that case, it is preferable that 20 mol% or more of the linear silicone compound (b) is included in the total number of moles of the other linear silicone compound having a hydrogen atom bonded to the silicon atom used.
  • the content of the linear silicone compound (b) is preferably 50 mol% or more, more preferably 80 mol% or more. preferable.
  • the number average molecular weight (Mn) of the linear silicone compound (b) is preferably 300 to 5,000,000, more preferably 400 to 1,000,000, and further preferably 500 to 500,000.
  • the number average molecular weight (Mn) of the linear silicone compound (b) is smaller than the number average molecular weight (Mn) of the linear silicone compound (a).
  • the viscosity of the linear silicone compound (b) at 25 ° C. is preferably 10 to 100 mPas, more preferably 20 to 50 mPas.
  • the cyclic silicone compound (c) contained in the curable silicone resin composition in the present invention is preferably a cyclic silicone compound (c1) having at least two alkenyl groups bonded to a silicon atom per molecule, and further bonded to a silicon atom. It is also preferable to include a cyclic silicone compound (c2) having a hydrogen atom.
  • the curable silicone resin composition to be the cured silicone resin layer further contains a cyclic silicone compound (c) in addition to the linear silicone compound (a) and the linear silicone compound (b) described above.
  • a cyclic silicone compound (c) in addition to the linear silicone compound (a) and the linear silicone compound (b) described above.
  • the linear silicone compound (a) and the linear silicone compound (b) are linear, when subjected to high-temperature heat treatment, the Si—O bond is broken in a bent state, and this Si A new Si—O bond is formed with other O atoms in the same molecule (hereinafter referred to as “replacement of Si—O bond”), and as a result, a cyclic low-molecular polysiloxane is formed. It may be volatilized.
  • the linear silicone compound (a) and the linear silicone compound (b) can further exchange Si—O bonds in one molecule by containing the cyclic silicone compound (c).
  • the cyclic silicone compound (c) is an organopolysiloxane in which a plurality of D units are bonded cyclically, and an alkenyl group bonded to a silicon atom or a hydrogen atom bonded to a silicon atom exists in the D unit.
  • the alkenyl group is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group, and the like. Groups are preferred.
  • the number of silicon atoms constituting the ring is preferably 3 to 10, more preferably 3 to 8, more preferably 3 to 6 from the viewpoints of ease of synthesis and heat resistance of the cured product. Individual is particularly preferred.
  • the concentration of the alkenyl group or the concentration of the hydrogen atom bonded to the silicon atom in the cyclic silicone compound (c) is preferably 0.5 to 44 mmol / g, because of the ease of synthesis, and is preferably 1.0 to 17 mol / g. Is more preferable.
  • cyclic silicone compound (c) which is the cyclic silicone compound (c), and the cyclic silicone compound (c2) will be described in more detail.
  • the number of alkenyl groups per molecule of the cyclic silicone compound (c1) is preferably 2 to 20 and more preferably 3 to 20 from the viewpoint of heat resistance of the cured product.
  • the number of hydrogen atoms bonded to the silicon group per molecule of the cyclic silicone compound (c2) is preferably 2 to 20, more preferably 3 to 20, in view of the heat resistance of the cured product.
  • Cyclic silicone compound (c1) A preferred embodiment of the cyclic silicone compound (c1) is, for example, a cyclic silicone compound represented by the following formula (c1-1).
  • Vi represents a vinyl group
  • R 11 to R 13 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • h represents 2 to 6 I represents an integer of 0 to 4
  • h + i represents an integer of 3 to 10.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 11 to R 13 in the formula (c1-1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, and an isobutyl group. , T-butyl group and the like.
  • Examples of the aryl group having 6 to 10 carbon atoms represented by R 11 to R 13 in the formula (c1-1) include a phenyl group, an ethylphenyl group, a tolyl group, a cumenyl group, a xylyl group, a pseudocumenyl group, a mesityl group, Examples thereof include t-butylphenyl group, benzyl group, phenethyl group and the like.
  • the group represented by R 11 to R 13 in formula (c1-1) is preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group, from the viewpoints of heat resistance, industrial availability, and the like. .
  • h is preferably an integer of 3 to 6 and more preferably 3 or 4 from the viewpoint of the hardness of the cured product.
  • I in the formula (c1-1) is preferably 0 or 1, more preferably 0, from the viewpoint of ease of synthesis.
  • cyclic silicone compound (c1) represented by the formula (c1-1) include 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6,8-tetra Methyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl -2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-8-phenyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4-dimethyl-6,8 -Diphenyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2-phenyl-4,6,8-trivinylcyclotetrasiloxane, 2,4,6,8-t
  • Cyclic silicone compound (c2) is, for example, a cyclic silicone compound represented by the following formula (c2-1).
  • R 11 to R 13 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • j represents an integer of 3 to 6
  • k is Represents an integer of 0 to 4
  • j + k represents an integer of 3 to 10.
  • R 11 ⁇ R 13 in the formula (c2-1) has the same meaning as R 11 ⁇ R 13 in the formula (c1-1), and preferred ranges are also the same.
  • J in formula (c2-1) is preferably 4 or 5, more preferably 4, from the viewpoint of the hardness of the cured product.
  • K in the formula (c2-1) is preferably 0 or 1, more preferably 0 from the viewpoint of ease of synthesis.
  • cyclic silicone compound (c2) represented by the formula (c2-1) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4 , 6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6-trimethyl-8-phenylcyclotetrasiloxane, etc., and these can be used alone. Or two or more of them may be used in combination.
  • the content ratio of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c) is not particularly limited. From the viewpoint of heat resistance at 450 ° C., the number of moles of alkenyl groups (C1 m ) in the cyclic silicone compound (c1) represented by the following formula (3) in the curable silicone resin composition and the cyclic silicone compound (c2) ratio of the moles of alkenyl groups (C2 m) in (mol%) is preferably 20 or more.
  • a m is the number of moles of alkenyl groups in the linear silicone compound (a)
  • B m is the number of moles of hydrogen atoms bonded to silicon atoms in the linear silicone compound (b)
  • C1 m cyclic silicone compound moles and C2 m of alkenyl groups in c1) represents the number of moles of hydrogen atoms bonded to silicon atoms of the cyclic silicone compound (c2) in.
  • the alkenyl group in the linear silicone compound (a) and the cyclic silicone compound (c1) is preferably 20 mol% or more.
  • the ratio (mol%) represented by the above formula (3) is preferably 20 to 100, more preferably 24 to 95, and 24 to 93 from the viewpoint of crack resistance. Further preferred.
  • the cyclic silicone compound (c) with respect to a total of 100 mass% of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c). ) Is preferably 0.1 to 60% by mass, more preferably 0.5 to 38% by mass, and particularly preferably less than 30% by mass. That is, if the content of the cyclic silicone compound (c) is too large, the cured silicone resin layer becomes too hard and there is a possibility that cracks may occur even with a thin film thickness. If the content of (c) is within the above range, the cured silicone resin layer does not become too hard, and the maximum film thickness that can be formed without causing cracks can be increased, that is, the crack resistance is improved. it can.
  • the cyclic silicone compound (c) in which the concentration of alkenyl groups or the concentration of hydrogen atoms bonded to silicon atoms in the cyclic silicone compound (c) is 0.5 to 44 mmol / g.
  • the content of is preferably 0.1 to 60% by mass with respect to 100% by mass in total of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c).
  • the cyclic silicone compound (c) consists only of the cyclic silicone compound (c1).
  • the content of the linear silicone compound (a) is 5 to 5% with respect to a total of 100% by mass of the linear organopolysiloxane (a), the linear silicone compound (b), and the cyclic organopolysiloxane (c). 95% by mass is preferable, and 10 to 90% by mass is more preferable.
  • the content of the linear silicone compound (b) is 3 to 75% by mass with respect to 100% by mass in total of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c). % Is preferable, and 8 to 65% by mass is more preferable.
  • the amounts of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c) were bonded to all silicon atoms relative to all alkenyl groups. It is preferable to adjust the molar ratio of hydrogen atoms (hydrogen atom / alkenyl group) to 0.7 to 1.05, and more preferable to adjust to 0.8 to 1.0. If the molar ratio exceeds 1.05, the peel strength of the cured silicone resin after standing for a long time tends to increase, and the peelability may not be sufficient. On the other hand, when the molar ratio is less than 0.7, the crosslinking density of the cured silicone resin is lowered, which may cause a problem in chemical resistance.
  • Various additives may be contained in the curable silicone resin composition in the present invention as long as the effects of the present invention are not impaired as necessary.
  • a catalyst addition reaction catalyst
  • the catalyst include metal catalysts, and it is preferable to use a platinum group metal catalyst.
  • the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity.
  • a known catalyst can be used as the platinum-based catalyst.
  • the catalyst has a mass ratio to the total mass of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c), preferably 2 to 400 ppm, more preferably 5 to 300 ppm, and more preferably 8 to 200 ppm. Is more preferable.
  • the curable silicone resin composition of the present invention is used together with a catalyst and an activity inhibitor (a compound also called a reaction inhibitor, a retarder, etc.) having an action of suppressing the catalyst activity for the purpose of adjusting the catalyst activity. It is preferable to do.
  • an activity inhibitor a compound also called a reaction inhibitor, a retarder, etc.
  • an activity inhibitor for example, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 2-ethynylisopropanol
  • Acetylenic alcohols such as 2-ethynylbutan-2-ol, 3,5-dimethyl-1-hexyn-3-ol; trimethyl (3,5-dimethyl-1-hexyne-3-oxy) silane, methylvinyl Silylated acetylenic alcohols such as bis (3-methyl-1-butyne-3-oxy) silane and ((1,1-dimethyl-2-propynyl) oxy) trimethylsilane; diallyl malate, dimethyl malate, diethyl Unsaturated carboxylic acid esters such as fumarate, diallyl fumarate, bis (methoxyisopropyl) malate; 2-iso Til-1-buten-3-yn
  • the content of the reaction inhibitor in the composition is not particularly limited, but is 100 parts by mass in total of the linear silicone compound (a), the linear silicone compound (b), and the cyclic silicone compound (c). It is preferably in the range of 0.00001 to 5 parts by mass.
  • an inorganic filler such as various silicas, calcium carbonates, iron oxides and the like may be contained within a range not impairing the effects of the present invention.
  • organic solvents such as hexane, heptane, octane, toluene and xylene, and dispersion media such as water are components that do not constitute a cured silicone resin, but include improved workability for application of the curable silicone resin composition. For the purpose, it can be blended and used in the curable silicone resin composition of the present invention.
  • ⁇ Formation of resin layer> it is preferable to cure the curable silicone resin composition on the first main surface 12A of the support substrate 12 to form the resin layer 14 made of a cured silicone resin.
  • a curable silicone resin composition is applied to one side of a supporting substrate to form a layer of the curable silicone resin composition, and then the curable silicone resin composition is cured to form a cured silicone resin layer.
  • the curable silicone resin composition is a fluid composition
  • the layer of the curable silicone resin composition is applied as it is, and the curable silicone resin composition has a low fluidity or a non-fluid composition.
  • an organic solvent is blended and applied.
  • an emulsion or dispersion of a curable silicone resin composition can also be used.
  • the coating film containing a volatile component such as an organic solvent is then evaporated to remove the volatile component to form a curable silicone resin composition layer. Curing of the curable silicone resin composition can be performed continuously with evaporation removal of volatile components.
  • Curing of the curable silicone resin composition is not limited to the above method.
  • a curable silicone resin composition can be cured on some peelable surface to produce a cured silicone resin film, and this film can be laminated to a support substrate to produce a support.
  • the curable silicone resin composition does not contain a volatile component, it can be cured by being sandwiched between the glass substrate 16 and the support base 12 as described above.
  • the application method is not particularly limited, and a conventionally known method can be mentioned.
  • known methods include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of composition.
  • a volatile component is not blended in the curable silicone resin composition
  • a die coating method, a spin coating method, or a screen printing method is preferable.
  • the composition is cured after removing the volatile component by heating or the like before curing.
  • the conditions for curing the curable silicone resin composition vary depending on the type of organopolysiloxane used and the optimum conditions are appropriately selected.
  • the heating temperature is preferably 50 to 300 ° C.
  • the treatment time is preferably 5 to 300 minutes.
  • the resin layer has low silicone migration, when the glass substrate is peeled off, the components in the resin layer are difficult to migrate to the glass substrate.
  • the reaction temperature and reaction time described above are preferable because substantially no unreacted organosilicone component remains in the resin layer. If the reaction time is too long or the reaction temperature is too high, the organosilicone component and the cured silicone resin are simultaneously oxidized and decomposed to produce a low molecular weight organosilicone component, resulting in high silicone migration. There is a possibility. It is also preferable to allow the curing reaction to proceed as much as possible so that no unreacted organosilicone component remains in the resin layer, in order to improve the peelability after the heat treatment.
  • a surface modification treatment may be performed on the support substrate 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 method such as a sandblast treatment
  • a mechanical treatment method for increasing the catch by increasing the roughness examples thereof include a mechanical treatment method for increasing the catch by increasing the roughness.
  • the thickness of the resin layer 14 made of the cured silicone resin is not particularly limited, and an optimum thickness is appropriately selected depending on the type of the glass substrate 16 and the like, but is preferably 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m. Is more preferable, and 1.0 to 20 ⁇ m is more preferable.
  • the resin layer 14 may be composed of two or more layers.
  • “the thickness of the resin layer” means the total thickness of all the layers.
  • the kind of resin which forms each layer may differ.
  • the surface tension of the peelable surface of the resin layer 14 is preferably 30 mN / m or less, more preferably 25 mN / m or less, and even more preferably 22 mN / m or less. Although there is no limitation in particular about a minimum, 15 mN / m or more is preferred. With such surface tension, it can be more easily peeled off from the surface of the glass substrate 16, and at the same time, adhesion to the surface of the glass substrate 16 is sufficient.
  • the resin layer 14 is preferably made of a material having a glass transition point lower than room temperature (about 25 ° C.) or a material having no glass transition point. If it is such a glass transition point, it can have moderate elasticity while maintaining non-adhesiveness, and can be more easily peeled off from the surface of the glass substrate 16, and at the same time, can be adhered to the surface of the glass substrate 16. It will be enough.
  • the thermal decomposition starting temperature of the resin layer 14 made of a cured silicone resin is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, and particularly preferably 430 ° C. to 450 ° C. in the laminated state of the glass substrate. If it is in the said range, decomposition
  • the cured silicone resin in the present invention has an elastic modulus that satisfies this required performance.
  • the support 20 of the present invention includes the support base 12 and the resin layer 14 described above. Since the surface of the resin layer 14 exhibits good peeling performance, it can be peeled without destroying the laminated glass substrate 16 thereon. Therefore, it can be suitably used as a support for supporting the glass substrate. Moreover, as another use, the support body of the glass substrate for organic EL lighting, etc. are mentioned.
  • the glass substrate 16 is a glass substrate for producing a display device panel by forming a constituent member 18 of the display device panel, which will be described later, on the glass substrate 16.
  • the manufacturing method of the glass substrate 16 used by this invention is not specifically limited, It can manufacture by a conventionally well-known method. For example, it can be obtained by melting a conventionally known glass raw material into a molten glass and then forming it into a plate shape by a float method, a fusion method, a slot down draw method, a redraw method, a pulling method or the like. Commercial products can also be used.
  • the thickness, shape, size, physical properties (heat shrinkage rate, surface shape, chemical resistance, etc.), composition, etc. of the glass substrate 16 are not particularly limited.
  • conventional glass for display devices such as LCDs and OLEDs. It may be the same as the substrate.
  • the thickness of the glass substrate 16 is not particularly limited, but is preferably less than 0.7 mm, more preferably 0.5 mm or less, and even more preferably 0.4 mm or less. Moreover, 0.05 mm or more is preferable, 0.07 mm or more is more preferable, and 0.1 mm or more is further more preferable.
  • the glass substrate 16 has a first main surface 16A and a second main surface 16B, and the shape thereof is not limited, but is preferably rectangular.
  • the rectangle is substantially a rectangle and includes a shape obtained by cutting off the corners of the peripheral portion (that is, a shape obtained by corner cutting).
  • the size of the glass substrate 16 is not limited, for example, in the case of a rectangle, it may be 100 to 2000 mm ⁇ 100 to 2000 mm, and preferably 500 to 1000 mm ⁇ 500 to 1000 mm.
  • the glass laminate 30 can easily peel the glass substrate 16 and the support 20.
  • the thermal contraction rate of the glass substrate 16 is preferably small.
  • the linear expansion coefficient which is an index of the thermal shrinkage rate, is preferably 150 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 100 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 45 ⁇ 10 ⁇ 7 / ° C. or less. .
  • the linear expansion coefficient means a value defined in JIS R3102 (1995).
  • the glass substrate 16 is made of, for example, alkali metal oxide-containing silicate glass or non-alkali silicate glass.
  • non-alkali silicate glass such as borosilicate glass containing no alkali metal oxide is preferable because of its low thermal shrinkage.
  • the surface of the glass substrate 16 described above may be a polished surface that has been subjected to polishing treatment, or may be a non-etched surface (fabric surface) that has not been subjected to polishing treatment. That is, a material that satisfies flatness may be selected as appropriate in accordance with the required accuracy of the display panel to be manufactured.
  • the glass laminate 30 in the present invention is composed of the above-mentioned support base 12, resin layer 14, and glass substrate 16.
  • the resin layer 14 has a peelable surface, and is a glass substrate 16 or a display device panel 40 (in the case of a display device panel, a glass substrate on which a constituent member 18 of the display device panel is formed. 16) can be easily peeled off.
  • the peel strength between the surface of the resin layer 14 and the surface of the glass substrate 16 is preferably 8.5 N / 25 mm or less, more preferably 7.8 N / 25 mm or less, and further preferably 4.5 N / 25 mm or less.
  • the glass substrate should just have the adhesive force of the grade which does not raise
  • the peel strength between the resin layer surface and the glass substrate surface is represented by the following measurement method.
  • the center part of the protruding glass substrate 25 ⁇ 25 mm is pushed vertically using a digital force gauge, Measure peel strength.
  • the peel strength between the surface of the resin layer 14 and the surface of the supporting substrate 12 is preferably 9.8 N / 25 mm or more, more preferably 14.7 N / 25 mm or more, and further preferably 19.6 N / 25 mm or more.
  • peeling between the supporting substrate and the resin layer hardly occurs when the glass substrate or the like is peeled from the resin layer, and the glass substrate or the like and the supporting body from the glass laminate (that is, the supporting substrate and the resin layer). Can be easily separated.
  • this peel strength can be easily achieved by curing the curable silicone resin composition on the support substrate.
  • the peel strength between the surface of the resin layer 14 and the surface of the support base 12 is preferably 29.4 N / 25 mm or less.
  • the peel strength between the surface of the resin layer 14 and the surface of the support base 12 is preferably 10 N / 25 mm or more higher than the peel strength between the surface of the resin layer 14 and the surface of the glass substrate 16, and 15 N / 25 mm. More preferably, it is higher.
  • the method for producing the glass laminate 30 is preferably a method (lamination method) in which the glass substrate 16 is laminated on the surface of the resin layer 14 of the support 20.
  • the method for manufacturing the glass laminate 30 is not limited to this lamination method.
  • the laminating method the first main surface 16A of the glass substrate and the peelable surface of the resin layer 14 are bonded by a force caused by van der Waals force between the adjacent solid molecules that are very close to each other, that is, by an adhesion force. It is considered possible. Therefore, in this case, the supporting base material and the glass substrate can be held in a state of being laminated via the resin layer.
  • a glass laminate having the support 20 and the glass substrate 16 in contact with the peelable surface side of the resin layer 14 is obtained.
  • stacking a glass substrate on the surface of the resin layer of a support body is demonstrated.
  • the method for laminating the glass substrate on the surface of the resin layer fixed to the support substrate is not particularly limited and can be carried out using a known method.
  • a non-contact pressure bonding method in which a glass substrate is stacked on the surface of a resin layer in a normal pressure environment, and then the resin layer and the glass substrate are pressure-bonded using a pressure chamber; the resin layer and the glass substrate using a roll or a press And the like.
  • a method of pressure bonding with a pressure chamber, a roll, a press or the like is preferable because the resin layer and the glass substrate are more closely adhered to each other.
  • pressurization with gas and pressure bonding with a roll or a press are preferable because air bubbles mixed between the resin layer and the glass substrate are relatively easily removed.
  • the surface of the glass substrate is sufficiently washed and laminated in a clean environment. Even if a foreign substance is mixed between the resin layer and the glass substrate, the resin layer is deformed and thus does not affect the flatness of the surface of the glass substrate. However, the higher the cleanness, the better the flatness. Therefore, it is preferable.
  • the constituent member 18 of the display device panel refers to a member formed on the glass substrate 16 or a part thereof in a display device such as an LCD or an OLED using the glass substrate 16.
  • a display device such as an LCD or OLED
  • various circuit patterns such as a TFT array (hereinafter simply referred to as “array”), a protective layer, a color filter, a liquid crystal, a transparent electrode made of ITO, etc. on the surface of the glass substrate 16. These members or a combination of these members is formed.
  • a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like formed on the glass substrate 16 can be used.
  • the display device panel 40 including the glass substrate 16 and the constituent member 18 is a glass substrate on which at least a part of the above members is formed. Therefore, for example, the glass substrate 16 on which the array is formed or the glass substrate 16 on which the transparent electrode or the like is formed is the display device panel 40.
  • the support-equipped display device panel 10 includes a support base 12, a resin layer 14, a glass substrate 16, and a display device panel constituent member 18.
  • the display-equipped display device panel 10 includes, for example, an array-forming surface of the support-equipped display device panel in which the array is formed on the first main surface 16A of the glass substrate 16, and a color filter that is the first of the glass substrate.
  • the form which bonded together the color filter formation surface of the panel for other display apparatuses with a support body formed in 2 main surface 16B via the sealing material etc. is also contained.
  • the display device panel 40 can be obtained from the support-equipped display device panel 10.
  • the display device panel 10 includes the display panel constituent member 18 and the glass substrate 16 by peeling the glass substrate 16 and the resin layer 14 fixed to the support base material 12 from the support-equipped display device panel 10.
  • Panel 40 can be obtained.
  • a display device can be obtained from such a display device panel.
  • the display device include an LCD and an OLED.
  • the LCD include TN type, STN type, FE type, TFT type, and MIM type.
  • the method for forming at least a part of the constituent members of the display device panel on the glass substrate surface of the glass laminate is not particularly limited, and a conventionally known method is performed according to the type of the constituent member of the display device panel. Is done.
  • a transparent electrode is formed on the second main surface 16B of the glass substrate. Step of forming, step of depositing a hole injection layer, hole transport layer, light emitting layer, electron transport layer, etc. on the surface on which the transparent electrode is formed, step of forming a back electrode, step of sealing using a sealing plate
  • Various layer formation and processing such as are performed.
  • these layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.
  • the formation of these constituent members may be part of the formation of all the constituent members necessary for the display device panel. In that case, after peeling the glass substrate which formed the one part structural member from the resin layer, the remaining structural members are formed on a glass substrate, and the panel for display apparatuses is manufactured.
  • the first main surface 16A of the glass substrate 16 and the peelable surface of the resin layer 14 in the display device panel 10 with the support are further peeled to obtain a display device.
  • Panel 40 can be obtained.
  • the constituent members on the glass substrate at the time of peeling are a part of the formation of all the constituent members necessary for the display device panel, the remaining constituent members are then formed on the glass substrate for display. Manufacture panels for equipment.
  • the method of peeling the 1st main surface of a glass substrate and the peelable surface of a resin layer is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate and the resin layer, and after peeling is given, a mixed fluid of water and compressed air is sprayed to peel off. Can do.
  • the support base of the display device panel with support is placed on the surface plate so that the support base is on the upper side and the panel side is on the lower side, and the panel side substrate is vacuum-sucked on the surface plate, and in this state, the blade is first attached. A blade is allowed to enter the glass substrate-resin layer interface.
  • the supporting substrate side is adsorbed 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. If it does so, an air layer will be formed in the interface of a resin layer and a panel side glass substrate, the air layer will spread over the whole surface of an interface, and a support base material can be peeled easily.
  • the support base material is laminated
  • a display device can be manufactured using the obtained display device panel.
  • the operation for obtaining the display device is not particularly limited.
  • the display device can be manufactured by a conventionally known method.
  • a step of forming an array on a conventionally known glass substrate, a step of forming a color filter, a glass substrate on which an array is formed, and a glass substrate on which a color filter is formed May be the same as various steps such as a step of bonding together through a sealing material or the like (array / color filter bonding step). More specifically, examples of the processing performed in these steps include pure water cleaning, drying, film formation, resist solution application, exposure, development, etching, and resist removal. Further, as a process performed after the array / color filter bonding process is performed, there are a liquid crystal injection process and an injection port sealing process performed after the above process, and a process performed in these processes is mentioned.
  • Example 1 A glass substrate having a length of 350 mm, a width of 300 mm, and a plate thickness of 0.5 mm (“AN100”, a glass plate made of borosilicate glass containing no alkali metal oxide and having a linear expansion coefficient of 38 ⁇ 10 ⁇ 7 / ° C .: manufactured by Asahi Glass Co., Ltd.) was prepared as a supporting substrate, and the surface was purified by washing with pure water and UV to obtain a supporting substrate with a cleaned surface.
  • AN100 a glass plate made of borosilicate glass containing no alkali metal oxide and having a linear expansion coefficient of 38 ⁇ 10 ⁇ 7 / ° C .: manufactured by Asahi Glass Co., Ltd.
  • a linear silicone compound (a) (hereinafter also referred to as “component (a)”), a vinyl group-containing methylpolysiloxane (vinyl group concentration: 0.904 mmol / g, viscosity at 25 ° C .: 560 mPas, number average molecular weight) (Mn): 10, 100 Average number of vinyl groups per molecule: 9, all organic groups bonded to silicon atoms other than vinyl groups are methyl groups, manufactured by Arakawa Chemical Co.) and linear silicone compound (b) (hereinafter referred to as “Mn”) Si-H group-containing methylpolysiloxane (Si—H group concentration: 6.85 mmol / g, viscosity at 25 ° C .: 20 mPas, number average molecular weight (Mn): 1,000, as “component (b)”) The average number of Si—H groups per molecule: 7, all organic groups bonded to silicon atoms are methyl groups, manufactured by
  • the obtained mixed liquid was coated on the first main surface of the supporting base material with a length of 200 mm and a width of 200 mm by a spin coater (a coating amount of 15 g / m 2 ). Furthermore, it was cured by heating at 210 ° C. for 30 minutes in the air to form a cured silicone resin layer, thereby obtaining a support. At this time, a plurality of supports having different thicknesses of the cured silicone resin layer of 1 to 12 ⁇ m were obtained by adjusting the spin coater rotation speed and the coating amount.
  • the silicon compound (boiling point: 120 ° C.) having an acetylenically unsaturated group represented by the formula (d-1) as a reaction inhibitor was removed in the heat curing treatment step.
  • a glass substrate having a length of 200 mm, a width of 200 mm, and a thickness of 0.2 mm (“AN100”, a glass plate made of the same glass as the glass having a linear expansion coefficient of 38 ⁇ 10 ⁇ 7 / ° C .: manufactured by Asahi Glass Co., Ltd.) UV cleaning was performed to clean the surface of the glass substrate. Then, after aligning the support and the glass substrate, using a vacuum press, the first main surface of the glass substrate and the peelable surface of the cured silicone resin layer of the support are brought into close contact with each other at room temperature, A glass laminate was obtained.
  • ⁇ Evaluation 1 >> First, about the support body before laminating
  • ⁇ “Maximum film thickness” is 8 ⁇ m or more and 12 ⁇ m or less. “ ⁇ ”: “Maximum film thickness” is 4 ⁇ m or more and less than 8 ⁇ m. “ ⁇ ”: “Maximum film thickness” is 1 ⁇ m or more and less than 4 ⁇ m.
  • ⁇ Evaluation 3-2 A peel test was conducted on the glass laminate after the heat treatment in Evaluation 3-1. Specifically, a glass laminate having a width of 25 mm and a length of 70 mm was prepared, and the glass substrate was peeled off using a precision universal testing machine “Autograph AG-20 / 50kNXDplus” (manufactured by Shimadzu Corporation) ( Peeling speed: 30 mm / min). At this time, a stainless steel knife having a thickness of 0.1 mm was inserted into the interface between the glass substrate and the cured silicone resin layer to form a notch for peeling, and then the glass substrate was completely fixed and the supporting base was pulled up. The peel state was evaluated according to the following criteria. In the case where the evaluation was not performed, “-” was described in Table 1 below. “ ⁇ ”: Interfacial peeling between the glass substrate and the cured silicone resin layer. “X”: A part of the cured silicone resin layer was adhered to the glass substrate.
  • the “molar ratio (C1 m ⁇ 100 / (A m + C1 m ))” shown in Table 1 above is a component with respect to the total amount of the alkenyl group of component (a) and the alkenyl group of component (c) ( This corresponds to the percentage of the alkenyl group ratio (molar ratio) in c).
  • Examples 1 to 4 in which the blending amount of component (c) is less than Example 5 are examples in which the “maximum film thickness” that can form a resin layer without causing cracks is an example. It was thicker than 5 and had better crack resistance. This is probably because the resin layer became slightly hard because the amount of component (c) was slightly too large in Example 5, but in Examples 1 to 4, the resin layer was not too hard with an appropriate amount of component (c). It is done.
  • Comparative Example 1 in which D4Vi was not used as the component (c), change in appearance was confirmed after heat treatment according to Evaluation 3-1, and interface peeling was observed according to Evaluation 3-2. A portion of the resin layer adhered to the glass substrate. Moreover, according to the evaluation 1, the comparative example 2 which did not use the component (a) was inferior in crack resistance. This is considered because the cured silicone resin layer became too hard. In Comparative Example 3 using DVB instead of the component (c), according to the evaluation 2, bubbles (bubbles having a diameter of more than 2 mm) were confirmed after the glass substrate was laminated, and the appearance evaluation after the lamination was inferior. It was. This is considered because the flatness of the cured silicone resin layer was not good.
  • disassembly was suppressed even after high temperature heat processing the support body containing the resin layer, the manufacturing method of the support body, and a glass laminated body can be provided.

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  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition adhésive grâce à laquelle la décomposition d'une couche de résine de silicone durcie est supprimée même après un traitement thermique à haute température. L'invention concerne une composition adhésive qui est caractérisée en ce qu'elle comprend : un composé de silicone linéaire (A) ayant un groupe alcényle lié à un atome de silicium ; un composé de silicone (B) ayant, par molécule, au moins trois atomes d'hydrogène liés à un atome de silicium ; et un composé de silicone cyclique (C) ayant un groupe alcényle lié à un atome de silicium.
PCT/JP2015/065644 2014-05-29 2015-05-29 Composition adhésive, corps support et procédé de production associé, et stratifié en verre WO2015182766A1 (fr)

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CN113165344A (zh) * 2018-11-28 2021-07-23 日产化学株式会社 粘接剂组合物、层叠体、层叠体的制造方法以及半导体形成基板的薄化方法

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JP7102899B2 (ja) * 2018-04-24 2022-07-20 Ａｇｃ株式会社 積層体および電子デバイスの製造方法

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JPH0275681A (ja) * 1988-08-04 1990-03-15 Minnesota Mining & Mfg Co <3M> シリコーン基剤感圧接着剤組成物
JPH0328269A (ja) * 1989-05-19 1991-02-06 Minnesota Mining & Mfg Co <3M> ハイドロシラン化方法
JP2011088982A (ja) * 2009-10-21 2011-05-06 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
JP2012041505A (ja) * 2010-08-23 2012-03-01 Shin-Etsu Chemical Co Ltd 無溶剤型付加型シリコーン粘着剤組成物及び粘着性物品

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Publication number Priority date Publication date Assignee Title
JPH0275681A (ja) * 1988-08-04 1990-03-15 Minnesota Mining & Mfg Co <3M> シリコーン基剤感圧接着剤組成物
JPH0328269A (ja) * 1989-05-19 1991-02-06 Minnesota Mining & Mfg Co <3M> ハイドロシラン化方法
JP2011088982A (ja) * 2009-10-21 2011-05-06 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
JP2012041505A (ja) * 2010-08-23 2012-03-01 Shin-Etsu Chemical Co Ltd 無溶剤型付加型シリコーン粘着剤組成物及び粘着性物品

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113165344A (zh) * 2018-11-28 2021-07-23 日产化学株式会社 粘接剂组合物、层叠体、层叠体的制造方法以及半导体形成基板的薄化方法
CN113165344B (zh) * 2018-11-28 2023-09-12 日产化学株式会社 粘接剂组合物、层叠体、层叠体的制造方法以及半导体形成基板的薄化方法

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