CN105980150A - Glass laminate - Google Patents

Glass laminate Download PDF

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Publication number
CN105980150A
CN105980150A CN201580007605.6A CN201580007605A CN105980150A CN 105980150 A CN105980150 A CN 105980150A CN 201580007605 A CN201580007605 A CN 201580007605A CN 105980150 A CN105980150 A CN 105980150A
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CN
China
Prior art keywords
glass substrate
silicone resin
layer
resin layer
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201580007605.6A
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Chinese (zh)
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CN105980150B (en
Inventor
山本今日子
佐佐木崇
下坂鹰典
闵庚薫
内田大辅
宫嶋达也
石川有希
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AGC Inc
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Asahi Glass Co Ltd
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Publication date
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Publication of CN105980150A publication Critical patent/CN105980150A/en
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Publication of CN105980150B publication Critical patent/CN105980150B/en
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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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • 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
    • B32B2457/00—Electrical equipment
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

Provided is a glass laminate wherein a glass substrate is able to be easily separated even after a high-temperature heat treatment, and wherein decomposition of a silicone resin layer is suppressed. A glass laminate which is provided with a supporting base layer, a silicone resin layer and a glass substrate layer in this order, and wherein: a silicone resin in the silicone resin layer has an organosiloxy unit represented by formula (T3); the ratio of the total organosiloxy units represented by formula (T3) to the total organosiloxy units is 80-100% by mole; the molar ratio of organosiloxy units (A-1) represented by formula (T3) wherein R is a phenyl group to organosiloxy units (B-1) represented by formula (T3) wherein R is a methyl group, namely (A-1):(B-1) is 80-20:20-80; and a specific peel strength relation is satisfied. T3: R-SiO3/2 (In the formula, R represents a phenyl group or a methyl group.)

Description

Glass laminate
Technical field
The present invention relates to glass laminate, particularly relate to possess the glass laminated of specific silicone resin layer Body.
Background technology
In recent years, solaode (PV), liquid crystal panel (LCD), organic EL panel (OLED) Slimming, lightweight is being carried out, the glass substrate used in these equipment Deng equipment (electronic equipment) The most carrying out thin plate.Because of thin plate during the intensity deficiency of glass substrate, in the manufacturing process of equipment In, the treatability of glass substrate reduces.
Recently, in order to tackle the problems referred to above, it is proposed that following method: preparation layer is laminated with sheet glass base Plate and the glass laminate of reinforcing plate, form display device etc. on the glass sheet substrate of glass laminate Electronic device member, then, separates gripper shoe (for example, referring to patent literary composition from glass sheet substrate Offer 1).Reinforcing plate has gripper shoe and the silicone resin layer being fixed in this gripper shoe, organic siliconresin Layer and glass sheet substrate are the most closely sealed.The silicone resin layer of glass laminate and sheet glass base The interface of plate peeling-off and from glass sheet substrate separate reinforcing plate can be with new sheet glass base Flaggy is folded, and recycles as glass laminate.
Prior art literature
Patent documentation
Patent documentation 1: International Publication the 2007/018028th
Summary of the invention
The problem that invention is to be solved
The glass laminate recorded about patent documentation 1, starts the higher thermostability of requirement in recent years.With The multifunction of electronic device member, the complication formed on the glass substrate of glass laminate, The while that temperature when forming electronic device member becoming higher, the time at such high temperatures that exposes also needs Situation that will be longer is a lot.
Glass laminate described in patent documentation 1 is resistant to 300 DEG C, the process of 1 hour in air. But, according to the research of the present inventor etc., the glass laminate described in patent documentation 1 is carried out 450 DEG C, in the case of the process of 1 hour, be intended to by glass substrate with support substrate separate time, exist as follows Situation: glass substrate is not from silicone resin layer sur-face peeling, when being intended to peel off by force, glass substrate A part is destroyed, and its result causes the productivity ratio of electronic equipment to reduce.
It addition, the silicone resin layer in glass laminate described in patent documentation 1 at 450 DEG C short Decompose in time, produce substantial amounts of aerofluxus.The generation of such aerofluxus can be polluted and is formed at glass base Electronic device member on plate, its result, the productivity ratio of electronic equipment can be caused to reduce.
The present invention is the invention made in view of above-mentioned problem, its object is to, it is provided that even if adding at high temperature It also is able to easily be peeled off by glass substrate, can also suppress the decomposition of silicone resin layer after heat treatment Glass laminate.
For solving the scheme of problem
The present inventor etc. are concentrated on studies to solve the problems referred to above, thus complete the present invention.
That is, the present invention is a kind of glass laminate, and it possesses the support layer of base material, organic siliconresin successively Layer and the layer of glass substrate, it is organic that the organic siliconresin in silicone resin layer has that T3 described later represents Siloxy group unit, relative to whole organosiloxane base unit, the organosiloxane base unit that T3 represents Overall ratio be 80～100 moles of %, the R in T3 be phenyl organosiloxane base unit (A-1) with R in T3 is that the mol ratio ((A-1)/(B-1)) of organosiloxane base unit (B-1) of methyl is 80/20～20/80, silicone resin layer is relative to the peel strength at the interface of the layer of glass substrate and organosilicon Resin bed is different relative to the peel strength at the interface of the layer supporting base material.
Present invention it is preferred that, organic siliconresin also has the organosiloxane base that Q described later represents Unit.
Present invention it is preferred that, organic siliconresin is the solidfied material of curable organopolysiloxane, should Curable organopolysiloxane is to comprise, with following ratio, the organosiloxane base that T1～T3 described later represents The organopolysiloxane of unit: in terms of the ratio (mole) of the number of unit, T1:T2:T3= 0～5:20～50:50～80 (wherein, meeting the relation of T1+T2+T3=100).
Present invention it is preferred that, the number-average molecular weight of curable organopolysiloxane is 500～2000.
Present invention it is preferred that, the matter average molecular weight/number-average molecular weight of curable organopolysiloxane is 1.00～2.00.
Present invention it is preferred that, utilize the curable organopolysiloxane that dynamic light scattering method records Particle diameter is 0.5～100nm.
Present invention it is preferred that, curable organopolysiloxane is for by making phenyl trichlorosilane and first The organopolysiloxane that base trichlorosilane hydrolyzes and obtains.
Present invention it is preferred that, the thickness of silicone resin layer is 0.1～30 μm.
Present invention it is preferred that, support base material is glass plate.
Present invention it is preferred that, silicone resin layer is relative to the stripping at the interface of the layer of glass substrate Strength ratio silicone resin layer is low relative to the peel strength at the interface of the layer supporting base material.Hereinafter, also will The present invention of this embodiment is referred to as the 1st embodiment.
It addition, present invention it is preferred that, silicone resin layer is relative to the interface of the layer of glass substrate Peel strength higher relative to the peel strength at interface of the layer supporting base material than silicone resin layer.With Under, also the present invention of this embodiment is referred to as the 2nd embodiment.
The effect of invention
Even if also being able to after high-temperature heating treatment easily by glass base in accordance with the invention it is possible to provide The glass laminate of the decomposition of silicone resin layer is peeled off, can also be suppressed to plate.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the 1st embodiment of the glass laminate of the present invention.
Fig. 2 is a reality of the manufacture method of the band member glass substrate representing the present invention according to process sequence Execute the schematic cross-section of mode.
Fig. 3 is the schematic cross-section of the 2nd embodiment of the glass laminate of the present invention.
Detailed description of the invention
Hereinafter, referring to the drawings the mode being used for implementing the present invention is illustrated, but the present invention does not limit In following embodiment, can be without departing from the scope of the invention to following embodiment Carry out various deformation and displacement.
As the characteristic point of the glass laminate of the present invention, can list: having in silicone resin layer The organosiloxane base unit that the T3 described later that machine silicones comprises ormal weight represents, and, the R in T3 Organosiloxane base unit (A-1) and the organosiloxane base unit that R is methyl in T3 for phenyl (B-1) mol ratio ((A-1)/(B-1)) is the scope of regulation.More specifically, organosilicon tree The organosiloxane base unit that fat represents by comprising the T3 of ormal weight, the thermostability of silicone resin layer carries High.
It addition, the present inventor etc. are to glass substrate and support in the glass laminate after high-temperature heating treatment The reason that substrate is not readily separated is studied, found that be owing to comprising on silicone resin layer surface Functional group produce impact.Such as, when silicone resin layer surface comprises Si-Me base, this group It is easier after high-temperature heating treatment more than 250 DEG C to become Si-OH base.Therefore, organic siliconresin When the amount of the Si-Me base comprised in Ceng is too much, after high-temperature heating treatment, at silicone resin layer table There is more Si-OH base in face, increases with the adhesion of adjacent substrate (such as glass substrate), its As a result, silicone resin layer and the substrate adjacent with this silicone resin layer are not susceptible to peel off.The opposing party Face, Si-Ph base is relatively difficult to be transformed to Si-OH base.But, when Si-Ph base is too much, due to substituent group Steric hindrance, curable organopolysiloxane is difficult to full cross-linked solidification, and the degree of cross linking of silicone resin layer reduces. Therefore, the mechanical strength of silicone resin layer reduces or in the remained on surface source of silicone resin layer In the unreacted Si-OH base of organopolysiloxane, its result, the fissility of glass substrate is deteriorated.This A person of good sense is based on above-mentioned opinion, by regulating above-mentioned mol ratio ((A-1)/(B-1)) even and if being found that The composition of the silicone resin layer that glass substrate is also easily peeled off after high-temperature heating treatment.
Inventive feature also resides in, and in glass laminate, silicone resin layer is relative to glass substrate The peel strength at the interface of layer is strong relative to the stripping at the interface of the layer supporting base material with silicone resin layer Degree difference.Such as, in the 1st embodiment, silicone resin layer is relative to the boundary of the layer of glass substrate The peel strength in face is lower relative to the peel strength at the interface of the layer supporting base material than silicone resin layer, has The layer of machine silicone layer and glass substrate is peeled off, and is separated into silicone resin layer and the stacking supporting base material Body and glass substrate.It addition, in the 2nd embodiment, silicone resin layer is relative to glass substrate The peel strength at interface of layer than silicone resin layer relative to the stripping at interface of the layer supporting base material Intensity is high, and the layer of silicone resin layer and support base material is peeled off, and is separated into glass substrate and organic siliconresin The duplexer of layer and support base material.
Hereinafter, the 1st embodiment and the 2nd embodiment it is divided into illustrate.
＜ the 1st embodiment ＞
Fig. 1 is the schematic cross-section of the 1st embodiment of the glass laminate of the present invention.
As it is shown in figure 1, glass laminate 10 be the layer having and supporting the layer of base material 12 and glass substrate 16 and The duplexer of the silicone resin layer 14 being present between them.The one side of silicone resin layer 14 and support While the layer of base material 12 connects, its another side connects with the 1st interarea 16a of glass substrate 16.
2 layer segments formed by the layer and silicone resin layer 14 that support base material 12 are manufacturing liquid crystal panel etc. Reinforced glass substrate 16 in the component formation process of electronic device member.It should be noted that will be in order to Manufacture glass laminate 10 and previously fabricated formed by the layer and silicone resin layer 14 that support base material 12 2 layer segments be referred to as the support base material 18 of tape tree lipid layer.
Use this glass laminate 10 till component formation process described later.That is, this glassy layer is used Stack 10 is until form the electricity such as liquid crystal indicator on the 2nd interarea 16b surface of described glass substrate 16 Till subset component.Thereafter, it is formed with the glass laminate of electronic device member to be separated into Support group material 12 and the glass substrate of band member, the base material 18 that supports of tape tree lipid layer not constitutes electronic equipment Part.Tape tree lipid layer support base material 18 can with new glass substrate 16 stacking and as new glassy layer Stack 10 recycles.
The interface supporting base material 12 and silicone resin layer 14 has peel strength (x), to supporting base material 12 During the stress of the peeling direction being applied above peel strength (x) with the interface of silicone resin layer 14, The interface of support group material 12 and silicone resin layer 14 is peeling-off.Silicone resin layer 14 and glass substrate 16 Interface there is peel strength (y), the interface of silicone resin layer 14 and glass substrate 16 is applied above During the stress of the peeling direction of peel strength (y), silicone resin layer 14 and the interface of glass substrate 16 Peeling-off.
In glass laminate 10, above-mentioned peel strength (x) is higher than above-mentioned peel strength (y).Therefore, Glass laminate 10 is applied by when supporting the stress in the direction that base material 12 and glass substrate 16 are peeled off, glass Duplexer 10, at silicone resin layer 14 and the interface peel of glass substrate 16, is separated into glass substrate 16 He The support base material 18 of tape tree lipid layer.
Peel strength (x) is preferably sufficiently high compared with peel strength (y).Improve peel strength (x) Refer to, improve the 1st silicone resin layer 14 adhesive force to support base material 12, and, in heat treated It also is able to afterwards maintain and adhesive force of a relatively high compared with glass substrate 16.
In order to improve the silicone resin layer 14 adhesive force to support base material 12, preferably make curable described later Organopolysiloxane crosslinking on support base material 12 is solidified to form silicone resin layer.Utilize crosslinking curing Time bonding force, it is possible to formed with high-bond and the support silicone resin layer 14 that is combined of base material 12.
On the other hand, the organic siliconresin after crosslinking curing is above-mentioned to the adhesion generally ratio of glass substrate 16 The adhesion produced during crosslinking curing is low.Therefore, by supporting formation silicone resin layer on base material 12 14 and laminated glass substrate 16 on the face of silicone resin layer 14 behind, it is possible to manufacture glass laminated Body 10.
Hereinafter, first, to constitute glass laminate 10 each layer (support base material 12, glass substrate 16, Silicone resin layer 14) it is described in detail, then, the manufacture method of glass laminate is carried out in detail Explanation.
[support base material]
Support base material 12 to support and reinforced glass substrate 16, be used for preventing in component formation process described later The change of glass substrate 16 when manufacturing electronic device member in (manufacturing the operation of electronic device member) Shape, damage, breakage etc..
As supporting base material 12, use the such as metallic plate etc. such as glass plate, plastic plate, SUS plate.Due to Component formation process would generally be with heat treatment, therefore, support base material 12 preferably by with glass substrate 16 The material that the difference of linear expansion coefficient is little is formed, and is more preferably formed by the material identical with glass substrate 16, Support group material 12 is preferably glass plate.Supporting base material 12 is particularly preferably by the glass identical with glass substrate 16 The glass plate that material is formed.
It should be noted that as described later, supporting base material 12 can also be formed by layer of more than two kinds Duplexer.
Support base material 12 thickness can thicker than glass substrate 16, can also be thinner than it.It is preferably based on glass The thickness of the thickness of substrate 16, the thickness of silicone resin layer 14 and glass laminate 10 selects to support The thickness of base material 12.Such as, existing component formation process be with the substrate to thickness 0.5mm at The mode of reason and the operation that designs, and the thickness sum of the thickness of glass substrate 16 and silicone resin layer 14 During for 0.1mm, the thickness supporting base material 12 is set as 0.4mm.Support the thickness of base material 12 generally In the case of be preferably 0.2～5.0mm.
Support in the case of base material 12 is glass plate, for the reason such as disposable, to be not easily broken, glass plate Thickness be preferably more than 0.08mm.It addition, shell for after forming electronic device member From time expectation can the reason of the appropriateness bending rigidity without rupturing, the thickness of glass plate is preferably 1.0mm Below.
The difference supporting base material 12 and the glass substrate 16 average coefficient of linear expansion at 25～300 DEG C is preferably 500×10-7/ DEG C below, more preferably 300 × 10-7/ DEG C below, more preferably 200 × 10-7/ DEG C below. When difference is excessive, it may occur that following situation: when the heating in component formation process cools down, glassy layer The violent warpage of stack 10 or support base material 12 and glass substrate 16 peeling-off.Support the material of base material 12 Expect that the material phase with glass substrate 16 is meanwhile, it is capable to suppress such problem to produce.
[glass substrate]
1st interarea 16a of glass substrate 16 connects with silicone resin layer 14, with silicone resin layer 14 Side is in the 2nd interarea 16b of opposition side and is provided with electronic device member.
The kind of glass substrate 16 can be general kind, such as can list LCD, OLED this The glass substrate etc. of the display device of sample.The chemical proofing of glass substrate 16, resistance to excellent moisture permeability, And percent thermal shrinkage is low.As the index of percent thermal shrinkage, use JIS R 3102 (nineteen ninety-five revision) rule Fixed linear expansion coefficient.
When the linear expansion coefficient of glass substrate 16 is big, owing to the many heat tracings of component formation process process, because of This easily produces various unfavorable conditions.Such as, when glass substrate 16 forms TFT, if will add The glass substrate 16 being formed with TFT under heat cools down, then exist and cause because of the thermal contraction of glass substrate 16 The position of TFT offsets excessive worry.
Glass substrate 16 makes frit melt and moltens glass into tabular and obtain.So Manufacturing process can be general method, such as use float glass process, fusion method, slot draw method, vertical Pulling method, Lubbers method etc..It addition, the extremely thin glass substrate 16 of thickness can be by will temporarily shape The temperature that can shape, and the thinning method by campus'cultures such as stretchings it is heated to for the glass of tabular (horizontal drawing (redraw) method) forms and obtains.
The kind of the glass of glass substrate 16 is not particularly limited, preferably alkali-free pyrex, borosilicic acid Glass, soda-lime glass, vagcor, other oxidation system glass with silicon oxide as main component. As oxidation system glass, preferably converted by oxide and the content of silicon oxide that obtains is 40～90 matter The glass of amount %.
As the glass of glass substrate 16, use be suitable for electronic device member kind, its manufacture work The glass of sequence.Such as, for the glass substrate of liquid crystal panel, due to the dissolution of alkali metal component Easily impacting liquid crystal, therefore glass substrate is by the glass (alkali-free being substantially free of alkali metal component Glass) form (wherein, generally comprising alkaline earth metal component).So, the glass of glass substrate 16 can Suitably select with the kind according to the equipment applied and manufacturing process thereof.
From the slimming of glass substrate 16 and/or light-weighted from the standpoint of, the thickness of glass substrate 16 is excellent Elect below 0.3mm, more preferably below 0.15mm as.During for below 0.3mm, can be to glass substrate 16 give good flexibility.During for below 0.15mm, glass substrate 16 can be rolled into a roll.
It addition, the process reason such as easily of easy to manufacture, the glass substrate 16 for glass substrate 16, glass The thickness of glass substrate 16 is preferably more than 0.03mm.
It should be noted that glass substrate 16 can be formed above by 2 layers, in the case of being somebody's turn to do, form each layer Material can be same material, it is also possible to be not same material.It addition, in the case of Gai, " glass base The thickness of plate 16 " refer to the gross thickness of all layers.
[silicone resin layer]
Silicone resin layer 14 offsets until carrying out glass substrate for preventing the position of glass substrate 16 16 and support base material 12 separate operation till, meanwhile, be used for preventing glass substrate 16 grade because of lock out operation And it is damaged.The surface 14a connected with glass substrate 16 of silicone resin layer 14 and the 1st of glass substrate 16 the Interarea 16a is closely sealed.Silicone resin layer 14 is with the 1st interarea 16a knot of weak adhesion with glass substrate 16 Closing, the peel strength (y) at its interface is than the interface between silicone resin layer 14 and support base material 12 Peel strength (x) is low.Silicone resin layer 14 is glass with the adhesion at the interface of glass substrate 16 Can before and after the upper formation in the face (the 2nd interarea 16b) of the glass substrate 16 of duplexer 10 electronic device member With change.Even it is preferable, however, that being formed after electronic device member, peel strength (y) Also lower than peel strength (x).
Think that silicone resin layer 14 and the layer of glass substrate 16 are with weak bonding force, produced by Van der Waals force Adhesion combine.In the situation of its surface layer laminated glass substrate 16 after forming silicone resin layer 14 Under, the situation of the full cross-linked degree for not showing bonding force of organic siliconresin of silicone resin layer 14 It is considered as that the adhesion to be produced by Van der Waals force combines.But, the organosilicon of silicone resin layer 14 Resin in most cases has a certain degree of weak bonding force.Even if thinking in the situation that cementability is extremely low Under, when manufacturing formation electronic device member in this glass laminate 10 after glass laminate 10, By heating operation etc., the organic siliconresin of silicone resin layer 14 is bonding with glass substrate 16 surface, has Adhesion between the layer of machine silicone layer 14 and glass substrate 16 raises.
Difference according to circumstances, it is also possible to before the surface of silicone resin layer 14 before stacking, stacking 1st interarea 16a of glass substrate 16 carries out stacking after the process making adhesion between the two weaken.By right The face wanting stacking carries out non-adhesive process etc. and carries out stacking behind, it is possible to weaken silicone resin layer 14 with the adhesion at the interface of the layer of glass substrate 16, reduce peel strength (y).
Silicone resin layer 14 is combined in support base material 12 table with the adhesion that bonding force, bonding force etc. are strong Face, as the method for the adaptation of both raisings, can use known method.Such as, as described later, (the energy shape of regulation more specifically, is made by forming silicone resin layer 14 on support base material 12 surface The curable organopolysiloxane becoming organic siliconresin is supporting crosslinking curing on base material 12), it is possible to make Organic siliconresin in machine silicone layer 14 is adhered to support base material 12 surface, it is thus achieved that high adhesion.Separately Outward, it is possible to implement make to produce between support base material 12 surface and silicone resin layer 14 place of strong adhesion Reason (such as using the process of coupling agent) improves between support base material 12 surface and silicone resin layer 14 Adhesion.
Silicone resin layer 14 is combined the boundary meaning both with the layer supporting base material 12 with high adhesion The peel strength (x) in face is high.
The thickness of silicone resin layer 14 is not particularly limited, the upper limit be preferably 30 μm (be 30 μm with Under), more preferably 20 μm, more preferably 8 μm.Just do not have as long as lower limit is the thickness that can peel off It is particularly limited to, is mostly more than 0.1 μm.The thickness of silicone resin layer 14 when such scope, Silicone resin layer 14 is not likely to produce crackle, even if pressing from both sides between silicone resin layer 14 and glass substrate 16 Miscellaneous QI bubble, impurity, it is also possible to suppression glass substrate 16 is deformed defect.
Above-mentioned thickness refers to average thickness, is utilize contact determining film thickness device to more than 5 any The thickness of the silicone resin layer 14 of position is measured, and they is carried out arithmetic average and obtains Value.
The surface roughness Ra on the surface of glass substrate 16 side of silicone resin layer 14 is not particularly limited, From the aspect that the stackability of glass substrate 16 and fissility are more excellent, preferably 0.1～20nm, more excellent Elect 0.1～10nm as.
It should be noted that as the assay method of surface roughness Ra, come according to JIS B 0601-2001 Carrying out, the value that the Ra recording the point more than at any 5 carries out arithmetic average and obtains is equivalent to above-mentioned Surface roughness Ra.
It should be noted that silicone resin layer 14 can also be formed above by 2 layers.In this case, " have The thickness of machine silicone layer 14 " refer to the gross thickness of all silicone resin layers.
Generally, the curable organopolysiloxane being coated on base material is by room temperature～less than the heat of base material Carry out heating thus hot under the temperature conditions of deformation temperature after solvent seasoning contained in material, removal Solidification, forms organic siliconresin.During this heat cure, contained in curable organopolysiloxane Silanol group (-Si-OH) between occur dehydration condensation and form siloxane bond (-Si-O-Si-), Solidify while cross-linking, form organic siliconresin.In temperature-rise period, due to because of solvent The capillary force evaporated and produce and the dehydration condensation carried out in film, gel film densification, film Volume slip reaches tens %.Gel film is not perfectly elastic body, but is regarded as and be approximately elastomer Time, when when being bound in direction in face because of base material, film shrinks, deformation is in the face of film Directional cumulation.Its result, in the face of film, direction produces tensile stress (hereinafter also referred to " shrinkage stress ").
The shrinkage stress of the silicone resin layer in the present invention refers to: uses and utilizes at temperature 25 DEG C around The radius of curvature of the Silicon Wafer before and after this silicone resin layer formation that membrane stress determinator records The value of the thickness of value and this silicone resin layer, the organosilicon that the formula utilizing following formula (1) to represent calculates The tensile stress values of the effect of direction along face of resin bed.It should be noted that determination step will implemented Example describes in detail.
σ = E · h 2 ( 1 - v ) · 6 · R · t ... ( 1 )
In formula, E/ (1-ν) is the twin shaft coefficient of elasticity (crystal face (100): 1.805 × 10 of Silicon Wafer11Pa), H is the thickness [m] of Silicon Wafer, and t is the thickness [m] of silicone resin layer, and R is for forming silicone resin layer The radius of curvature of the radius of curvature of Silicon Wafer before and the Silicon Wafer formed after silicone resin layer it Difference [m].
Wherein, difference R of the radius of curvature of the Silicon Wafer before and after formation silicone resin layer is by Silicon Wafer Thickness h, the elastic modulus E of Silicon Wafer, Poisson's ratio ν of Silicon Wafer, thickness t, tensile stress σ determine. When in the face of the film that the one side of Silicon Wafer is formed, direction produces tensile stress σ, from above-mentioned formula (1), The stress σ that direction produces in the face of film is the biggest, and difference R of above-mentioned radius of curvature is the biggest, i.e. the sticking up of Silicon Wafer Qu Yue great.
Therefore, as long as obtaining and being formed with the radius of curvature R of the Silicon Wafer before and after machine silicone layer and organic The thickness t of silicone layer, just can obtain the shrinkage stress of silicone resin layer.It should be noted that curvature Radius R can obtain as follows: the one side at monocrystalline silicon wafer crystal forms silicone resin layer, uses thin film to answer Power determinator, is scanned being formed in the silicon wafer surface of silicone resin layer with laser, from instead R is read in the direction penetrating light, thus obtains.
The size of the shrinkage stress of silicone resin layer 14 is not particularly limited, and makes solidification from being prevented from Property organopolysiloxane crosslinking curing and carry out the process cooled down after forming the technique of silicone resin layer 14 In crack, the warpage of prepared glass laminate 10 can be suppressed further from the standpoint of, preferably For below 50MPa, more preferably below 45MPa.Lower limit is not particularly limited, and mostly generally is 15MPa Above.
Silicone resin layer 14 is formed by the organic siliconresin of the organosiloxane base unit comprising regulation.Separately Outward, organic siliconresin is typically to enable that formed the curable of this organic siliconresin by cured organic Silicone cross solidifies and obtains.
The curable organopolysiloxane of the present invention is to make the water-disintegrable organic silane compound as monomer Mixture (monomer mixture) there is part hydrolysis-condensation reaction and the partial hydrolysis condensate that obtains (has Machine polysiloxanes).It addition, partial hydrolysis condensate can also contain unreacted monomer.
In order to make curable organopolysiloxane crosslinking curing, generally by heating promote cross-linking reaction from And make it solidify (that is, heat cure).By making curable organopolysiloxane heat cure, can be had Machine silicones.Wherein, there is also solidification it is not always necessary that carry out situation about heating, it is possible to so that its room temperature Solidification.
General organic siliconresin (organopolysiloxane) can organic silica by 1 official being referred to as M unit Alkyl unit, be referred to as D unit 2 officials can organosiloxane base unit, be referred to as 3 official's energy of T unit Organosiloxane base unit, be referred to as Q unit 4 officials can organosiloxane base unit constitute.Need explanation , Q unit is that the organic group not having and being bonded to silicon atom (has that to be bonded to the carbon of silicon atom former The organic group of son) unit, but the present invention is regarded as organosiloxane base unit (linkage containing silicon list Unit).Hereinafter the monomer forming T unit is referred to as T monomer.Form M unit, D unit, the list of Q unit Body is referred to as M monomer, D monomer, Q monomer similarly.
In organosiloxane base unit, siloxane bond is 2 silicon atoms keys by 1 oxygen atoms bond, Therefore, the oxygen atom that 1 silicon atom in siloxane bond is corresponding is considered as 1/2, is expressed as O in formula1/2。 More specifically, such as, in 1 D unit, its 1 silicon atom and 2 oxygen atoms bond, each oxygen is former Son and the silicon atom bonding of other unit, therefore, its formula is-O1/2-(R)2Si-O1/2-.Owing to having 2 Individual O1/2, D unit is typically expressed as (R)2SiO2/2。
It should be noted that in the following description, with the oxygen atom O of other silicon atom bonding*For by 2 Between individual silicon atom, the oxygen atom of bonding, refers to the oxygen atom in the key that Si-O-Si represents.Therefore, at 2 1 O is there is between the silicon atom of organosiloxane base unit*。
It is said that in general, T unit refers to R-SiO3/2It is organic that (R represents hydrogen atom or organic group) represents Siloxy group unit.That is, T unit is to have 1 silicon atom, have 1 hydrogen being bonded to this silicon atom Atom or 1 valency organic group and 3 oxygen atom O being bonded to other silicon atom*Unit.
But, in this manual, replace the oxygen atom O being bonded to other silicon atom*A part or complete Portion and there is the situation of the functional group that can be bonded to other silicon atom and be also considered as T unit.Can be bonded to other The functional group of silicon atom is hydroxyl or group (the most water-disintegrable base being become hydroxyl by hydrolysis Group).More specifically, in this manual, in T unit, it is bonded to the oxygen atom O of other silicon atom*It it is 3 with the summation of the functional group that can be bonded to other silicon atom, according to the oxygen being bonded to other silicon atom Atom O*With the difference of the number of the functional group that can be bonded to other silicon atom, T unit is divided into and is referred to as T1 Unit, T2 unit, 3 kinds of unit of T3 unit.T1 unit is bonded to the oxygen atom O of other silicon atom* Number is 1, oxygen atom O described in T2 unit*Number is 2, oxygen atom O described in T3 unit*Number is 3 Individual.It should be noted that in this manual, 1 valency functional group Z of other silicon atom can will be bonded to Represent.
Monomer (water-disintegrable organic silane compound) generally use (R '-)aSi(-Z)4-aRepresent.Wherein, A represent 0～3 integer, R ' represent that hydrogen atom or 1 valency organic group, Z represent hydroxyl or hydrolization group. In this chemical formula, the compound of a=3 is the chemical combination that compound is D monomer, a=1 of M monomer, a=2 Thing be T monomer, the compound of a=0 be Q monomer.In monomer, Z group is usually hydrolization group.Separately Outward, when there is 2 or 3 R ' (when a is 2 or 3), multiple R ' can be different.
Curable organopolysiloxane as partial hydrolysis condensate is by by the one of the Z group of monomer Partial Transformation is oxygen atom O*Reaction and obtain.The Z group of monomer is the situation of hydrolization group Under, Z group is transformed to hydroxyl by hydrolysis, then, by being bonded to the 2 of different silicon atom Dehydration condensation between individual hydroxyl, 2 silicon atoms are by oxygen atom O*Bonding.Curable is organic poly- Residual hydroxyl (or unhydrolysed Z group) in siloxanes, when the solidification of curable organopolysiloxane, These hydroxyls, Z group react as described above and solidify.The solidfied material of curable organopolysiloxane It is usually formed the polymer (organic siliconresin) of 3-dimensional crosslinking.Think when solidification, the organic poly-silicon of curable The Z group of oxygen alkane is transformed to O*, but a part of Z group (particularly hydroxyl) can be remained, formed and there is hydroxyl The solidfied material of base.When making curable organopolysiloxane at high temperature solidify, the most also formed the most residual Stay the solidfied material of hydroxyl.
When the Z group of monomer is hydrolization group, as this Z group, can list: alkoxyl, chlorine Atom, acyloxy, NCO etc..In most cases, as monomer, use Z group is alcoxyl The monomer of base.Compared with alkoxyl and chlorine atom etc., for the hydrolization group that reactivity is relatively low, using Z Group is in the curable organopolysiloxane that the monomer of alkoxyl obtains, and there is hydroxyl as Z group More with the situation of unreacted alkoxyl.The Z group of monomer is reactive higher hydrolization group (example Such as chlorine atom) in the case of, use this monomer and Z group in the curable organopolysiloxane that obtains Nearly all become hydroxyl.Therefore, for common curable organopolysiloxane, constitute each of its The situation that Z group in unit is made up of hydroxyl or is made up of hydroxyl and alkoxyl is more.
(organic siliconresin)
Constitute the organic siliconresin of silicone resin layer 14 have organosiloxane base unit that T3 represents (with It is also referred to as down T3 unit), relative to whole organosiloxane base unit, the organosiloxane that T3 represents The overall ratio of base unit is 80～100 moles of %, from the excellent heat resistance of the silicone resin layer 14 obtained, From the standpoint of the stripping of glass substrate 16 is easier to make for, preferably 82～100 moles %, more preferably 85～100 moles of %.That is, organic siliconresin comprises organosiloxane base unit that T3 represents as main constituent.
T3:R-SiO3/2
In formula, R represents phenyl or methyl.
It should be noted that the organosiloxane base unit that T3 represents is equivalent to the one of above-mentioned T unit. Organic siliconresin can also comprise other unit in addition to the organosiloxane base unit that T3 represents, as Other unit, can list M unit, D unit, T1 unit, T2 unit and Q unit.
Wherein, in time peeling off, there is not the cohesional failure of silicone resin layer 14, silicone resin layer 14 Mechanical strength, glass substrate 16 fissility more excellent from the standpoint of, preferably comprise following Q table The organosiloxane base unit (so-called Q unit) shown.The content of Q unit is not particularly limited, relatively In whole organosiloxane base unit, preferably 1 mole more than %, more preferably 5 moles of more than %.On Limit is not particularly limited, from exist because the degree of cross linking increase and the fragility of silicone resin layer 14 reduce, organic The aspect of the worry of cohesional failure is there is and there is generation because of with solidification in silicone layer 14 when peeling off The increase of shrinkage stress shunk and from the standpoint of the worry of the warpage of glass composite that causes, preferably It is 20 moles of below %.
Q:SiO4/2
It should be noted that above-mentioned whole organosiloxane base unit refers to M contained in organic siliconresin Unit, D unit, T unit and the summation of Q unit.M unit, D unit, (T1～T3 is mono-for T unit Unit), the ratio of the number (mole) of Q unit can by based on29The peak area ratio that Si-NMR obtains Value calculate.
For the organic siliconresin in silicone resin layer 14, the R in T3 is the organosiloxane base of phenyl The mol ratio ((A-1) of organosiloxane base unit (B-1) that R is methyl in unit (A-1) and T3 / (B-1)) it is 80/20～20/80 (it should be noted that meet the pass of (A-1)+(B-1)=100 System).Wherein, from the standpoint of can more easily glass substrate being peeled off, mol ratio ((A-1)/ (B-1) 75/25～20/80, more preferably 70/30～20/80) it is preferably.
R is that organosiloxane base unit (A-1) of phenyl refers to the organosiloxane base that following P-T3 represents Unit.Ph represents phenyl.
P-T3:Ph-SiO3/2
It addition, organosiloxane base unit (B-1) that R is methyl to refer to that following M-T3 represents organic Siloxy group unit.
M-T3:Me-SiO3/2
Above-mentioned organic siliconresin can use known material manufacture.
As the organic poly-silicon of curable that can form above-mentioned organic siliconresin as described above by cured Oxygen alkane, uses the mixture generation partial hydrolysis such as making the water-disintegrable organic silane compound as monomer Condensation reaction and the partial hydrolysis condensate (organopolysiloxane) that obtains.As this monomer, more specifically For, use (Me-) Si (-Z)3The water-disintegrable organic silane compound represented and (Ph-) Si (-Z)3The water-disintegrable organic silane compound represented.It should be noted that Z group represents hydroxyl or water-disintegrable base Group, such as, as hydrolization group, can list the halogen atoms such as chlorine atom, alkoxyl, acyl group, Amino, alkyloxy-alkoxy etc..
It should be noted that hydrolysis-condensation reaction is to be generated T1 unit by T monomer, generated T2 by T1 unit Unit, by T2 unit generate T3 unit reaction.Think and be transformed to hydroxyl by more than the 1 of hydrolization group The T monomer of base generates the condensation reaction of T1 unit, is generated the condensation reaction of T2 unit by T1 unit, by T2 The response speed of the condensation reaction that unit generates T3 unit is the most slack-off.Think, even if considering water-disintegrable base The hydrolysis of group, along with reaction is carried out, the peak of the amount of each unit is also gradually mono-to T3 from T monomer Unit is mobile.Think reaction condition comparatively gentle in the case of amount peak movement the most without any confusion Carry out.
As forming the curable organopolysiloxane of above-mentioned organic siliconresin, as it has been described above, from reaction Control, from the standpoint of process etc., use the portion obtained by the mixture of water-disintegrable organic silane compound Divide hydrolytic condensate (organopolysiloxane).Partial hydrolysis condensate is to make water-disintegrable organic-silylation The monomer mixing that compound is obtained by mixing in the way of becoming the ratio of above-mentioned each organosiloxane base unit Thing partial hydrolysis is condensed and obtains.The method carrying out partial hydrolysis condensation is not particularly limited.Generally, Make the mixture of water-disintegrable organic silane compound in a solvent, react in the presence of catalyst and manufacture.Make For catalyst, it is possible to use acid catalyst, base catalyst.It addition, hydrolysis generally preferably uses water. The partial hydrolysis condensate used in the present invention is preferably and makes water-disintegrable organic silane compound in a solvent Mixture acid or aqueous alkali in the presence of reaction and prepare material.
As the water-disintegrable organic silane compound used, above-mentioned (Me-) Si (-Z) can be listed3The water-disintegrable organic silane compound represented and (Ph-) Si (-Z)3The water-disintegrable organosilan represented Compound, wherein, thermostability height, energy excellent from the treatability of the curable organopolysiloxane obtained From the standpoint of more easily being peeled off by glass substrate 16, phenyl trichlorosilane (following formula (1) is preferably used The compound represented) and methyl trichlorosilane (compound that following formula (2) represents).Need explanation It is that the Ph in formula (1) represents phenyl.
It should be noted that as described later, when forming the layer of curable organopolysiloxane, use bag Compositions containing curable organopolysiloxane, but from improving curable organopolysiloxane further in group From the standpoint of stability in compound, it is also possible to the end-capped (cap) of cured silicone is changed. More specifically, the end Si-OH in curable organopolysiloxane can be made in presence of an acid catalyst (such as in the presence of acetic acid) reacts with alcohol, is removed by water, simultaneously by Si-OH protection end-blocking.Such as, When using methanol, form Si-OMe base.It should be noted that the kind of the alcohol used limits the most especially Fixed, the low-boiling point alcohols such as methanol, ethanol, 1-propanol, n-butyl alcohol can be listed.Wherein, from Si-OH The reactivity of base, curable organopolysiloxane favorable solubility from the standpoint of, preferably methanol, second Alcohol.
(optimal way of curable organopolysiloxane)
One of optimal way as above-mentioned curable organopolysiloxane, can list following organic Polysiloxanes (hereinafter also referred to organopolysiloxane X): there is the organosiloxane that following T1～T3 represents At least any of in base unit, relative to whole organosiloxane base unit, following T1～T3 represents The overall ratio of organosiloxane base unit is 80～100 moles of %, and the R in following T1～T3 is having of phenyl Organic siloxane base unit (A-2) and organosiloxane base unit (B-2) that R is methyl in following T1～T3 Mol ratio ((A-2)/(B-2)) be 80/20～20/80.During for this organopolysiloxane, it is possible to hold Change places and obtain desired organic siliconresin.
T1:R-Si (-OX)2O1/2
T2:R-Si (-OX) O2/2
T3:R-SiO3/2
It should be noted that in formula, R represents phenyl or methyl.X represents hydrogen atom or the alkane of carbon number 1～6 Base.
R in above-mentioned formula is not limited to a kind, and the R in T1, T2, T3 can be respectively different.
It addition ,-OX can be the same or different between T1 unit and T2 unit.In T1 unit 2 Individual-OX can also be different, for example, it is possible to one for hydroxyl, another is alkoxyl.It addition, 2-OX When being alkoxyl, these alkoxyls can be different alkoxyls.
To not have the oxygen atom (O of 2 silicon atom bondings below*), only there is the T unit of 3-OX It is referred to as T0.T0 is effectively equivalent to unreacted T monomer, is not that organosiloxane base unit is (siliceous Key unit).This T0 measures in the parsing of T1～T3 unit in the same manner as T1～T3.
T1～T3 unit in organopolysiloxane X can pass through nuclear magnetic resonance spectroscopy (29Si-NMR) survey The bond styles determining silicon atom resolves.The ratio of the number (mole) of T0～T3 unit by29Si-NMR Peak area ratio obtain.
It should be noted that the matter average molecular weight Mw of organopolysiloxane X, number-average molecular weight Mn and point Divergence Mw/Mn refers to utilize gel permeation chromatography, be measured using polystyrene as standard substance and The value obtained.The characteristic of such organopolysiloxane X does not implies that the characteristic of 1 molecule, but conduct The characteristic that the average characteristics of each molecule is obtained.
The overall ratio of the organosiloxane base unit that above-mentioned T1～T3 in organopolysiloxane X represents is as above Described, relative to whole organosiloxane base unit, preferably 80～100 moles %, organic from obtain From the standpoint of the excellent heat resistance of silicone layer 14, the stripping of glass substrate 16 are easier to make for, preferably It is 82～100 moles of %, more preferably 85～100 moles of %.
It should be noted that in organopolysiloxane X, from the standpoint of treatability, preferably at least wrap Containing above-mentioned T3 unit, more preferably at least comprise above-mentioned T2 unit and T3 unit.Knot through each side's research Fruit finds, when Ph base (phenyl) becomes many, the ratio of T1 unit becomes many.When T1 unit becomes many, organosilicon During solidification in resin bed manufacturing process, shrinkage stress becomes big, when therefore T1 unit is less, it is possible to reduce Shrinkage stress, so more preferably.
It addition, organopolysiloxane X goes back in addition to the organosiloxane base unit that above-mentioned T1～T3 represents Other unit can be comprised, as other unit, M unit, D unit and Q unit can be listed.
As the curable organopolysiloxane of T body, commonly known polyphenylene polysiloxanes, poly-methyl are poly- Siloxanes etc., silanol end polyphenylene polysiloxanes is to make PhSiCl3During hydrolysis hundreds of with molecular weight～ The form of the oligomer of thousands of left and right obtains.This oligomer is used to make the solidification of more than thickness 0.1mm During thing, use cannot be tolerated because of the most fragile.But, it forms the organic siliconresin of excellent heat resistance.
On the other hand, when the substituent group on silicon atom is the aliphatic alkyls such as methyl, it is provided that silanol end RSiZ3The monomer of type reactive high, the molecular weight of the hydrolysis-condensation thing obtained be nearly all 10,000 with On.Therefore, dissolubility in a solvent is poor, in order to make this condensation substance dissolve, needs substantial amounts of solvent, Although the thin film of coating applications etc. can be obtained, but it is difficult to obtain to have certain owing to can crack etc. The solidfied material of degree thickness.
It is therefore preferable that use taken into account thermostability and reactive, improve deliquescent above-mentioned curable and have Machine polysiloxanes X.
In curable organopolysiloxane X, the R in preferably T1～T3 is the organosiloxane base unit of phenyl (A-2) mol ratio ((A-2) of organosiloxane base unit (B-2) that R is methyl and in T1～T3 / (B-2)) it is 80/20～20/80 (it should be noted that meet the pass of (A-2)+(B-2)=100 System).Wherein, from the dissolubility excellence of this curable organopolysiloxane, can prepare cleaned Glass substrate has capillary (i.e. coating is good) coating liquid of appropriateness, can reduce solidification Time shrinkage stress from the standpoint of, mol ratio ((A-2)/(B-2)) be preferably 75/25～20/80, More preferably 70/30～20/80.
It is (following that R is that organosiloxane base unit (A-2) of phenyl refers to the T1 unit that R is phenyl P-T1), R be the T2 unit (following P-T2) of phenyl and T3 unit that R is phenyl (following P-T3) concept.In following formula P-T1～P-T3, Ph represents phenyl.
P-T1:Ph-Si (-OX)2O1/2
P-T2:Ph-Si (-OX) O2/2
P-T3:Ph-SiO3/2
Therefore, the content of above-mentioned organosiloxane base unit (A-2) refers to the unit that above-mentioned P-T1 represents The total amount of the content of unit that represents of content, the content of unit that represents of above-mentioned P-T2 and above-mentioned P-T3.
It addition, organosiloxane base unit (B-2) that R is methyl refers to the T1 unit that R is methyl (following M-T1), R be the T2 unit (following M-T2) of methyl and T3 unit that R is methyl (with Under M-T3) concept.In following formula M-T1～M-T3, Me represents methyl.
M-T1:Me-Si (-OX)2O1/2
M-T2:Me-Si (-OX) O2/2
M-T3:Me-SiO3/2
Therefore, the content of above-mentioned organosiloxane base unit (B-2) refers to the unit that above-mentioned M-T1 represents The content of unit that represents of content, the content of unit that represents of above-mentioned M-T2 and above-mentioned M-T3 total Amount.
Curable organopolysiloxane (the most above-mentioned curable organopolysiloxane X) is preferably with as follows Ratio comprise the organosiloxane base unit that above-mentioned T1～T3 represents: (rub with the ratio of the number of unit You measure) meter, T1:T2:T3=0～5:20～50:50～80 (wherein, meets T1+T2+T3=100 Relation.).During for above-mentioned scope, it is possible to more easily glass substrate 16 is peeled off.Above-mentioned T1:T2: The ratio of T3 is in other words: the ratio of T1 unit be the ratio of 0～5 mole of %, T2 unit be 20～50 to rub Your ratio of %, T3 unit is 50～80 moles of %.
From the warpage that glass substrate 16 easily can be peeled off, can make glass laminate 10 little in terms of examine Consider, it is preferred that (A-2) unit in curable organopolysiloxane X and the ratio of (B-2) unit ((A-2)/(B-2)) is 80/20～20/80 and the ratio (mole) of number with T1～T3 unit Meter T1:T2:T3=0～5:20～50:50～80.
During it should be noted that use curable organopolysiloxane X-shaped to become silicone resin layer, according to The difference of condition of cure, the methyl in T1～T3, phenyl can depart from and form Q unit sometimes.
Number for curable organopolysiloxane (the most above-mentioned curable organopolysiloxane X) is equal Molecular weight, excellent from the dissolubility of curable organopolysiloxane, few organic of foreign body defect can be made Silicone layer 14 or from the standpoint of can more easily being peeled off by glass substrate 16, it is (solidifying based on GPC Glue penetration chromatograph) measure the number-average molecular weight of polystyrene conversion obtained be preferably 500～2000, more excellent Elect 600～2000, more preferably 800～1800 as.
It addition, for curable organopolysiloxane (the most above-mentioned curable organopolysiloxane X) Matter average molecular weight/number-average molecular weight, excellent from the dissolubility of curable organopolysiloxane, can manufacture Silicone resin layer 14 that foreign body defect is few or can more easily the aspect that glass substrate 16 is peeled off be examined Consider, preferably 1.00～2.00, more preferably 1.00～1.70, more preferably 1.00～1.50.
The molecular weight of curable organopolysiloxane (the most above-mentioned curable organopolysiloxane X) Regulation can be carried out by controlling reaction condition.Such as, solvent during regulation manufacture curable oligomer Amount, when improving the concentration of water-disintegrable organic silane compound, obtains high molecular thing, when reducing concentration, Obtain low-molecular-weight thing.
The shape of curable organopolysiloxane (the most above-mentioned curable organopolysiloxane X) does not has It is particularly limited to, can be granular.Add curable organopolysiloxane i.e., in a solvent (especially to go up State curable organopolysiloxane X) time, can be presented in microgranule.
In this case, the curable organopolysiloxane utilizing dynamic light scattering method to record (is especially gone up State curable organopolysiloxane X) particle diameter be not particularly limited, from manufacturing, foreign body defect is few This silicone resin layer or from the standpoint of can more easily being peeled off by glass substrate 16, is preferably 0.5～100nm, 0.5nm it is more preferably less than 40nm.
It should be noted that as the assay method of above-mentioned dynamic light scattering method, with at PEGMEA solution (propylene glycol-1-monomethyl ether-2-acetas) is the mode of 20 mass % allocates the organic poly-silica of curable Alkane (the most above-mentioned curable organopolysiloxane X) makes sample, uses high concentration particle size analyzer (manufacture of big Electronics Co., Ltd, FPAR-1000), obtains rectangular histogram mean diameter (D50), makees For particle diameter.
The manufacture method of above-mentioned silicone resin layer 14 is not particularly limited, and can use known method. Manufacture method as silicone resin layer 14, it is preferred that as described later, is supporting shape on base material 12 One-tenth can become the layer of the curable organopolysiloxane of above-mentioned organic siliconresin, makes the organic poly-silicon of this curable Oxygen alkane crosslinking curing, thus form silicone resin layer 14.In order to support formation curable on base material 12 The layer of organopolysiloxane, it is preferred that make curable organopolysiloxane be dissolved in solvent and obtain To solution (comprising the compositions of curable organopolysiloxane), this solution is coated on support base material On 12, form the layer of solution, then, solvent is removed, form the layer of curable organopolysiloxane. By the regulation etc. of solution concentration, it is possible to control the thickness of the layer of curable organopolysiloxane.Wherein, From the standpoint of the control of treatability excellence, the thickness of silicone resin layer 14 is easier, comprise solidification The content of the curable organopolysiloxane in the compositions of property organopolysiloxane is total relative to compositions Quality, preferably 1～100 mass %, more preferably 1～50 mass %.
As solvent, as long as curable organopolysiloxane can be made under working environment the most molten Solve and can easily volatilize the solvent removed, and is just not particularly limited.Specifically can exemplify such as: Butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetas etc..
It addition, from the side that can improve curable organopolysiloxane stability in the composition further Face considers, the preferably pH in control composition.Known usual silanol group can stable existence pH tool There is certain limit, near neutral, readily facilitate gelation, in acidic side (pH2～4) or alkalescence (pH11～14) more stably exists in side.From improve further curable organopolysiloxane stability, And from the standpoint of curing catalysts when solidifying as curable organopolysiloxane works, the control of pH System is preferably used acid.As adding acid, can list: hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, nitrous The mineral acids such as acid, perchloric acid, sulfamic acid；Formic acid, acetic acid, propanoic acid, butanoic acid, oxalic acid, succinic acid, The organic acid, preferably acetic acid such as maleic acid, lactic acid, p-methyl benzenesulfonic acid.Poly-silica organic relative to curable Alkane compositions 100 mass parts, the usage amount of acid is preferably 0.1～50 mass parts, particularly preferably 1～20 matter Amount part.
And then, examine in terms of raising curable organopolysiloxane stability in the composition further Consider, it is also possible to add boiling point than the coating higher alcohol of solvent.The kind of the alcohol used is not particularly limited, Can list: n-butyl alcohol, 1-methoxy-2-propanol, 2-amylalcohol, 3-methyl-1-butanol, 1-amylalcohol, Diacetone alcohol, 2-(2-ethoxy ethoxy) ethanol etc..Wherein, from curable organopolysiloxane From the standpoint of favorable solubility, preferably 1-methoxy-2-propanol, diacetone alcohol, 2-(2-ethyoxyl second Epoxide) ethanol.
It addition, for the purpose improving the coating to base material, it is also possible to comprise defoamer, viscosity adjustment Agent, for the purpose improving the adaptation to base material, it is also possible to contain adaptation imparting agent etc. further and add Add agent, for improving coating and the purpose of the flatness of film obtained, it is also possible to compounding levelling agent. For the compounding amount of these additives, relative to curable organopolysiloxane 100 mass parts, respectively Composition is respectively the amount of 0.01～2 mass parts.It addition, within the scope without prejudice to the object of the present invention, it is possible to To add filler etc..
It should be noted that for using curable organopolysiloxane to form the step of silicone resin layer Suddenly, will be described in detail later.
[glass laminate and manufacture method thereof]
The glass laminate 10 of the present invention is as it has been described above, support base material 12, glass substrate 16 for having and deposit The duplexer of the silicone resin layer 14 being between them.
The manufacture method of the glass laminate 10 of the present invention is not particularly limited, in order to obtain peel strength X duplexer that () is higher than peel strength (y), is preferably supporting formation organosilicon tree on base material 12 surface The method of lipid layer 14.Following method: curable organopolysiloxane is coated on a support group The surface of material 12, forms silicone resin layer 14 supporting, then, in organosilicon tree on base material 12 surface The organic siliconresin surface layer laminated glass substrate 16 of lipid layer 14, thus manufacture glass laminate 10.
Think make curable organopolysiloxane support base material 12 surface cure time, during by curing reaction With support the interaction on base material 12 surface and bonding, organic siliconresin and the stripping supporting base material 12 surface Intensity uprises.Therefore, even if glass substrate 16 is formed by identical material with supporting base material 12, it is also possible to Silicone resin layer 14 is made to there are differences with peel strength between the two.
Hereinafter, the layer of curable organopolysiloxane will be formed on the surface supporting base material 12, in a support group The operation forming silicone resin layer 14 on material 12 surface is referred to as resin bed formation process, will be in organosilicon tree The organic siliconresin surface layer laminated glass substrate 16 of lipid layer 14 and form the operation of glass laminate 10 and be referred to as layer Folded operation, is described in detail to the step of each operation.
(resin bed formation process)
In resin bed formation process, form curable organopolysiloxane on the surface supporting base material 12 Layer, form silicone resin layer 14 on base material 12 surface supporting.
In order to support the layer forming curable organopolysiloxane on base material 12, it is preferred that make The coating composition that curable organopolysiloxane is dissolved in solvent and obtains (is equivalent to above-mentioned comprising admittedly The compositions of the property changed organopolysiloxane), said composition is coated on and supports formation solution on base material 12 Layer, then implements cured, forms silicone resin layer 14.
Do not have supporting the method for the compositions that coating comprises curable organopolysiloxane on base material 12 surface It is particularly limited to, it is possible to use known method.Such as can list: spraying process, die coating method, rotation Coating, Dipcoat method, rolling method, stick coating method, silk screen print method, gravure coating process etc..
Then, make the curable organopolysiloxane on support base material 12 solidify, form silicone resin layer 14.More specifically, as shown in (A) of Fig. 2, in this operation, supporting at least the one of base material 12 Silicone resin layer 14 is formed on individual surface.
The method of solidification is not particularly limited, and is generally processed by heat cure and carries out.
The temperature conditions of heat cure is improving the thermostability of silicone resin layer 14, can control as described above It is not particularly limited, preferably in the range of peel strength (y) after system and glass substrate 16 stacking 150～550 DEG C, more preferably 200～450 DEG C.It addition, be preferably generally heat time heating time 10～300 minutes, More preferably 20～120 minutes.It should be noted that heating condition can also change temperature conditions and sublevel Section is implemented.
By being set as the scope of said temperature scope and heat time heating time, it is possible to control T1 unit, T2 unit And T3 unit and the generation ratio of Q unit that easily generated by the heating of more than 250 DEG C.
It should be noted that in heat cure processes, preferably carrying out the laggard of precuring (precure) Row solidifies (main solidification) and makes curable organopolysiloxane solidify.By carrying out precuring, it is possible to Silicone resin layer 14 to excellent heat resistance.The removal of precuring the most and then solvent and carry out, should In the case of, from layer, remove solvent and form the operation of the layer of cross-linking agent and carry out the operation of precuring and do not make Distinguish especially.The removal of solvent is preferably heated to more than 100 DEG C and carries out, can be by being heated to 150 DEG C Carry out precuring above and and then.The removal of solvent and carry out the temperature of precuring and heat time heating time is preferred It is 100～420 DEG C, 5～60 minutes, more preferably 150～300 DEG C, 10～30 minutes.When being less than 420 DEG C, The silicone resin layer being easily peeled off can be obtained.
(lamination process)
Lamination process is following operation: at the organic siliconresin obtained by above-mentioned resin bed formation process Laminated glass substrate 16 on the organic siliconresin face of layer 14, is possessed the layer of support base material 12 successively, is had The glass laminate 10 of the layer of machine silicone layer 14 and glass substrate 16.More specifically, such as (B) of Fig. 2 Shown in, being in silicone resin layer 14 the surface 14a of opposition side with support base material 12 side and having the 1st 1st interarea 16a of the glass substrate 16 of interarea 16a and the 2nd interarea 16b is as lamination surface, by organosilicon tree Lipid layer 14 and glass substrate 16 stacking, obtain glass laminate 10.
The method that glass substrate 16 is layered on silicone resin layer 14 is not particularly limited, can use Known method.
Such as can list under atmospheric pressure environment overlapping glass base on the surface of silicone resin layer 14 The method of plate 16.It should be noted that as required, it is also possible on the surface of silicone resin layer 14 After overlapping glass substrate 16, roller, press is used to make glass substrate 16 be crimped on silicone resin layer 14. By utilizing roller or press to crimp, it is easier removal and is mixed into silicone resin layer 14 and glass base Bubble between the layer of plate 16, so preferably.
When utilizing vacuum layer platen press, Vacuum Pressure preparation method to crimp, it is possible to suppression bubble be mixed into, guarantee good Good is closely sealed, so more preferably.By crimping under vacuo, even if remaining small bubble, Bubble also will not be grown up because of heating, the advantage also with the deformation defect not being easily caused glass substrate 16.
During laminated glass substrate 16, the preferably surface to the glass substrate 16 contacted with silicone resin layer 14 Fully clean, and stacking in the environment of cleanliness factor height.Cleanliness factor is the highest, putting down of glass substrate 16 Smooth property is the best, so preferably.
It should be noted that after laminated glass substrate 16, as required, it is also possible to carry out pre-anneal treatment (heat treated).By carrying out this pre-anneal treatment, the glass substrate 16 of stacking is to silicone resin layer The adaptation of 14 improves, it is possible to obtain the peel strength (y) being suitable for, when component formation process described later Being not susceptible to the position skew etc. of electronic device member, the productivity ratio of electronic equipment improves.
The condition of pre-anneal treatment suitably can select according to the kind of the silicone resin layer 14 used Optimal condition, from the peel strength (y) made between glass substrate 16 and silicone resin layer 14 more From the standpoint of He Shi, preferably more than 300 DEG C (preferably 300～400 DEG C) carry out more than 5 minutes (excellent Select 5～30 minutes) heat treated.
It should be noted that make the peel strength of the 1st interarea to glass substrate 16 and to supporting base material 12 The formation of silicone resin layer 14 that there are differences of the peel strength of the 1st interarea be not limited to above-mentioned side Method.
Such as, propping up of the material that the adaptation to silicone resin layer 14 surface is higher than glass substrate 16 is used During support group material 12, above-mentioned curable organopolysiloxane can be made to solidify on any fissility surface and make Make the thin film of organic siliconresin, make this thin film be mixed in glass substrate 16 and support between base material 12, simultaneously Carry out stacking.
It addition, the cementability being solidified by curable organopolysiloxane and bringing is of a sufficiently low to glass substrate 16 And described cementability to support base material 12 sufficiently high in the case of, can be at glass substrate 16 with support base material The chien shih cross-linking agent of 12 is solidified to form silicone resin layer 14.
And then, even supporting the situation that base material 12 is formed by the glass material as glass substrate 16, Can also implement to improve the process of the cementability supporting base material 12 surface and improve silicone resin layer 14 Peel strength.For example, it is possible to illustrate following method: the raising chemistry of silane coupler etc is fixed The increase surface active groups of the chemical method (prime treatment) of power, flame (flame) process etc Physical method, blasting treatment etc by increase surface roughness and increase the mechanical processing method of attachment Deng.
(glass laminate)
The glass laminate 10 of the 1st embodiment of the present invention may be used for various uses, such as, can arrange Enumerate manufacture display device panel described later, PV, thin-film secondary battery, be formed with circuit on surface The purposes etc. of the electronic units such as semiconductor crystal wafer.It should be noted that in this purposes, glass laminate 10 Usually expose (such as more than 1 hour) under hot conditions (such as more than 450 DEG C).
Here, display device panel includes LCD, OLED, Electronic Paper, plasma scope face Plate, field emission panel, quantum dot LED panel, MEMS (microelectromechanical systems, Micro Electro Mechanical Systems) shutter face plate etc..
＜ the 2nd embodiment ＞
Fig. 3 is the schematic section of the 2nd embodiment of the glass laminate of the present invention.
As it is shown on figure 3, glass laminate 100 be have support the layer of base material 12, the layer of glass substrate 16 and The duplexer of the silicone resin layer 14 being present between them.
Glass laminate 100 shown in Fig. 3 is different from the glass laminate 10 shown in above-mentioned Fig. 1, organosilicon Resin bed 14 is fixed on glass substrate 16, and the glass substrate 20 of tape tree lipid layer is with the glass of tape tree lipid layer Silicone resin layer 14 in substrate 20 is directly (close with the mode strippingly stacking that support base material 12 connects Close) supporting on base material 12.This is fixing and strippable closely sealed in peel strength (that is, needed for stripping Stress) aspect there are differences, and fixing refers to that peel strength is higher compared with closely sealed.That is, glass laminated In body 100, silicone resin layer 14 compares silicone resin layer with the peel strength at the interface of glass substrate 16 14 is high with the peel strength at the interface supporting base material 12.
More specifically, glass substrate 16 has peel strength (z) with the interface of silicone resin layer 14, The peeling direction of peel strength (z) it is applied above at the interface of glass substrate 16 with silicone resin layer 14 Stress time, the interface peel of glass substrate the 16 and the 1st silicone resin layer 14.Silicone resin layer 14 With the interface supporting base material 12, there is peel strength (w), to silicone resin layer 14 and support base material 12 The stress of the interface peeling direction that is applied above peel strength (w) time, silicone resin layer 14 with The interface peel of support group material 12.
In glass laminate 100, above-mentioned peel strength (z) is higher than above-mentioned peel strength (w).Cause This, apply when supporting the stress in the direction peeled off with glass substrate 16 of base material 12 to glass laminate 100, The glass laminate 100 of the present invention, at silicone resin layer 14 and the interface peel supporting base material 12, separates Glass substrate 20 and support base material 12 for tape tree lipid layer.
Peel strength (z) is preferably sufficiently high compared with peel strength (w).Improve peel strength (z) Refer to, improve the silicone resin layer 14 adhesive force to glass substrate 16, and, the most also Adhesive force of a relatively high compared with the adhesive force to support base material 12 can be maintained.
In order to improve the silicone resin layer 14 adhesive force to glass substrate 16, above-mentioned curable is preferably made to have Machine polysiloxanes cross-links on glass substrate 16 and is solidified to form silicone resin layer 14.Utilize crosslinking curing Time bonding force, it is possible to form the silicone resin layer 14 that is combined with high-bond with glass substrate 16.
On the other hand, the organic siliconresin after crosslinking curing is above-mentioned to the adhesion generally ratio supporting base material 12 The adhesion produced during crosslinking curing is low.Therefore, by forming silicone resin layer on glass substrate 16 14, then the surface stacking at silicone resin layer 14 supports base material 12, it is possible to manufacture glass laminate 100。
The each layer constituting glass laminate 100 (supports base material 12, glass substrate 16, silicone resin layer 14) identical with each layer implication of above-mentioned composition glass laminate 10, here omit the description.
Wherein, the surface roughness Ra on the surface supporting base material 12 side of silicone resin layer 14 is the most especially Limit, from the standpoint of the stackability of glass substrate 16 and fissility are more excellent, preferably 0.1～20nm, More preferably 0.1～10nm.
It should be noted that as the assay method of surface roughness Ra, based on JIS B 0601-2001 Carry out, on the value that the Ra recording the point more than at any 5 carries out arithmetic average and obtains is equivalent to State surface roughness Ra.
The manufacture method of glass laminate 100 is not particularly limited, in the manufacture of above-mentioned glass laminate 10 In method, support base material 12 by using glass substrate 16 to replace, use support base material 12 to replace glass base Plate 16, it is possible to manufacture desired glass laminate 100.More specifically, glass substrate 16 is formed Silicone resin layer 14, then on silicone resin layer 14, stacking supports base material 12, it is possible to manufacture glass Duplexer 100.
[glass substrate of band member and manufacture method thereof]
In the present invention, use above-mentioned glass laminate (glass laminate 10 or glass laminate 100), Electronic equipment can be manufactured.
Hereinafter, the mode using above-mentioned glass laminate 10 is described in detail.
By using glass laminate 10, the band structure comprising glass substrate and electronic device member can be manufactured The glass substrate (glass substrate of having electronic equipment component) of part.
The manufacture method of the glass substrate of this band member is not particularly limited, excellent from the productivity ratio of electronic equipment From the standpoint of different, the method being preferably as follows: form electricity on the glass substrate in above-mentioned glass laminate Subset component, manufactures the duplexer of having electronic equipment component, with the glass base of silicone resin layer As release surface inside interface, plate side or resin bed, divide the duplexer of the having electronic equipment component obtained From the glass substrate and the support base material of tape tree lipid layer that become band member.It should be noted that more preferably basis Need being cleaned of release surface of then glass substrate to band member.
Hereinafter, manufacture forming electronic device member on the glass substrate in above-mentioned glass laminate The operation of the duplexer of having electronic equipment component is referred to as component formation process, by with silicone resin layer Interface, glass substrate side, as release surface, is separated into band member by the duplexer of having electronic equipment component The operation supporting base material of glass substrate and tape tree lipid layer is referred to as separation circuit, by the glass base to band member The operation of being cleaned of release surface of plate is referred to as cleaning treatment process.It should be noted that as above institute Stating, cleaning treatment process is the optional process steps implemented as desired.
Hereinafter, material and the step used in each operation is described in detail.
(component formation process)
Component formation process is the glass substrate in the glass laminate 10 obtained in above-mentioned lamination process The operation of electronic device member is formed on 16.More specifically, as shown in (C) of Fig. 2, at glass 2nd interarea 16b (exposing surface) of substrate 16 is upper forms electronic device member 22, obtains having electronic and sets The duplexer 24 of standby component.
First, the electronic device member 22 used in this operation is described in detail, thereafter to operation Step be described in detail.
(electronic device member (functional element))
Electronic device member 22 is formed on the glass substrate 16 in glass laminate 10, is to constitute electronics At least one of component of equipment.More specifically, as electronic device member 22, can enumerate Go out to be formed with on display device panel, solaode, thin-film secondary battery or surface the half of circuit The component that uses in the electronic units such as semiconductor wafer etc. (such as display device component, used for solar batteries Component, thin-film secondary battery component, electronic component-use circuit).
Such as, as component used for solar batteries, during for silicon type, the stannum oxide etc. of positive pole can be listed Transparency electrode, with the silicon layer that p layer/i layer/n-layer represents and the metal etc. of negative pole, furthermore it is also possible to enumerate Go out the various components etc. corresponding with compound type, dye sensitization type, quantum point type etc..
It addition, as thin-film secondary battery component, during for type lithium ion, positive pole can be listed and bears The transparency electrodes such as the metal of pole or metal-oxide, the lithium compound of dielectric substrate, the metal of current collection layer, As the resin etc. of sealant, furthermore it is also possible to list and ni-mh type, polymer-type, pottery electrolysis The various components etc. that matter type etc. are corresponding.
It addition, as electronic component-use circuit, during for CCD, CMOS, conductive part can be listed Metal, the silicon oxide of insulation division, silicon nitride etc., furthermore it is also possible to list and pressure transducer/add The various sensor such as velocity sensor, rigidity printed base plate, flexible printing substrate, rigid-flexible printed base plate etc. Corresponding various components etc..
(step of operation)
The manufacture method of the duplexer 24 of above-mentioned having electronic equipment component is not particularly limited, can basis The kind of the member of formation of electronic device member, utilizes existing known method in glass laminate 10 Electronic device member 22 is formed on 2nd interarea 16b surface of glass substrate 16.
It should be noted that electronic device member 22 may not be the 2nd interarea at glass substrate 16 Whole (hereinafter referred to as " whole components ") of the component ultimately formed on 16b, but the one of whole component Partly (hereinafter referred to as " partial component ").The band portion structure that can also will peel off from silicone resin layer 14 The glass substrate that the glass substrate of part is formed with whole components by operation thereafter (is equivalent to electricity described later Subset).
It addition, for from silicone resin layer 14 stripping glass substrate with whole components, can be at it Release surface (the 1st interarea 16a) forms other electronic device member.Furthermore it is also possible to assembled belt is whole The duplexer of component, then peels off support base material 12 from the duplexer with whole components, manufactures electronics and sets Standby.And then, it is possible to use 2 duplexers with whole components assemble, thereafter, from band all 2 support base materials 12 are peeled off by the duplexer of component, manufacture the glass of the band member with 2 glass substrates Substrate.
Such as, in case of manufacturing OLED, for the glass substrate 16 in glass laminate 10 It is on the surface of opposition side with silicone resin layer 14 side and (is equivalent to the 2nd interarea of glass substrate 16 16b) form organic EL structure, carry out following various layers and formed, process: formation transparency electrode, Hole injection layer/hole transmission layer/luminescent layer/electronics it is deposited with further on the face define transparency electrode Transport layers etc., the backplate that formed, use package board are packaged.Formed as these layers, process, Specifically can list such as film forming process, vapor deposition treatment, the bonding process etc. of package board.
It addition, such as, when manufacturing TFT-LCD, have such as inferior various operations: TFT formation process, On the 2nd interarea 16b of the glass substrate 16 of glass laminate 10, use anti-corrosion liquid to utilize CVD and The metal film of the membrane formation process formation that sputtering method etc. are general and metal oxide film etc. carry out pattern formation, are formed thin Film transistor (TFT)；CF formation process, other glass laminate 10 glass substrate 16 the 2nd On interarea 16b, use anti-corrosion liquid to form pattern, form color filter (CF)；Bonding process, will be The duplexer of the band TFT obtained in TFT formation process and the layer of band CF obtained in CF formation process Stack stacking.
In TFT formation process, CF formation process, use known photoetching technique, etching technique etc., 2nd interarea 16b of glass substrate 16 is formed TFT, CF.Now, the coating formed as pattern Liquid, uses anti-corrosion liquid.
It should be noted that before forming TFT, CF, as required, can be to glass substrate 16 2nd interarea 16b is carried out.As cleaning method, it is possible to use known dry clean, wet-cleaned.
In bonding process, the thin film transistor (TFT) of the duplexer of band TFT is made to form the duplexer in face and band CF Color filter formed face in opposite directions, use sealant (such as unit (cell) formation ultraviolet hardening Sealant) fit.Thereafter, to the unit formed by the duplexer of band TFT and the duplexer of band CF Interior injection liquid crystal material.As the method injecting liquid crystal material, such as, decompression injection method, dropping is had to inject Method.
(separation circuit)
Separation circuit is following operation: using the interface of silicone resin layer 14 and glass substrate 16 as stripping From face, the duplexer 24 of the having electronic equipment component obtained in above-mentioned component formation process it is separated into It is laminated with glass substrate 16 (glass substrate of band member) and the organosilicon of electronic device member 22 Resin bed 14 and support base material 12, obtain comprising electronic device member 22 and the band member of glass substrate 16 Glass substrate 26.
Electronic device member on glass substrate 16 during stripping 22 required whole constitutes structure for being formed During part a part of, it is also possible to form remaining member of formation after isolation on glass substrate 16.
The method glass substrate 26 of band member and the support base material 18 of tape tree lipid layer peeled off is the most especially Limit.Specifically, for example, it is possible to insert cutting edge of a knife or a sword to the interface of glass substrate 16 and silicone resin layer 14 Profit cutter shape object and give stripping starting point after, blow water and compressed-air actuated fluid-mixing etc. and carry out Peel off.Preferably, so that the support base material 12 of the duplexer 24 of having electronic equipment component be upside, Electronic device member 22 side is that the mode of downside is arranged on platform, makes electronic device member 22 side true Suction invests and (carries out successively when being laminated with support base material on two sides), in this condition, first on platform Cutter is made to invade glass substrate 16-silicone resin layer 14 interface.Then, adsorb with multiple vacuum cups Support base material 12 side, make vacuum cup gradually rise successively near the position inserting cutter.Thus, Form air layer at the interface of resin bed 14 and glass substrate 16, and this air layer expands to whole boundary Face, such that it is able to easily peel off the support base material 18 of tape tree lipid layer.
It addition, the support base material 18 of tape tree lipid layer can manufacture the present invention's with new glass substrate stacking Glass laminate 10.
It should be noted that from the duplexer 24 of having electronic equipment component by the glass substrate 26 of band member During separation, by controlling based on ion generator to blow, humidity, it is possible to suppression organosilicon tree further The fragment Electrostatic Absorption of lipid layer 14 is on the glass substrate 26 of band member.
[cleaning treatment process]
Cleaning treatment process is in the glass substrate 26 to the band member obtained in above-mentioned separation circuit The release surface (the 1st interarea 16a) of glass substrate 16 implement to clean the operation of process.Should by enforcement Operation, it is possible to will be attached to the organic siliconresin of release surface, be attached to silicone resin layer, release surface The sheet metal that produces in above-mentioned component formation process, the Impurity removal such as dust, it is possible to maintain the clear of release surface Clean property.Its result, is attached to the viscous of the phase difference film in the release surface of glass substrate 16, polarizing film etc. Conjunction improves.
For the method cleaning process, it is attached to the resin of release surface, dust etc. as long as can remove, its Method is just not particularly limited.Such as can list: the method that makes attachment thermally decompose, pass through etc. from Son irradiates or light irradiates (such as UV treatment with irradiation) by the method for the Impurity removal in release surface, use Solvent is carried out the method etc. processed.
The manufacture method of the glass substrate 26 of above-mentioned band member is suitable for mobile phone, the such mobile terminal of PDA The manufacture of the compact display apparatus of middle use.Display device is mainly LCD or OLED, as LCD, Including TN type, STN type, FE type, TFT type, mim type, IPS type, VA type etc..Substantially in nothing Source is driving, can apply in any display device of active-drive.
As the glass substrate 26 of the band member utilizing said method to prepare, can list and there is glass base The display device panel of plate and display device component, there is glass substrate and component used for solar batteries Solaode, there is glass substrate and the thin-film secondary battery of thin-film secondary battery component, have Glass substrate and the electronic unit etc. of electronic device member.As display device panel, including liquid crystal Panel, organic EL panel, plasm display panel, field emission panel etc..
Above the mode using glass laminate 10 is described in detail, it is possible to use glass laminated Body 100, manufactures electronic equipment according to step same as described above.
It should be noted that in the case of using glass laminate 100, when above-mentioned separation circuit, with The interface of support base material 12 and silicone resin layer 14, as release surface, is separated into support base material 12 and comprises Silicone resin layer 14, glass substrate 16 and the electronic equipment of electronic device member 22.
Embodiment
Hereinafter, utilize embodiment etc. that the present invention is specifically described, but the present invention is not limited to these examples Son.It addition, in this manufacture example, carry out the organic poly-silicon of curable according to project shown below and method The evaluation of oxygen alkane.
(1) parsing (ratio of T unit) of the bond styles of the silicon atom in curable organopolysiloxane
Use NMR analysis devices (solution29Si-NMR:JEOL RESONANCE Co., Ltd. Manufacture, ECP400) obtain the ratio of T1～T3.
The ratio of T1～T3 is by solution29The peak area ratio of Si-NMR is obtained respectively.Condition determination is set as: arteries and veins Rush width 20 microsecond, 30 seconds waiting time of pulse repetition, cumulative frequency 256scan.First is used to solvent Benzo is deployed in the solution of concentration 30wt% the Cr (acac) adding the 0.1wt% as relaxation reagent3。 For the benchmark of chemical shift, using the peak that derives from TMS as 0ppm.
The integral and calculating scope of each structure is as follows.
T1 (Me yl) :-44～-49ppm, T1 (Ph yl) :-60～-61ppm
T2 (Me yl) :-50～-60ppm, T2 (Ph yl) :-67～-74ppm
T3 (Me yl) :-61～-67ppm, T3 (Ph yl) :-74～-83ppm
(2) % of the phenyl mole in curable organopolysiloxane/methyl mole % (above-mentioned (A-2)/ (B-2)) the parsing of ratio of components
Use NMR analysis devices (solution1H-NMR:JEOL RESONANCE Co., Ltd. system Make, ECP400) obtain phenyl mole %/methyl mole % (above-mentioned (A-2)/(B-2)) ratio of components.
Phenyl mole %/methyl mole % (above-mentioned (A-2)/(B-2)) ratio of components by1The peak of H-NMR Area is obtained respectively.Condition determination is set as: the waiting time 5 that pulse width 6.7 microsecond, pulse repeat Second, cumulative frequency 16scan.Solvent uses deuterochloroform, is deployed into concentration 1wt%.For chemical shift Benchmark, the peak deriving from chloroform is set to 7.26ppm.It addition, derive from each structure1H-NMR Chemical shift as follows.
A-2 (Ph yl): 8.2～6.4ppm
B-2 (Me yl): 0.6～-0.7ppm
(3) number-average molecular weight Mn, matter average molecular weight Mw and the evaluation of dispersion Mw/Mn
Utilize gel permeation chromatography (GPC, HLC8220, RI detection of TOSOH Co., Ltd's manufacture, color Spectrum post: TSK-GEL SuperHZ, eluent: oxolane) obtain.
(4) evaluation of the particle diameter that dynamic light scattering method carries out is utilized
Curable organopolysiloxane is made the PGMEA (propylene glycol-1-monomethyl ether-2-of 20 mass % Acetas) solution, use high concentration particle size analyzer (manufacture of big Electronics Co., Ltd, FPAR-1000), Obtain rectangular histogram mean diameter (D50), as particle diameter.
In below example 1～10, comparative example 1,2, as glass substrate, use by alkali-free borosilicate Glass plate (long 274mm, wide 274mm, thickness of slab 0.2mm, the linear expansion coefficient that acid glass is formed 38×10-7/ DEG C, Asahi Glass Co., Ltd manufacture trade name " AN100 ").It addition, as gripper shoe, Use glass plate (long 274mm, wide 274mm, the thickness of slab formed by alkali-free pyrex equally 0.4mm, linear expansion coefficient 38 × 10-7/ DEG C, Asahi Glass Co., Ltd manufacture trade name " AN100 ").
＜ manufactures example 1: the manufacture ＞ of curable organopolysiloxane
In the reaction vessel possessing reflux condensing tube, Dropping funnel and blender add sodium carbonate (12.7g, 0.12 mole) and water (80mL), it is stirred, adds methyl iso-butyl ketone (MIBK) (80mL) the most further, Obtain reaction solution.Then, to reaction solution, methyl trichlorosilane was dripped from Dropping funnel with 30 minutes (7.5g, 0.05 mole) and phenyl trichlorosilane (10.6g, 0.05 mole).At this moment, reaction solution is made Temperature rise to 40 DEG C.Then, after completion of dropwise addition, reaction vessel is immersed in the oil bath of 60 DEG C, Heated and stirred 24 hours.After reaction terminates, organic facies is carried out till rinse water becomes neutrality, Then, use desiccant that organic facies is dried.Then desiccant is removed, afterwards, by decompression Solvent distillation being removed, carry out night vacuum drying further, (curable is organic to obtain white solid Polysiloxanes (U1)).
＜ manufactures example 2～8 ＞
For curable organopolysiloxane (U2)～(U8), operate, with table 1 as manufacturing example 1 Shown ratio of components manufacture.It should be noted that for (U4), the response time was adjusted by 24 hours It is 1 hour, for (U6), by the response time by within 24 hours, being adjusted to 3 hours, in addition, according to Step manufacture as manufacturing example 1.And then, (U5) is to make 50 mass % after manufacturing (U4) Methanol solution, add relative to the acetic acid that solid constituent is 2 mass % after, again by decompression will The solid of the white that solvent distillation is removed and obtained.
It should be noted that in table 1 below, " phenyl mole %/methyl mole % " hurdle represents To curable organopolysiloxane in, the organosiloxane base unit that R is phenyl in T1～T3 with R in T1～T3 is the mol ratio of the organosiloxane base unit of methyl.
It addition, " ratio of T unit " hurdle represents T1～T3 in the curable organopolysiloxane obtained The ratio (mole %) of number of each unit, with the summation of the ratio of the number of T1～T3 each unit for 100 Mode represent.
" particle diameter " hurdle is the grain of the curable organopolysiloxane utilizing above-mentioned dynamic light scattering method to record Footpath, " ＜ 40 " refers to that particle diameter is less than 40nm, and " ＞ 100 " refers to that particle diameter is more than 100nm.
It should be noted that the content of above-mentioned each unit according to29Si-NMR、1H-NMR calculates.
[table 1]
＜ embodiment 1 ＞
Make the curable organopolysiloxane (U1) obtained be dissolved in PEGMEA, make and comprise solidification Property organopolysiloxane (U1) fraction (solid component concentration: 40 mass %) (need explanation Be, curable organopolysiloxane presented in the microgranule of particle diameter shown in table 1 in fraction.).
After supporting base material pure water cleaning, then carry out UV cleaning, thus clean.
Then, on the 1st interarea supporting base material, with long 278mm and the size of wide 278mm, pass through Spin coater coating comprises fraction (the coated weight 30g/m of curable organopolysiloxane (U1)2)。
Then, gains are heating and curing 30 minutes at 350 DEG C in an atmosphere, are supporting the 1st of base material Interarea forms the silicone resin layer of thickness 2.8 μm, the body A that is supported (the support base material of tape tree lipid layer).
Then, make supporter A silicone resin layer fissility surface with and this silicone resin layer The glass substrate (" AN100 " of equivalently-sized thickness 0.2mm.Asahi Glass Co., Ltd manufacture) the 1st Interarea in opposite directions, at room temperature, under atmospheric pressure, utilizes stacked laminator in the way of the center of gravity coincidence of two substrates Two substrates is overlapped, obtains glass laminate S1.
It should be noted that glass laminate S1 obtained is equivalent to the glass laminate 10 of above-mentioned Fig. 1, In glass laminate S1, support the peel strength (x) of the layer of base material and the interface of silicone resin layer Higher with the peel strength (y) at the interface of glass substrate than silicone resin layer.
Hereinafter, implement to employ the following mensuration of glass laminate S1 obtained.Following evaluation result Collect and be shown in table 1 described later.
[fissility evaluation]
Cut the square sample of 50mm from glass laminate S1, this sample is placed in and is heated to 450 DEG C In the hot-air oven of (under nitrogen atmosphere), take out after placing 60 minutes.Then, glass laminate is made 2nd interarea vac sorb of the glass substrate of S1 is in platform, then, to the 1 of glass laminate S1 corner The stainless steel cutter of interface inserting thickness 0.1mm of glass substrate and silicone resin layer, above-mentioned Rising of stripping is given between 1st interarea and the fissility surface of above-mentioned silicone resin layer of glass substrate Point.Afterwards, the support base material of multiple vacuum cup absorption glass laminate S1 is utilized with 90mm spacing 2nd interarea, then starts to make sucker raise successively, thus by glass base from the sucker near above-mentioned corner 1st interarea of plate and the fissility sur-face peeling of silicone resin layer.
Even if by the above results it has been confirmed that after high-temperature heating treatment, glass substrate also is able to peel off.
It should be noted that the major part of silicone resin layer is together divided from glass substrate with supporting base material From, by this result it has been confirmed that support peel strength (x) ratio of the layer of base material and the interface of resin bed Silicone resin layer is high with the peel strength (y) at the interface of glass substrate.
[Evaluation of Heat Tolerance]
Cut the square sample of 50mm from glass laminate S1, this sample is positioned in and is heated to 450 DEG C In the hot-air oven of (under nitrogen atmosphere), take out after placing 60 minutes, evaluate and whether confirm in sample To foaming or coloring.
＜ embodiment 2～10 ＞
Use respectively and comprise curable organopolysiloxane (U2)～the liquid of (U6) shown in table 2 below Shape thing replaces the fraction comprising curable organopolysiloxane (U1), and changes heat cure process bar Part, in addition, according to step same as in Example 1, manufactures glass laminate S2～S10.
Table 2 below shows kind and the solid component concentration etc. of the solvent used when manufacturing fraction. It addition, for embodiment 7 and 8, by heat cure treatment conditions when being heating and curing by " 350 DEG C, 30 points Clock " it is changed to " be heating and curing in an atmosphere at 150 DEG C 30 minutes, the most again at air at 350 DEG C In be heating and curing 60 minutes ".And then, for embodiment 9, by heat cure treatment conditions when being heating and curing It is changed to " be heating and curing in an atmosphere at 150 DEG C 30 minutes, the most again by " 350 DEG C, 30 minutes " It is heating and curing in an atmosphere at 350 DEG C 60 minutes, and then is heating and curing in an atmosphere at 500 DEG C 60 points Clock ".
It should be noted that glass laminate S2 obtained～S10 are equivalent to the glass laminate of above-mentioned Fig. 1 10, in glass laminate S2～S10, support the peel strength of the layer of base material and the interface of silicone resin layer X () is higher with the peel strength (y) at the interface of glass substrate than silicone resin layer.
It addition, use glass laminate S2 that obtains～S10 implements above-mentioned [fissility evaluation] and [thermostability is commented Valency].Result is collected and is shown in table 2.
＜ comparative example 1 ＞
The fraction comprising curable organopolysiloxane (U8) shown in table 2 below is used to replace comprising The fraction of curable organopolysiloxane (U1), in addition, according to step same as in Example 1 Suddenly, the manufacture of glass laminate C1 is carried out.Use glass laminate C1 obtained, implement above-mentioned [stripping Property evaluate] and [Evaluation of Heat Tolerance].Result is collected and is shown in table 2.
＜ comparative example 2 ＞
Use solvent-free addition reaction-type peeling paper organosilicon (manufacture of organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI, business Name of an article KNS-320A) (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI manufactures, commodity for 100 mass parts and platinum group catalyst Name CAT-PL-56) 2 mass parts mixture (U9) replace comprise curable organopolysiloxane (U1) Fraction, in addition, according to step same as in Example 1, manufacture glass laminate C2.Make By glass laminate C2 obtained, implement above-mentioned [fissility evaluation] and [Evaluation of Heat Tolerance].Result is converged Always it is shown in table 2.
It should be noted that the mode of above-mentioned glass laminate C2 is equivalent to the mode that patent documentation 1 is recorded.
In table 2, in " coating evaluation " hurdle, coating is comprised the aqueous of curable organopolysiloxane Thing also can form the situation of silicone resin layer and is designated as "○", will be unable to form silicone resin layer Situation is designated as "×".
It addition, in " fissility evaluation " hurdle, will insert at the interface of glass substrate and silicone resin layer Enter stainless steel cutter and give the moment glass substrate of the starting point of stripping and the big portion of silicone resin layer Divide stripping, easily the information slip that glass substrate is peeled off can be shown as " ◎ ", glass substrate is not had The only starting point by peeling off just is peeled off but the information slip that glass substrate is peeled off can be shown as "○", will Glass substrate cannot be peeled off or the information slip of glass substrate breakage is shown as "×".
And then, in " Evaluation of Heat Tolerance " hurdle, the situation that there is not " coloring " " foaming " represents It is shown as " having " for "None", the information slip that there is " coloring " " foaming ".
It addition, in table 2, show in " silicone resin layer " hurdle by based on29Si-NMR obtains The T3 unit that calculates of peak area ratio and mole % of Q unit.
It should be noted that in this manufacture example and comparative example, enter according to project shown below and method The parsing of row silicone resin layer.
(1) parsing of the bond styles of the silicon atom of silicone resin layer
Use NMR analysis devices (solid29Si-NMR:JEOL RESONANCE Co., Ltd. Manufacture, ECP600) obtain the content (mole %) of T3 unit and Q unit.
The content (mole %) of T3 unit and Q unit is by solid29The peak area ratio of Si-NMR is obtained respectively. Silicone resin layer uses the solid sample obtained as follows: on the glass substrate, each by spin coater coating The fraction comprising curable organopolysiloxane used in embodiment and comparative example, in each embodiment and Be heating and curing under the heating condition of comparative example, thus on the glass substrate formed silicone resin layer it After, utilize razor to cut and take this silicone resin layer and obtain solid sample.Algoscopy uses DDMAS method, Condition determination is set as: pulse width 1.9 microsecond, 300 seconds waiting time of pulse repetition, cumulative frequency More than 300scan, MAS rotary speed 10KHz.For the benchmark of chemical shift, diformazan will be derived from The peak of base organosilicon is set to-22ppm.It addition, derive from the solid of each structure29The chemical shift of Si-NMR As follows.
T3:-48～-88ppm
Q:-96～-116ppm
(2) parsing of (A-1) of silicone resin layer/(B-1) ratio
Use NMR analysis devices (solid1H-NMR:JEOL RESONANCE Co., Ltd. system Make, ECP600), origin comes from the peak area ratio of Ph base and Me base and obtains.Silicone resin layer uses such as Under the solid sample that obtains: on the glass substrate, coated in each embodiment and comparative example by spin coater and make The fraction comprising curable organopolysiloxane, under the heating condition of each embodiment and comparative example It is heating and curing, thus after forming silicone resin layer on the glass substrate, utilizes razor to cut and take this Silicone resin layer and obtain solid sample.Algoscopy uses Depth2, and condition determination is set as: pulse Width 2.3 microsecond, 15 seconds waiting time of pulse repetition, cumulative frequency 16scan, MAS rotary speed 22KHz.For the benchmark of chemical shift, the peak deriving from diamantane (obsolete) is set to 1.7ppm.It addition, come Come from the solid of each structure1The chemical shift of H-NMR is as follows.
A-1 (Ph yl): 18～4ppm
B-1 (Me yl): 4～-10ppm
(3) thickness of silicone resin layer
The thickness of silicone resin layer uses the surface roughness/contour shape of contact mould device to measure Machine (manufacture of Tokyo Precision Co., Ltd, Surfcom 1400G-12) measures.
(4) shrinkage stress of silicone resin layer
By external diameter be 4 inches, thickness be 525 ± 25 μm the location plane of Silicon Wafer on the basis of, be contained in After assigned position in membrane stress determinator FLX-2320 (KLA Tencor company manufacture), The radius of curvature of Silicon Wafer is measured at environment temperature 25 DEG C.
Then, take out Silicon Wafer, use spin-coating method to be coated with on Silicon Wafer in each embodiment and comparative example and make The fraction comprising curable organopolysiloxane after, at each embodiment and the fire-bar of comparative example It is heating and curing under part, forms silicone resin layer.Grasp as before formation silicon-type curing overlay film Make, at temperature 25 DEG C, measure the radius of curvature of the Silicon Wafer defining silicone resin layer around.
The shrinkage stress at 25 DEG C of silicone resin layer is calculated by following formula.
σ = E · h 2 ( 1 - v ) · 6 · R · t . . . ( 1 )
(in formula, E/ (1-ν) is the twin shaft coefficient of elasticity (crystal face (100): 1.805 × 10 of Silicon Wafer11Pa), H is the thickness [m] of Silicon Wafer, and t is the thickness [m] of silicone resin layer, and R is for forming silicone resin layer The radius of curvature of the radius of curvature of Silicon Wafer before and the Silicon Wafer formed after silicone resin layer it Difference [m].).
It should be noted that the organosiloxane base list of the silicone resin layer in glass composite S1～S9 Unit is made up of Q unit and T3 unit.In above-described embodiment 10 and comparative example 1, being not detected by Q unit (is Below determination limit).
[table 2]
As shown in Table 2 above, in the glass laminate of the present invention, silicone resin layer demonstrates excellence Thermostability, and, the fissility (separation property) of glass substrate is also excellent.Especially comprise Q unit In embodiment 1～9, fissility is more excellent.
On the other hand, as shown in comparative example 1,2, when not using the silicone resin layer of composition requirement ratio, Intended effect cannot be obtained.
＜ embodiment 11 ＞
In this example, use glass laminate S1 obtained in embodiment 1 to manufacture OLED.
First, on the 2nd interarea of the glass substrate in glass laminate S1, plasma CVD is utilized Method is with silicon nitride, silicon oxide, the order film forming of non-crystalline silicon.Then, utilize ion doping apparatus by low dense The boron of degree injects amorphous silicon layer heat treated, carries out Dehydroepiandrosterone derivative.Then, laser anneal device is utilized The crystallization carrying out amorphous silicon layer processes.Then, by employing photolithographic etching and ion doping dress Put, the phosphorus of low concentration is injected amorphous silicon layer, form N-type and the TFT zone of p-type.Afterwards, at glass 2nd interarea side of substrate, utilizes plasma CVD method to form silicon oxide film thus forms gate insulating film After, utilize sputtering method to form molybdenum film, form grid by employing photolithographic etching.Then, utilize Photoetching process and ion doping apparatus, inject N-type, the respective desired region of p-type by boron and the phosphorus of high concentration, Form source region and drain region.Then, in the 2nd interarea side of glass substrate, by utilize wait from The film forming of the silicon oxide that daughter CVD is carried out forms interlayer dielectric, is carried out the one-tenth of aluminum by sputtering method Film, forms TFT electrode by employing photolithographic etching.Then, heat treated under an atmosphere of hydrogen, After carrying out hydrogenation treatment, form passivation by the film forming utilizing silicon nitride that plasma CVD method carries out Layer.Then, at the 2nd interarea side coated UV line curable resin of glass substrate, by photoetching process shape Become planarization layer and contact hole.Then, sputtering method is utilized to form indium oxide tin film, by employing photoetching The etching of method forms pixel electrode.
Then, utilize vapour deposition method, make successively as hole injection layer in the 2nd interarea side of glass substrate 4,4 ', 4 "-three (3-methylphenylphenyl amino) triphenylamine, double [(N-naphthyls) as hole transmission layer -N-phenyl] benzidine, as luminescent layer at 8-hydroxyquinoline aluminium complex (Alq340 it are mixed with in) Double [4-[N-(4-the methoxyphenyl)-N-phenyl] aminostyryl] naphthalene-1,5-dimethoxy nitrile of the 2,6-of volume % (BSN-BCN) material, Alq as electron transfer layer3Film forming.Then, formed by sputtering method Aluminum film, by employing photolithographic etching shape paired electrode.Then, at the 2nd interarea of glass substrate Side, fits another glass substrate by the adhesive linkage of ultraviolet hardening, is packaged.By above-mentioned Step, forms organic EL structure on the glass substrate.There is organic EL structure on the glass substrate Glass laminate S1 (hereinafter referred to as panel A.) it is the duplexer of the having electronic equipment component of the present invention.
Then, make the encapsulation side vac sorb of panel A after platform, at the glass in the corner of panel A The stainless steel cutter of the interface inserting thickness 0.1mm of glass substrate and resin bed, to glass substrate and resin The interface of layer gives the starting point peeled off.Then, adsorb the support substrate surface of panel A with vacuum cup, And make sucker raise.Here, while blow to this interface from ionizer (KEYENCE JAPAN manufacture) Except electronic fluids limit carries out the insertion of cutter.Then, while continue to blow from ionizer remove to the space formed Electronic fluids, and inject water, edge height vacuum cup to stripping borderline line.Its result, on platform Only residual is formed with the glass substrate of organic EL structure, it is possible to peeled off by the support base material of tape tree lipid layer.
Then, the glass that laser cutter or scribing and breaking (scribe-break method) will separate is used Glass substrate cutting, after being divided into multiple unit, assembles and is formed with the glass substrate of organic EL structure and right To substrate, implement module formation process, make OLED.Thus obtained OLED does not characteristically have Come into question.
＜ embodiment 12 ＞
In this example, use glass laminate S1 obtained in embodiment 1 to manufacture LCD.
First, prepare 2 glass laminate S1, the glass substrate in glass laminate S1-1 On 2nd interarea, by plasma CVD method successively by silicon nitride, silicon oxide, non-crystalline silicon film forming.Connect , utilize ion doping apparatus that the boron of low concentration is injected amorphous silicon layer, in a nitrogen atmosphere heat treated, Carry out Dehydroepiandrosterone derivative.Then, the crystallization utilizing laser anneal device to carry out amorphous silicon layer processes.Then, Utilization employs photolithographic etching and ion doping apparatus, and the phosphorus of low concentration is injected amorphous silicon layer, shape Become N-type and the TFT zone of p-type.Then, in the 2nd interarea side of glass substrate, plasma CVD is utilized Method forms silicon oxide film, forms gate insulating film, then, utilizes sputtering method to form molybdenum film, by using Photolithographic etching forms grid.Then, photoetching process and ion doping apparatus are utilized, by high concentration Boron and phosphorus inject N-type, the respective desired region of p-type, form source region and drain region.Then, exist 2nd interarea side of glass substrate, is formed by the film forming utilizing silicon oxide that plasma CVD method carries out Interlayer dielectric, carries out the film forming of aluminum by sputtering method, forms TFT by employing photolithographic etching Electrode.Then, heat treated under an atmosphere of hydrogen, carry out hydrogenation treatment, then, by utilize wait from The film forming of the silicon nitride that daughter CVD is carried out forms passivation layer.Then, at the 2nd interarea of glass substrate Side coated UV line curable resin, forms planarization layer and contact hole by photoetching process.Then, utilize Sputtering method forms indium oxide tin film, forms pixel electrode by employing photolithographic etching.
Then, under atmospheric atmosphere, another glass laminate S1-2 is carried out heat treated.Then, exist On 2nd interarea of the glass substrate in glass laminate S1, sputtering method is utilized to form chromium film, by using Photolithographic etching forms light shield layer.Then, the 2nd interarea side at glass substrate is coated with by die coating method Cloth colour resist, forms color-filter layer by photoetching process and heat cure.Afterwards, sputtering method is utilized to be formed Indium oxide tin film, shape paired electrode.Then, in the 2nd interarea side of glass substrate, die coating method is utilized to be coated with Cloth ultraviolet curable resin liquid, forms column spacer by photoetching process and heat cure.Then, roller is utilized Coating coating polyimide resin liquid, forms oriented layer by heat cure, rubs.
Then, utilize allotter method to depict sealing resin liquid as frame-shaped, by distributor process frame Dropping liquid crystal, then, uses above-mentioned glass laminate S1-1 being formed with pixel electrode, by 2 glass Fitting each other in 2nd interarea side of the glass substrate of duplexer S1, is obtained by ultraviolet curing and heat cure LCD.
Then, make glass laminate S1-1 support base material the 2nd interarea vac sorb in platform, to glass The stainless steel of the interface inserting thickness 0.1mm of the glass substrate in the corner of glass duplexer S1-2 and resin bed Cutter, gives stripping starting point to the 1st interarea of glass substrate with the fissility surface of resin bed.Here, While blow except electronic fluids limit carries out cutter to this interface from ionizer (KEYENCE JAPAN manufacture) Insertion.Then, while continue to blow except electronic fluids to the space formed from ionizer, and to stripping Water is injected in boundary line, while make vacuum cup raise.Further, glass laminate S1-2 is adsorbed with vacuum cup Support base material the 2nd interarea after, make sucker raise.Its result, only remains with glass on platform The dummy cell of the LCD supporting base material of duplexer S1-1, it is possible to the support base material of tape tree lipid layer is peeled off.
Then, make to be formed with the 2nd interarea vac sorb of glass substrate of color filter in flat at the 1st interarea The interface inserting thickness 0.1mm's of platform, the glass substrate to the corner of glass laminate S1-1 and resin bed Stainless steel cutter, gives stripping starting point to the 1st interarea of glass substrate with the fissility surface of resin bed. Then, after the 2nd interarea supporting base material by vacuum cup absorption glass laminate S1-1, while to glass Water is blowed, while make sucker raise between substrate and resin bed.Its result, only remains LCD mono-on platform Unit, it is possible to the support base material being fixed with resin bed is peeled off.Thereby, it is possible to obtain by thickness 0.1mm's Multiple LCD cell that glass substrate is constituted.
Then, by cut off procedure division be multiple LCD cell.The each LCD cell completed is implemented patch The operation of attached Polarizer, is then carried out module formation process, obtains LCD.Thus obtained LCD is spy Do not come into question in property.
＜ embodiment 13 ＞
In this example, glass laminate S1 obtained in embodiment 1 is used to manufacture OLED.
First, on the 2nd interarea of the glass substrate in glass laminate S1, utilize sputtering method to form molybdenum Film, utilizes and employs photolithographic etching formation grid.Then, sputtering method is utilized, at glass substrate 2nd interarea side forms pellumina further, thus forms gate insulating film, then utilizes sputtering method shape Become indium gallium zinc film, form oxide semiconductor layer by employing photolithographic etching.Then, profit Form pellumina with sputtering method further in the 2nd interarea side of glass substrate, form channel protective layer, Then, utilize sputtering method to form molybdenum film, form source electrode and drain electrode by employing photolithographic etching.
Then, heat treated is carried out in an atmosphere.Then, the 2nd interarea side at glass substrate is further Form pellumina by sputtering method and form passivation layer, form indium oxide tin film followed by sputtering method, Pixel electrode is formed by employing photolithographic etching.
Then, vapour deposition method is utilized to make successively as hole injection layer in the 2nd interarea side of glass substrate 4,4 ', 4 "-three (3-methylphenylphenyl amino) triphenylamine, double [(N-naphthyls) as hole transmission layer -N-phenyl] benzidine, as luminescent layer at 8-hydroxyquinoline aluminium complex (Alq340 it are mixed with in) Double [4-[N-(4-the methoxyphenyl)-N-phenyl] aminostyryl] naphthalene-1,5-dimethoxy nitrile of the 2,6-of volume % (BSN-BCN) material, Alq as electron transfer layer3Film forming.Then, sputtering method is utilized to be formed Aluminum film, by employing photolithographic etching shape paired electrode.Then, at the 2nd interarea of glass substrate Side, fits another glass substrate by the adhesive linkage of ultraviolet hardening, is packaged.By above-mentioned Step, forms organic EL structure on the glass substrate.There is organic EL structure on the glass substrate Glass laminate S1 (hereinafter referred to as panel B.) it is the duplexer of the having electronic equipment component of the present invention (the display device panel of band support base material).
Then, make the encapsulation side vac sorb of panel B after platform, at the glass in the corner of panel B The stainless steel cutter of the interface inserting thickness 0.1mm of glass substrate and resin bed, to glass substrate and resin The interface of layer gives peels off starting point.Then, adsorb the support substrate surface of panel B with vacuum cup, and Sucker is made to raise.Here, while blow to this interface from ionizer (KEYENCE JAPAN manufacture) and remove Electronic fluids limit carries out the insertion of cutter.Then, while persistently blow except electricity to the space formed from ionizer Property fluid, and to stripping borderline line inject water, edge height vacuum cup.Its result, on platform only Residual is formed with the glass substrate of organic EL structure, it is possible to tape tree lipid layer is supported base material and peels off.
Then, use laser cutter or scribing and breaking to be cut off by the glass substrate separated, be divided into many After individual unit, assemble glass substrate and the opposite substrate being formed with organic EL structure, implement module and formed Operation, makes OLED.Thus obtained OLED does not the most come into question.
It should be noted that go out to be willing to No. 2014-022697 by Japanese Patent filed in 7 days February in 2014 The full content of description, claims, summary and accompanying drawing is referenced in the application, as the present invention The disclosure of description and be incorporated to.
Description of reference numerals
10,100,200 glass laminate
12 support base material
14 silicone resin layers
16 glass substrates
The support base material of 18 tape tree lipid layer
The glass substrate of 20 tape tree lipid layer
22 electronic device members
The duplexer of 24 having electronic equipment components
The glass substrate of 26 band members

Claims (11)

1. a glass laminate, it possesses the support layer of base material, silicone resin layer and glass base successively The layer of plate,
Organic siliconresin in described silicone resin layer has the organosiloxane base list that following T3 represents Unit, relative to whole organosiloxane base unit, the organosiloxane base unit that following T3 represents always than Rate is 80～100 moles of %,
R in following T3 be the R in organosiloxane base unit (A-1) and the following T3 of phenyl be methyl The mol ratio ((A-1)/(B-1)) of organosiloxane base unit (B-1) be 80/20～20/80,
Described silicone resin layer relative to the peel strength at the interface of the layer of described glass substrate with described Silicone resin layer is different relative to the peel strength at the interface of the layer of described support base material,
T3:R-SiO3/2
In formula, R represents phenyl or methyl.
Glass laminate the most according to claim 1, wherein, under described organic siliconresin also has State the organosiloxane base unit that Q represents,
Q:SiO4/2。
Glass laminate the most according to claim 1 and 2, wherein, described organic siliconresin is solidification The solidfied material of property organopolysiloxane,
Described curable organopolysiloxane is to comprise, with following ratio, the organosilicon that following T1～T3 represents The organopolysiloxane of oxyalkyl unit: in terms of the ratio (mole) of the number of described unit, T1: T2:T3=0～5:20～50:50～80, wherein, meets the relation of T1+T2+T3=100,
T1:R-Si (-OX)2O1/2
T2:R-Si (-OX) O2/2
T3:R-SiO3/2
In formula, R represents phenyl or methyl, and X represents hydrogen atom or the alkyl of carbon number 1～6.
Glass laminate the most according to claim 3, wherein, described curable organopolysiloxane Number-average molecular weight be 500～2000.
5. according to the glass laminate described in claim 3 or 4, wherein, the organic poly-silica of described curable Matter average molecular weight/the number-average molecular weight of alkane is 1.00～2.00.
6. according to the glass laminate according to any one of claim 3～5, wherein, utilize dynamic optical to dissipate The particle diameter of the described curable organopolysiloxane that the method for penetrating records is 0.5～100nm.
7., according to the glass laminate according to any one of claim 3～6, wherein, described curable has Machine polysiloxanes be by make phenyl trichlorosilane and methyl trichlorosilane cohydrolysis condensation obtain have Machine polysiloxanes.
8. according to the glass laminate according to any one of claim 1～7, wherein, described organosilicon tree The thickness of lipid layer is 0.1～30 μm.
9. according to the glass laminate according to any one of claim 1～8, wherein, described support base material For glass plate.
10. according to the glass laminate according to any one of claim 1～9, wherein, described organosilicon tree Lipid layer is more relative than described silicone resin layer relative to the peel strength at the interface of the layer of described glass substrate Peel strength in the interface of the layer of described support base material is low.
11. according to the glass laminate according to any one of claim 1～9, wherein, described organosilicon tree Lipid layer is more relative than described silicone resin layer relative to the peel strength at the interface of the layer of described glass substrate Peel strength in the interface of the layer of described support base material is high.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10543662B2 (en) 2012-02-08 2020-01-28 Corning Incorporated Device modified substrate article and methods for making
US10086584B2 (en) 2012-12-13 2018-10-02 Corning Incorporated Glass articles and methods for controlled bonding of glass sheets with carriers
US9340443B2 (en) 2012-12-13 2016-05-17 Corning Incorporated Bulk annealing of glass sheets
US10014177B2 (en) 2012-12-13 2018-07-03 Corning Incorporated Methods for processing electronic devices
TWI617437B (en) 2012-12-13 2018-03-11 康寧公司 Facilitated processing for controlling bonding between sheet and carrier
US10510576B2 (en) 2013-10-14 2019-12-17 Corning Incorporated Carrier-bonding methods and articles for semiconductor and interposer processing
JP6770432B2 (en) 2014-01-27 2020-10-14 コーニング インコーポレイテッド Articles and methods for controlled binding of thin sheets to carriers
KR20160145062A (en) 2014-04-09 2016-12-19 코닝 인코포레이티드 Device modified substrate article and methods for making
JP2018524201A (en) 2015-05-19 2018-08-30 コーニング インコーポレイテッド Articles and methods for bonding sheets with carriers
JP7106276B2 (en) 2015-06-26 2022-07-26 コーニング インコーポレイテッド Articles and methods with sheets and carriers
CN109070549B (en) * 2016-04-28 2021-07-06 Ａｇｃ株式会社 Glass laminate and method for producing same
TW201825623A (en) 2016-08-30 2018-07-16 美商康寧公司 Siloxane plasma polymers for sheet bonding
TWI810161B (en) 2016-08-31 2023-08-01 美商康寧公司 Articles of controllably bonded sheets and methods for making same
CN111615567B (en) 2017-12-15 2023-04-14 康宁股份有限公司 Method for treating substrate and method for producing article including adhesive sheet
CN111533464B (en) * 2020-05-07 2023-01-31 索菲立(福建)新材料科技有限公司 Preparation method of impact-resistant glass with coating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101242951A (en) * 2005-08-09 2008-08-13 旭硝子株式会社 Thin sheet glass laminate and method for manufacturing display using thin sheet glass laminate
CN102596566A (en) * 2009-08-28 2012-07-18 旭硝子株式会社 Support, glass substrate laminate, support-equipped display device panel, and method for manufacturing a display device panel
CN102596565A (en) * 2009-08-27 2012-07-18 旭硝子株式会社 Multilayer structure with flexible base material and support, panel for use in electronic device provided with support and production method for panel for use in electronic device
CN103003725A (en) * 2010-08-11 2013-03-27 三菱树脂株式会社 Metal foil laminate, substrate for mounting LED, and light source device
WO2013058217A1 (en) * 2011-10-18 2013-04-25 旭硝子株式会社 Laminate, method for producing laminate, and method for producing glass substrate having member for electronic devices attached thereto

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2819162B2 (en) * 1989-08-11 1998-10-30 大三工業株式会社 Scratching agent for glass containers
WO2009111196A1 (en) * 2008-03-04 2009-09-11 Dow Corning Corporation Silicone composition, silicone adhesive, coated and laminated substrates
JP2001240800A (en) * 2000-02-25 2001-09-04 Nippon Sheet Glass Co Ltd Preparation process of article having predetermined surface form
WO2008079179A1 (en) * 2006-12-20 2008-07-03 Dow Corning Corporation Glass substrates coated or laminated with cured silicone resin compositions
JP4882854B2 (en) * 2007-04-27 2012-02-22 セントラル硝子株式会社 Glass coating composition
TW201004795A (en) * 2008-07-31 2010-02-01 Dow Corning Laminated glass
US8742009B2 (en) * 2010-06-04 2014-06-03 Shin-Etsu Chemical Co., Ltd. Temporary adhesive composition, and method of producing thin wafer
JP2015231668A (en) * 2012-09-27 2015-12-24 旭硝子株式会社 Glass laminate and method for producing the same, and supporting substrate having silicone resin layer and method for producing the same
JP2015147376A (en) * 2014-02-07 2015-08-20 旭硝子株式会社 Glass composite body

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101242951A (en) * 2005-08-09 2008-08-13 旭硝子株式会社 Thin sheet glass laminate and method for manufacturing display using thin sheet glass laminate
CN102596565A (en) * 2009-08-27 2012-07-18 旭硝子株式会社 Multilayer structure with flexible base material and support, panel for use in electronic device provided with support and production method for panel for use in electronic device
CN102596566A (en) * 2009-08-28 2012-07-18 旭硝子株式会社 Support, glass substrate laminate, support-equipped display device panel, and method for manufacturing a display device panel
CN103003725A (en) * 2010-08-11 2013-03-27 三菱树脂株式会社 Metal foil laminate, substrate for mounting LED, and light source device
WO2013058217A1 (en) * 2011-10-18 2013-04-25 旭硝子株式会社 Laminate, method for producing laminate, and method for producing glass substrate having member for electronic devices attached thereto

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110315814A (en) * 2018-03-30 2019-10-11 Skc株式会社 Glass engagement plural layers, laminated glass and its manufacturing method including it
CN110315814B (en) * 2018-03-30 2022-03-22 Skc株式会社 Multilayer film for glass bonding, laminated glass including the same, and method for producing the same

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