CN104736340A

CN104736340A - Glass laminate and manufacturing method therefor, and support base with silicone resin layer

Info

Publication number: CN104736340A
Application number: CN201380054462.5A
Authority: CN
Inventors: 宫古强臣; 山内优; 照井弘敏
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2012-10-17
Filing date: 2013-10-10
Publication date: 2015-06-24
Anticipated expiration: 2033-10-10
Also published as: WO2014061565A1; TWI613073B; KR20150073976A; TW201429709A; CN104736340B; JPWO2014061565A1; JP6194893B2

Abstract

The present invention relates to a glass laminate provided with a support base layer, a silicone resin layer and a glass substrate layer in said order, in which the peel strength of the interface between the support base layer and the silicone resin layer is higher than the peel strength of the interface between the silicone resin layer and the glass substrate. The silicone resin of the silicone resin layer is a crosslinked product of a cross-linking organopolysiloxane. The silicone resin layer contains a silicone oil. Either the silicone resin or the silicone oil of the silicone resin layer comprises aromatic groups and the other comprises substantially no aromatic groups.

Description

Glass laminate and manufacture method thereof and there is the support base material of silicone layer

Technical field

The present invention relates to glass laminate and manufacture method thereof, particularly relate to glass laminate and the manufacture method thereof of the silicone layer had containing silicone oil.

In addition, the present invention relates to the support base material with silicone layer, particularly relate to the support base material with silicone layer and manufacture method thereof that glass substrate strippingly waits to be laminated in its surface.

Background technology

In recent years, the device (electronic equipment) of solar cell (PV), liquid crystal panel (LCD), organic EL panel (OLED) etc. is advancing slimming, lightweight, and the glass substrate used in these devices advances thin plate.Because of thin plate cause glass substrate intensity not enough time, the operability of the glass substrate in the manufacturing process of device declines.

Therefore, extensively adopted with the following method since the past: form device component (such as thin film transistor (TFT)) on the glass substrate thicker than final thickness after, by chemical etching process by glass substrate thin plate.

But in the method, such as, making the thickness of 1 sheet glass substrate from 0.7mm thin plate to 0.2mm or 0.1mm, more than half meeting of the material of original glass substrate eliminate by etching solution, from the viewpoint of productivity ratio, raw-material service efficiency is such is not preferred.In addition, above-mentionedly utilize in the thin plate method of the glass substrate of chemical etching, when glass baseplate surface exists trickle scar, be that starting point forms trickle pit (pit) sometimes with scar due to etch processes, become optical defect.

Recently, in order to tackle above-mentioned problem, propose following method: the glass laminate preparing to be laminated with glass sheet substrate and reinforcement plate, after the glass sheet substrate of glass laminate is formed the component used for electronic device of display unit etc., gripper shoe is separated (reference example is as patent document 1 or patent document 2) from glass sheet substrate.Reinforcement plate has gripper shoe and is fixed to the silicone layer in this gripper shoe, closely sealed in a releasable manner between silicone layer and glass sheet substrate.By the silicone layer of glass laminate and the interface peel of glass sheet substrate, the reinforcement plate be separated from glass sheet substrate can carry out stacked with new glass sheet substrate, reuses as glass laminate.

It should be noted that, in patent document 2 (especially embodiment 7), specifically disclose and use containing the scheme of dimethyl polysiloxane as the silicone layer of silicone oil.

Prior art document

Patent document

No. 2007/018028, patent document 1:WO

No. 2011/142280, patent document 2:WO

Summary of the invention

The problem that invention will solve

For the glass laminate described in patent document 1 and 2, require higher heat resistance in recent years.Along with the multifunction of the component used for electronic device formed on the glass substrate of glass laminate and complicated, the further high temperature of temperature when forming component used for electronic device, and the time exposed at such high temperatures also need long situation many.In addition, the glass substrate used is further filming also, and its treatability becomes difficulty.

Glass laminate described in patent document 1 and 2 can tolerate the process of 300 DEG C in an atmosphere, 1 hour.But, according to the research of the present inventor, with reference to patent document 1 and 2, when carrying out the process of 350 DEG C, 1 hour to using the glass laminate of the thinner glass substrate of thickness, during by glass substrate from silicone layer sur-face peeling, sometimes glass substrate not to be peeled off and its part is destroyed or a part for the resin of resin bed is residual on the glass substrate from resin layer surface, and the productivity ratio of electronic device can be caused as a result to decline.

The present invention completes in view of above-mentioned problem, object is to provide glass laminate and manufacture method thereof, even if the rising of this glass laminate peel strength of glass substrate and silicone layer after high-temperature heating treatment condition is also suppressed, can easily glass substrate be peeled off.

In addition, the present invention relates to the support base material with silicone layer used in the manufacture of this glass laminate.

For the means of dealing with problems

The present inventor conducts in-depth research to solve above-mentioned problem, and result completes the present invention.

Namely, the 1st aspect of the present invention is a kind of glass laminate, possesses the layer of the layer of support base material, silicone layer and glass substrate successively, the peel strength at the layer of support base material and the interface of silicone layer is higher than the peel strength at the interface of silicone layer and glass substrate, wherein the silicones of silicone layer is the cross-linking agent of bridging property organopolysiloxane, silicone layer contains silicone oil, one in the silicones contained in silicone layer and silicone oil has aromatic series base, and another one does not have aromatic series base in fact.

In first method, preferred silicone oil has phenyl, is preferably 5 ~ 50 % by mole in silicone oil with the containing ratio of phenyl in whole organic groups of silicon atom bonding.

In first method, in silicone layer, the content of silicone oil is preferably 6 ~ 20 mass parts relative to silicones 100 mass parts.

In first method, silicone oil is preferably 100 ~ 6000cP the viscosity of 25 DEG C.

In first method, the thickness of silicone layer is preferably 2 ~ 100 μm.

In first method, support base material is preferably glass plate.

The 2nd aspect of the present invention is the method for the glass laminate manufacturing first method, it is characterized in that, the layer comprising bridging property organopolysiloxane and silicone oil is formed at the one side of support base material, make described bridging property organopolysiloxane crosslinked on the surface at support base material thus form silicone layer, then at the superficial layer laminated glass substrate of silicone layer.

The 3rd aspect of the present invention is a kind of support base material with silicone layer, there is support base material and be arranged on the silicone layer with fissility surface on support base material face, the silicones of silicone layer is the cross-linking agent of bridging property organopolysiloxane, silicone layer contains silicone oil, one in the silicones contained in silicone layer and silicone oil has aromatic series base, and another one does not have aromatic series base in fact.

In Third Way, preferred silicone oil has phenyl, is preferably 5 ~ 50 % by mole, more preferably 5 ~ 30 % by mole in silicone oil with the containing ratio of phenyl in whole organic groups of silicon atom bonding.

In Third Way, in silicone layer, the content of silicone oil is preferably 6 ~ 20 mass parts relative to silicones 100 mass parts.

In Third Way, silicone oil is preferably 100 ~ 6000cP the viscosity of 25 DEG C.

Invention effect

According to the present invention, can provide glass laminate and manufacture method thereof, even if this glass laminate is after high-temperature heating treatment condition, the rising of the peel strength of glass substrate and silicone layer is also suppressed, and can easily be peeled off by glass substrate.

In addition, according to the present invention, can be provided in the support base material with silicone layer used in the manufacture of this glass laminate.

Accompanying drawing explanation

Fig. 1 is the schematic sectional view of an embodiment of glass laminate of the present invention.

Fig. 2 (A) ~ Fig. 2 (D) illustrates the schematic sectional view with an embodiment of the manufacture method of the glass substrate of component of the present invention according to sequence of steps.

Detailed description of the invention

Below, be described for implementing mode of the present invention with reference to accompanying drawing, but the invention is not restricted to following embodiment, various distortion and displacement can be applied to following embodiment under the condition not departing from the scope of the invention.

Glass laminate of the present invention possesses the layer of the layer of support base material, silicone layer and glass substrate successively.That is, between the layer and the layer of glass substrate of support base material, have silicone layer, therefore, the side of silicone layer connects with the layer of support base material, and opposite side connects with the layer of glass substrate.

One of characteristic point of glass laminate of the present invention can enumerate following point: containing silicone oil in silicone layer, and the one in silicone layer only in silicones and silicone oil has aromatic series base, and another one does not have aromatic series base in fact.By only importing aromatic series base to the one in silicones or silicone oil, both compatibilities are declined.Its result, silicone oil becomes and is easy to ooze out into silicone layer surface at short notice, even if short to the time between laminated glass substrate after being formed from silicone layer, still be easy to the silicone layer obtaining glass substrate being demonstrated to good fissility, even if its result is after high-temperature heating, the rising of the peel strength of glass substrate and silicone layer also can be suppressed.In addition as described later, when using the silicone oil of regulation, further ensure that the transparency on silicone layer surface, and the transparency of the glass baseplate surface be stripped is also more excellent.

In addition, silicone layer of the present invention demonstrates good fissility, even if thus have the lower thickness of glass substrate, during stripping after high-temperature heating, glass substrate is also difficult to the feature of breaking.

Fig. 1 is the schematic sectional view of an example of glass laminate of the present invention.

As shown in Figure 1, glass laminate 10 is the duplexers having the layer of support base material 12, the layer of glass substrate 16 and silicone layer 14 between which.A face of silicone layer 14 connects with the layer of support base material 12, and its another side connects with the 1st interarea 16a of glass substrate 16.In other words, silicone layer 14 connects with the 1st interarea 16a of glass substrate 16.

The double-deck part reinforcing glass substrate 16 in the component formation process of component used for electronic device manufacturing liquid crystal panel etc. be made up of layer and the silicone layer 14 of support base material 12.It should be noted that, the double-deck part be made up of layer and the silicone layer 14 of support base material 12 manufactured in advance for manufacturing glass laminate 10 is called the support base material 18 with silicone layer.

This glass laminate 10 is used till component formation process described later.That is, this glass laminate 10 is used till the 2nd interarea 16b of its glass substrate 16 forms the component used for electronic device of liquid crystal indicator etc. on the surface.Afterwards, the glass laminate being formed with component used for electronic device is separated into the support base material 18 with silicone layer and the glass substrate with component, and the support base material 18 with silicone layer can not become the part forming electronic device.Can on the support base material 18 with silicone layer stacked new glass substrate 16, thus to reuse as new glass laminate 10.

Support base material 12 has peel strength (x) with the interface of silicone layer 14, when being applied above the direction of delaminate stress of peel strength (x) to the interface of support base material 12 and silicone layer 14, support base material 12 is peeled off with the interface of silicone layer 14.Silicone layer 14 has peel strength (y) with the interface of glass substrate 16, when being applied above the direction of delaminate stress of peel strength (y) to the interface of silicone layer 14 and glass substrate 16, silicone layer 14 is peeled off with the interface of glass substrate 16.

In glass laminate 10 (also referring to the duplexer with component used for electronic device described later), above-mentioned peel strength (x) is higher than above-mentioned peel strength (y).Therefore, when glass laminate 10 being applied to the stress on the direction of support base material 12 and glass substrate 16 being peeled off, glass laminate 10 of the present invention is peeled off at the interface of silicone layer 14 with glass substrate 16, is separated into glass substrate 16 and the support base material 18 with silicone layer.

Peel strength (x) is preferably high fully compared to peel strength (y).Improve peel strength (x) and mean the adhesive force that can improve silicone layer 14 pairs of support base materials 12, and the adhesive force relatively higher than the adhesive force to glass substrate 16 can be maintained after a heating treatment.

In order to improve the adhesive force of silicone layer 14 pairs of support base materials 12, as described later, preferably make bridging property organopolysiloxane on support base material 12 crosslinking curing thus formed silicone layer 14.Cohesive force during crosslinking curing can be utilized to form the silicone layer 14 combined support base material 12 with high-bond.

On the other hand, the adhesion that the adhesion of solidfied material to glass substrate 16 of the bridging property organopolysiloxane after crosslinking curing produces when being usually less than above-mentioned crosslinking curing.Therefore, preferably make bridging property organopolysiloxane on support base material 12 crosslinking curing thus formed silicone layer 14, afterwards laminated glass substrate 16 on the face of silicone layer 14, thus manufacture glass laminate 10.

Below, first each layer (support base material 12, glass substrate 16, silicone layer 14) forming glass laminate 10 is described in detail, afterwards the manufacture method of glass laminate with the glass substrate with component is described in detail.

[support base material]

Support base material 12 support glass substrate 16 strengthens, and prevents the distortion, damage, breakage etc. of glass substrate 16 when manufacturing component used for electronic device in component formation process described later (manufacturing the operation of component used for electronic device).

As support base material 12, the metallic plates etc. such as such as glass plate, plastic plate, SUS plate can be used.Usually, component formation process is attended by heat treatment, and therefore support base material 12 is preferably formed by the material that the difference of the linear expansion coefficient with glass substrate 16 is little, and more preferably formed by the material identical with glass substrate 16, support base material 12 is preferably glass plate.Especially, the glass plate be preferably made up of the glass material identical with glass substrate 16 of support base material 12.

The thickness of support base material 12 can be thicker than glass substrate 16, also can be thinner.Be preferably based on the thickness of glass substrate 16, the thickness of silicone layer 14 and the thickness of glass laminate 10 to select the thickness of support base material 12, such as, existing component formation process is the patten's design of substrate according to process thickness 0.5mm, when the thickness of glass substrate 16 and the thickness sum of silicone layer 14 are 0.1mm, the thickness of support base material 12 is set to 0.4mm.The thickness of support base material 12 is preferably 0.2 ~ 5.0mm under normal conditions.

When support base material 12 is glass plate, for easily processing, being difficult to reasons such as breaking, the thickness of glass plate is preferably more than 0.08mm.In addition, can not to break, can the reason of rigidity of appropriateness flexure for expecting to have when peeling off after component used for electronic device is formed, the thickness of glass plate is preferably below 1.0mm.

Support base material 12 and glass substrate 16 are preferably 500 × 10 in the difference of the average coefficient of linear expansion of 25 ~ 300 DEG C ^-7/ DEG C below, be more preferably 300 × 10 ^-7/ DEG C below, more preferably 200 × 10 ^-7/ DEG C below.When difference is excessive, when the heating in component formation process cools, glass laminate 10 likely violent warpage or support base material 12 is likely peeled off with glass substrate 16.When the material of support base material 12 is identical with the material of glass substrate 16, the generation of this problem can be suppressed.

[glass substrate]

1st interarea 16a of glass substrate 16 connects with silicone layer 14, with the 2nd interarea 16b of silicone layer 14 side opposite side on component used for electronic device is set.

The kind of glass substrate 16 can be conventional kind, such as, can enumerate the glass substrate etc. of LCD, OLED and so on display unit.Chemical-resistant, the resistance to poisture-penetrability of glass substrate 16 are excellent, and percent thermal shrinkage is low.As the index of percent thermal shrinkage, use the linear expansion coefficient of regulation in JIS R 3102 (nineteen ninety-five revision).

When the linear expansion coefficient of glass substrate 16 is large, because component formation process is in most cases attended by heating, therefore easily produce various bad.Such as, glass substrate 16 forms TFT, to formed under heating the glass substrate after TFT 16 cool time, likely make due to the thermal contraction of glass substrate 16 position of TFT offset excessive.

Glass substrate 16 by by frit melting, melten glass is configured as tabular and obtains.This manufacturing process can be conventional method, such as, can use float glass process, fusion method, discharge orifice glass tube down-drawing, Fu Ke (Fourcault) method, Lu Bai (Lubbers) method etc.In addition, especially for the thin glass substrate 16 of thickness, can by the glass heats of tabular temporarily will be configured as to the temperature that can be shaped, the means such as utilization extension carry out stretching and thinning method (under again drawing (redraw) method) forms and obtains.

The kind of the glass of glass substrate 16 is not particularly limited, preferably without alkali borosilicate glass, borosilicate glass, soda-lime glass, high silicon dioxide glass, other take silica as the oxide-based glass of main component.As oxide-based glass, the silica content being preferably based on oxide conversion is the glass of 40 ~ 90 quality %.

As the glass of glass substrate 16, adopt and be suitable for the kind of component used for electronic device or the glass of its manufacturing process.Such as, because the stripping of alkali metal component easily impacts liquid crystal, thus the glass substrate of liquid crystal panel is made up of (but usually containing alkaline earth metal component) the glass (alkali-free glass) of alkali-free metal ingredient in fact.Thus, the glass of glass substrate 16 is selected suitably based on the kind of applied device and manufacturing process thereof.

From slimming and/or the light-weighted viewpoint of glass substrate 16, the thickness of glass substrate 16 is preferably below 0.3mm, is more preferably below 0.15mm, more preferably below 0.10mm.When below 0.3mm, good flexibility can be given to glass substrate 16.When below 0.15mm, glass substrate 16 can be coiled into web-like.

In addition, for easily manufacturing the reasons such as glass substrate 16, easily process glass substrate 16, the thickness of glass substrate 16 is preferably more than 0.03mm.

It should be noted that, glass substrate 16 above can be made up of two-layer, and in the case, the material forming each layer can be same material, also can be not same material.In addition, in the case " thickness of glass substrate 16 " refers to the aggregate thickness of all layers.

[silicone layer]

Silicone layer 14 prevents the position of glass substrate 16 from offseting and prevents the breakages because of lock out operation such as glass substrate 16, till carrying out the operation be separated with support base material 12 by glass substrate 16.Surface (the 1st interarea of the silicone layer) 14a connected with glass substrate 16 of silicone layer 14 is sealed at the 1st interarea 16a of glass substrate 16 in a releasable manner.Silicone layer 14 is combined with the 1st interarea 16a of glass substrate 16 with weak binding power, and the peel strength (y) at its interface is lower than the peel strength (x) at the interface between silicone layer 14 and support base material 12.

That is, when being separated with support base material 12 by glass substrate 16, the 1st interarea 16a of glass substrate 16 and the interface of silicone layer 14 are peeled off, and support base material 12 is difficult to peel off with the interface of silicone layer 14.Therefore, silicone layer 14 has closely sealed with the 1st interarea 16a of glass substrate 16 but can easily by surface characteristic that glass substrate 16 is peeled off.Namely, silicone layer 14 to combine with adhesion to a certain degree relative to the 1st interarea 16a of glass substrate 16 thus prevents the position skew etc. of glass substrate 16, simultaneously again can not destroy glass substrate 16 when being peeled off by glass substrate 16 and the adhesion of the degree that can easily peel off combines.In the present invention, the character that can easily peel off on this silicone layer 14 surface is called fissility.On the other hand, the 1st interarea of support base material 12 combines with the relative adhesion being difficult to peel off with between silicone layer 14.

It should be noted that, the upper front and back forming component used for electronic device in the face (the 2nd interarea 16b) of the glass substrate 16 of glass laminate 10, silicone layer 14 can change (that is, peel strength (x), peel strength (y) can change) with the adhesion at the interface of glass substrate 16.But even if after formation component used for electronic device, peel strength (y) is also lower than peel strength (x).

Silicone layer 14 and the layer of glass substrate 16 it is believed that and to be combined with weak cohesive force, the adhesion of Van der Waals force of resulting from.When being formed after silicone layer 14 at its superficial layer laminated glass substrate 16, the silicones of silicone layer 14 is full cross-linked when reaching the degree not showing cohesive force, and the adhesion thinking to result from Van der Waals force combines.But, there is in the many situations of silicones of silicone layer 14 weak cohesive force to a certain degree.Even if when caking property is extremely low, when forming component used for electronic device on this duplexer after manufacturing glass laminate 10, think that the silicones of silicone layer 14 bonds with glass substrate 16 due to heating operation etc., the adhesion between the layer of silicone layer 14 and glass substrate 16 rises.

Optionally, carry out stacked after also can weakening the process of adhesion between the two to the 1st interarea 16a of the surface of stacked front silicone layer 14, stacked front glass substrate 16.Carry out non-adhesive process etc. by treating stacked face, then carry out stacked, the adhesion at silicone layer 14 and the interface of the layer of glass substrate 16 can be weakened thus, thus reduce peel strength (y).

In addition, silicone layer 14 is with the strong adhesion such as cohesive force, bonding force and support base material 12 surface conjunction.Such as, as mentioned above, by making bridging property organopolysiloxane crosslinking curing on support base material 12 surface, the silicones as cross-linking agent can be bonded in support base material 12 surface and obtain high-bond thus.In addition, can be embodied in produce strong adhesion between support base material 12 surface and silicone layer 14 process (such as using the process of coupling agent) to improve the adhesion between support base material 12 surface and silicone layer 14.

The layer of silicone layer 14 and support base material 12 is combined the interface meaning both peel strength (x) with high-bond is high.

The thickness of silicone layer 14 is not particularly limited, and is preferably 2 ~ 100 μm, is more preferably 3 ~ 50 μm, more preferably 7 ~ 20 μm.When the thickness of silicone layer 14 is this scope, even if there is bubble, foreign matter between silicone layer 14 and glass substrate 16, glass substrate 16 also can be suppressed to produce strain defect.In addition, when the thickness of silicone layer 14 is blocked up, it forms needs and expends time in and material, be uneconomic, and heat resistance declines sometimes.In addition, when the thickness of silicone layer 14 is crossed thin, silicone layer 14 declines sometimes with the adaptation of glass substrate 16.

It should be noted that, silicone layer 14 can be formed more than two-layer.In the case, " thickness of silicone layer 14 " refers to the aggregate thickness of all layers.

In addition, at silicone layer 14 by when forming more than two-layer, the resin forming each layer can be made up of not identical cross-linked silicone.

The silicones contained in silicone layer 14 is the cross-linking agent of bridging property organopolysiloxane, and silicones forms tridimensional network.

The kind of bridging property organopolysiloxane is not particularly limited, as long as the cross-linking reaction via regulation is understood crosslinking curing thus is formed the cross-linking agent (solidfied material) forming silicones, then its structure is not particularly limited, as long as have the bridging property of regulation.Crosslinked form is not particularly limited, and can adopt suitable known forms according to the kind of the crosslinkable groups contained in bridging property organopolysiloxane.Such as hydrosilylation reactions can be enumerated; Condensation reaction; Or utilize heat, the radical reaction of high-energy rays process or radical polymerization initiator; Etc..

More particularly, when bridging property organopolysiloxane has the free-radical reactive groups such as alkenyl or alkynyl, by the free-radical reactive group reaction each other via above-mentioned radical reaction, thus be cross-linked to form solidfied material (cross-linked silicone).

In addition, when bridging property organopolysiloxane has silanol group, be cross-linked by silanol group condensation reaction each other, thus form solidfied material.

In addition, when bridging property organopolysiloxane contain have with the organopolysiloxane of the thiazolinyl of silicon atom bonding (vinyl etc.) (i.e. olefinic organic based polysiloxane) and have with the hydrogen atom of silicon atom bonding (hydrogen silicyl) organopolysiloxane (i.e. organic hydrogen polysiloxanes), be cross-linked by hydrosilylation reactions under the existence of hydrosilylation catalysts (such as platinum class catalyst), thus form solidfied material.

Wherein, from the viewpoint of easily forming silicone layer 14 and making the fissility of glass substrate more excellent, preferred bridging property organopolysiloxane is included in two ends and/or side chain to be had the organopolysiloxane (being hereafter also called organopolysiloxane A suitably) of thiazolinyl and has the scheme of organopolysiloxane (being hereafter also called organic polysiloxane B suitably) of hydrogen silicyl at two ends and/or side chain.

It should be noted that, be not particularly limited as thiazolinyl, but wherein from excellent heat resistance aspect, such as, can enumerate vinyl (vinyl group), pi-allyl (2-acrylic), cyclobutenyl, pentenyl, hexenyl etc., be preferably vinyl.

In addition, as the group beyond the dehydrogenation silicyl contained in the group except thiazolinyl contained in organopolysiloxane A and organic polysiloxane B, alkyl (especially carbon number is the alkyl of less than 4) can be enumerated.

The position of the thiazolinyl in organopolysiloxane A is not particularly limited, and when organopolysiloxane A is straight-chain, thiazolinyl both can exist in the one of the M unit shown in hereafter and D unit, also can exist in M unit and D unit.From curing rate aspect, preferably at least exist in M unit, preferably exist in both two M unit.

It should be noted that, M unit and D unit are the examples of the basic structural unit of organopolysiloxane, and M unit is the siloxane unit of the mono-functional being combined with three organic groups, and D unit is the siloxane unit of two functionalities being combined with two organic groups.In siloxane unit, siloxane bond be two silicon atoms via an oxygen atom key of bonding, in siloxane bond, the oxygen atom of each silicon atom is considered as 1/2 thus, in formula, be expressed as O _1/2.

The quantity of the thiazolinyl in organopolysiloxane A is not particularly limited, and is preferably 1 ~ 3, more preferably 2 in a part.

The position of the hydrogen silicyl in organic polysiloxane B is not particularly limited, and when organopolysiloxane A is straight-chain, hydrogen silicyl both can exist in the one of M unit and D unit, also can exist in M unit and D unit.From the aspect of curing rate, preferably at least exist in D unit.

The quantity of the hydrogen silicyl in organic polysiloxane B is not particularly limited, and preferably at least has 3, is more preferably 3 in a part.

The mixed proportion of organopolysiloxane A and organic polysiloxane B is not particularly limited, but is preferably adjusted to and makes in organic polysiloxane B with the mol ratio (hydrogen atom/thiazolinyl) of whole thiazolinyls in the hydrogen atom of silicon atom bonding and organopolysiloxane A to be 0.7 ~ 1.05.Wherein, preferably mixed proportion is adjusted to and is 0.8 ~ 1.0.

As hydrosilylation catalysts, preferably use platinum group metal class catalyst.As platinum group metal class catalyst, the catalyst such as platinum class, palladium class, rhodium class can be enumerated, from economy, reactive aspect, particularly preferably use platinum class catalyst.As platinum group metal class catalyst, known platinum group metal class catalyst can be used.Specifically, platinum micro mist can be enumerated; Platinum black; The chloroplatinic acid such as Tetrachloroplatinate, chloroplatinic acid; Platinum tetrachloride; The alcoholic compound of chloroplatinic acid, aldehyde compound; Or the alkene complex of platinum, alkenyl siloxane complex compound, carbonyl complex; Etc..

As the use amount of hydrosilylation catalysts, relative to total quality 100 mass parts of organopolysiloxane A and organic polysiloxane B, be preferably 0.1 ~ 20 mass parts, be more preferably 1 ~ 10 mass parts.

The weight average molecular weight of bridging property organopolysiloxane is not particularly limited, from the excellent and film forming of treatability also excellent and more suppress the decomposition of silicones under high-temperature process condition in consider, the weight average molecular weight of the polystyrene conversion measured by GPC (gel permeation chromatography) is preferably 1,000 ~ 5,000,000,2 are more preferably, 000 ~ 3,000,000.

The viscosity of bridging property organopolysiloxane is preferably 10 ~ 5000mPas, is more preferably 15 ~ 3000mPas.It should be noted that, when being not particularly illustrated, the value of the viscosity described in this description is the value measured at 25 DEG C.

In addition, for the specifically commercially available trade name of bridging property organopolysiloxane or model, as the bridging property organopolysiloxane without aromatic series base, KNS-320A can be enumerated, KS-847 (being organosilicon Inc. of SHIN-ETSU HANTOTAI), TPR6700 (Mo Mendifu functional material (Momentive Performance Materials) Japanese contract Inc.), the combination of vinyl organosilicon " 8500 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system), the combination of vinyl organosilicon " 11364 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system), the combination etc. of vinyl organosilicon " 11365 " (Huang Chuan chemical industrial company system) and methylhydrogenpolysi,oxane " 12031 " (Huang Chuan chemical industrial company system).

Containing silicone oil in silicone layer 14.Silicone oil is different from above-mentioned bridging property organopolysiloxane and do not react, do not have non-crosslinked (non-reacted) organopolysiloxane of bridging property with bridging property organopolysiloxane.

The kind of silicone oil is not particularly limited, and can exemplify: the pure silicon oil such as dimethyl polysiloxane, methyl phenyl silicone, diphenylpolysiloxane; The modified silicon oil of the gained such as polyether-based, halogen group has been imported at the side chain of pure silicon oil or end.

It should be noted that, for the specifically commercially available trade name of silicone oil or model, as the silicone oil with aromatic series base (such as phenyl), KTSF433 (contract Inc. of Mo Mendifu functional material Japan), KF-50, KF-53, KF-54 (chemical industrial company of SHIN-ETSU HANTOTAI system), SH550 (Dong Li Dow Corning Corporation system) etc. can be enumerated.

As the silicone oil without aromatic series base, SH200 (Dong Li Dow Corning Corporation system), KNS-330 (chemical company of SHIN-ETSU HANTOTAI system) etc. can be enumerated.

Silicon oil viscosity is not particularly limited, from being easy to ooze out into silicone layer 14 surface and the more excellent aspect of the transparency of the more excellent aspect of the fissility of glass substrate 16 and the glass substrate 16 after peeling off is considered, being preferably 100 ~ 6000cP, being more preferably 100 ~ 3000cP, more preferably 125 ~ 1000cP.

In silicone layer 14, the content of silicone oil is not particularly limited, excellent from the viewpoint of the fissility of glass substrate 16 and the transparency of glass substrate after peeling off is more excellent, be preferably 6 ~ 20 mass parts relative to silicones 100 mass parts, be more preferably 6 ~ 15 mass parts, more preferably 8 ~ 15 mass parts.

The one formed in the silicone oil contained in the silicones of above-mentioned silicone layer 14 and silicone layer 14 has aromatic series base, and another one does not have aromatic series base in fact.In other words, the one only in silicones and silicone oil has aromatic series base.As mentioned above, if this mode, then the compatibility of silicones and silicone oil is bad, thus its result, and silicone oil easily oozes out into silicone layer 14 surface, even if glass substrate 16 is also easily peeled off after high-temperature heating treatment.

It should be noted that, silicones or silicone oil do not have in fact aromatic series base and refer to can have aromatic series base in the scope not affecting effect of the present invention, more particularly, refer in silicones or silicone oil and be less than 1 % by mole with the containing ratio of aromatic series base in whole organic groups of silicon atom bonding.

Silicones or silicone oil have aromatic series base and refer to, the aromatic series base contained is more than above-mentioned containing ratio.

The kind of aromatic series base is not particularly limited, and can enumerate the aromatic series base (such as aromatic hydrocarbyl or aromatic heterocycle) etc. of monovalence.Wherein, from the aspect easily preparing silicones or silicone oil, be preferably aromatic hydrocarbyl, be particularly preferably phenyl.

As aforesaid way, more particularly, the following two kinds pattern is had: silicone oil has aromatic series base and silicones does not have in fact the situation (mode A) of aromatic series base; Silicones has aromatic series base and silicone oil does not have in fact the situation (mode B) of aromatic series base.Wherein, from the viewpoint of more easily preparing silicone layer 14 and the fissility of glass substrate 16 is more excellent, be preferably mode A.

When mode A, the aromatic series base contained in silicone oil is preferably phenyl, wherein, and aspect that the transparency of glass substrate 16 of peel off after more excellent more excellent from the fissility of the glass substrate 16 after high-temperature heating treatment, is preferably 5 ~ 50 % by mole with the containing ratio of aromatic series base (particularly phenyl) in whole organic groups of silicon atom bonding, is more preferably 5 ~ 30 % by mole, more preferably 10 ~ 30 % by mole in silicone oil.

It should be noted that, when mode A, in silicone oil, the bonding position of aromatic series base is not particularly limited, and can enumerate two ends and/or side chain.In addition, as the group beyond the phenyl contained in silicone oil, such as, can enumerate alkyl (such as methyl, ethyl, propyl group etc.).

On the other hand, when mode B, the aromatic series base contained in silicones is preferably phenyl, wherein, more excellent from the viewpoint of the fissility of the glass substrate 16 after high-temperature heating treatment, be preferably 5 ~ 90 % by mole with the containing ratio of aromatic series base (particularly phenyl) in whole organic groups of silicon atom bonding, be more preferably 30 ~ 90 % by mole in silicones.It should be noted that, when mode B, as the group except phenyl contained in silicones, such as, can enumerate alkyl (such as methyl, ethyl, propyl group etc.).

It should be noted that, as the silicone oil with aromatic series base, from the viewpoint of excellent with the compatibility relation of silicones, such as, preferably can enumerate methyl phenyl silicone oil.

In addition, as the silicones with aromatic series base, such as, can enumerate the silicones that the bridging property organopolysiloxane with phenyl is cross-linked.

[glass laminate and manufacture method thereof]

As mentioned above, glass laminate 10 of the present invention is the duplexers having support base material 12, glass substrate 16 and the silicone layer between them 14.

The manufacture method of glass laminate 10 of the present invention is not particularly limited, in order to obtain the duplexer of peel strength (x) higher than peel strength (y), preferably making the bridging property organopolysiloxane crosslinking curing of regulation on the surface at support base material 12 thus forming the method for silicone layer 14.I.e. following method: form the layer comprising bridging property organopolysiloxane and silicone oil on the surface of support base material 12, make bridging property organopolysiloxane crosslinked on the surface at support base material 12 thus form silicone layer 14 (cross-linked silicone), then, at the silicones surface layer laminated glass substrate 16 of silicone layer 14, thus manufacture glass laminate 10.

It is believed that, when making bridging property organopolysiloxane solidify on support base material 12 surface, by during curing reaction and the interaction on support base material 12 surface and boning, the peel strength on silicones and support base material 12 surface improves.Therefore, even if glass substrate 16 is made up of identical material with support base material 12, also difference can be set to silicone layer 14 and peel strength between the two.

Below, by formed on the surface of support base material 12 comprise bridging property organopolysiloxane and silicone oil layer, make bridging property organopolysiloxane be cross-linked on the surface thus the operation forming silicone layer 14 is called resin bed formation process at support base material 12, operation silicones surface layer laminated glass substrate 16 at silicone layer 14 being formed glass laminate 10 is called lamination process, is described in detail the flow process of each operation.

(resin bed formation process)

In resin bed formation process, form the layer comprising bridging property organopolysiloxane and silicone oil on the surface of support base material 12, make bridging property organopolysiloxane crosslinked on the surface at support base material 12 thus form silicone layer 14.

In order to form the layer comprising bridging property organopolysiloxane and silicone oil on support base material 12, be preferably used in solvent the coating composition being dissolved with bridging property organopolysiloxane and silicone oil, said composition is coated on layer support base material 12 being formed solution, then except desolventizing, the layer comprising bridging property organopolysiloxane and silicone oil is formed.By the adjustment etc. of the concentration to the bridging property organopolysiloxane in composition and silicone oil, the thickness of the layer comprising bridging property organopolysiloxane and silicone oil can be controlled.

As solvent, as long as bridging property organopolysiloxane and silicone oil easily can be dissolved and the solvent of removing of can easily carrying out volatilizing under operating environment, be just not particularly limited.Specifically, such as butyl acetate, heptane, 2-HEPTANONE, 1-methoxy-2-propanol acetic acid esters, toluene, dimethylbenzene, THF, chloroform etc. can be exemplified.

Be coated with at support base material 12 method comprising the composition of bridging property organopolysiloxane and silicone oil to be on the surface not particularly limited, can known method be used.Such as can enumerate spraying process, mould is coated with method, spin-coating method, Dipcoat method, rolling method, stick coating method, silk screen print method, gravure coating process etc.

Afterwards, also can implement as required for the drying process except desolventizing.The method of dry process is not particularly limited, such as, can enumerate at reduced pressure conditions except the method etc. of carrying out heating at the method for desolventizing, the temperature that can not be cured at bridging property organopolysiloxane.

Then, make the bridging property organopolysiloxane on support base material 12 crosslinked thus form silicone layer 14.More particularly, as shown in Fig. 2 (A), in this operation, form silicone layer 14 on the surface at least one of support base material 12.

As mentioned above, the method for solidification (being cross-linked) suitably selects the suitableeest method according to the cross-linked form of bridging property organopolysiloxane, such as, can enumerate heating, exposure-processed.Wherein, when bridging property organopolysiloxane is cross-linked by hydrosilylation reactions, condensation reaction, radical reaction, from the viewpoint of what can obtain the adaptation of glass substrate 16 and the silicones of excellent heat resistance, manufacture silicone layer 14 preferably by heat cure.

Below, the mode of heat cure is described in detail.

As long as make the temperature conditions of bridging property organopolysiloxane heat cure can improve silicone layer 14 heat resistance and can control as mentioned above stacked with glass substrate 16 after peel strength (y) scope in be just not particularly limited, be preferably 150 ~ 300 DEG C, be more preferably 180 ~ 250 DEG C.In addition, the heat time be usually preferably 10 ~ 120 minutes, be more preferably 30 ~ 60 minutes.When the temperature of heat cure is too low, the flatness of heat resistance, silicone layer 14 declines, and on the other hand when temperature is too high, peel strength (y) is too low, all likely weakens the adaptation of glass substrate 16 and silicone layer 14.

It should be noted that, bridging property organopolysiloxane can carry out Post RDBMS (formally solidifying) after carrying out precuring (preparation solidification), is cured thus.By carrying out precuring, the more excellent silicone layer of heat resistance 14 can be obtained.Preferably then carry out precuring after removal of the solvent, in this case, not intended distinction from layer except desolventizing formed containing the layer of bridging property organopolysiloxane and silicone oil operation and carry out the operation of precuring.

(lamination process)

Lamination process is laminated glass substrate 16 on the silicones face of the silicone layer 14 obtained by above-mentioned resin bed formation process, is possessed the operation of the glass laminate 10 of the layer of the layer of support base material 12, silicone layer 14 and glass substrate 16 successively.More particularly, as shown in Fig. 2 (B), using silicone layer 14 with surface (the 1st interarea of the silicone layer) 14a of support base material 12 side opposite side and there is the 1st interarea 16a and the 2nd interarea 16b the 1st interarea 16a of glass substrate 16 as lamination surface, by stacked to silicone layer 14 and glass substrate 16, obtain glass laminate 10.

The method that glass substrate 16 is layered on silicone layer 14 is not particularly limited, known method can be adopted.

Such as, the method for superimposed glass substrate 16 on the surface of silicone layer 14 under atmospheric pressure environment can be enumerated.It should be noted that, on the surface of silicone layer 14 after superimposed glass substrate 16, roller can be used as required, glass substrate 16 is pressure bonded to silicone layer 14 by press (press).By utilizing the pressing of roller or press, the bubble between the layer being mixed into silicone layer 14 and glass substrate 16 can be removed with comparalive ease, because of but preferred.

When carrying out pressing by vacuum layer platen press, Vacuum Pressure method for making, bubble can be suppressed to be mixed into, guarantee good closely sealed, because of but preferred.By carrying out pressing under vacuo, also have the following advantages: even if when remaining micro-bubble, bubble also can not grow because of heating, is difficult to the strain defect causing glass substrate 16.

During laminated glass substrate 16, preferably fully clean the surface of the glass substrate 16 contacted with silicone layer 14 and carry out stacked in the environment that cleanliness factor is high.Cleanliness factor is higher, and the flatness of glass substrate 16 is better, because of but preferred.

It should be noted that, after laminated glass substrate 16, pre-anneal treatment (heating) can be carried out as required.By carrying out this pre-anneal treatment, the adaptation of stacked glass substrate 16 pairs of silicone layers 14 can be improved, obtain suitable peel strength (y), be difficult to when component formation process described later the position skew etc. producing component used for electronic device, the productivity ratio of electronic device improves.

The condition of pre-anneal treatment suitably selects the suitableeest condition according to the kind of used silicone layer 14, from more suitably arranging the aspect of glass substrate 16 with the peel strength (y) of silicone layer 14, preferably more than 300 DEG C, (preferably 300 ~ 400 DEG C) carry out the heating of more than 5 minutes (being preferably 5 ~ 30 minutes).

It should be noted that, the formation of silicone layer 14 is not limited to said method.

Such as, when using to the adaptation of the silicone surface material higher than glass substrate 16 support base material 12, bridging property organopolysiloxane can be made at certain fissility to solidify the film manufacturing silicones on the surface, make this film between glass substrate 16 and support base material 12, carry out stacked simultaneously.

In addition, when solidified by bridging property organopolysiloxane the caking property that obtains for glass substrate 16 fully low and fully high for support base material 12, bridging property organopolysiloxane can be made to solidify between glass substrate 16 and support base material 12 and to form silicone layer 14.

In addition, even if when support base material 12 is made up of the glass material same with glass substrate 16, also can implements to improve the close-burning process on support base material 12 surface and improve peel strength to silicone layer 14.Such as illustrative have: the chemical method (primary coat process) chemically improving bed knife as silane coupler; The physical method of the increase surface active groups as processed in flame (flame); The mechanical processing method increasing grip by increasing surface roughness as blasting treatment; Etc..

(glass laminate)

Glass laminate 10 of the present invention may be used for various uses, such as, can enumerate and manufacture display unit panel described later, PV, thin-film secondary battery, be formed with the purposes etc. of the electronic unit such as semiconductor wafer of circuit on surface.It should be noted that, in this purposes, glass laminate more than 10 is exposed (such as more than 1 hour) under hot conditions (such as more than 350 DEG C).

Herein, display unit panel comprises: LCD, OLED, Electronic Paper, plasma display device, field emission panel, quantum dot LED panel, MEMS (MEMS (MicroElectro Mechanical Systems)) shutter (シャッター) panel etc.

[there is glass substrate and the manufacture method thereof of component]

In the present invention, use above-mentioned duplexer to manufacture the glass substrate (there is the glass substrate of component used for electronic device) with component comprising glass substrate and component used for electronic device.

This manufacture method with the glass substrate of component is not particularly limited, from the aspect that the productivity ratio of electronic device is excellent, be preferably as follows method: the glass substrate in above-mentioned glass laminate forms component used for electronic device, manufacture the duplexer with component used for electronic device, using the interface, glass substrate side of silicone layer as release surface, isolate the glass substrate with component and the support base material with silicone layer from the obtained duplexer with component used for electronic device.

Below, operation glass substrate in above-mentioned glass laminate forming component used for electronic device to manufacture the duplexer with component used for electronic device is called component formation process, the operation isolating the glass substrate with component and the support base material with silicone layer using the interface, glass substrate side of silicone layer as release surface from the duplexer with component used for electronic device is called separation circuit.

Below, the material used in each operation and flow process are described in detail.

(component formation process)

Component formation process is the operation glass substrate 16 in the glass laminate 10 obtained in above-mentioned lamination process being formed component used for electronic device.More particularly, as shown in Fig. 2 (C), at the upper formation of the 2nd interarea 16b (exposing surface) component 20 used for electronic device of glass substrate 16, obtain the duplexer 22 with component used for electronic device.

First, the component used for electronic device 20 used in this operation is described in detail, afterwards the flow process of operation is described in detail.

(component used for electronic device (functional element))

Component 20 used for electronic device to be formed on the glass substrate 16 in glass laminate 10 and to form the component at least partially of electronic device.More particularly, as component 20 used for electronic device, can enumerate at display unit panel, solar cell, thin-film secondary battery or be formed with the component (such as display device component, component used for solar batteries, thin-film secondary battery component, electronic component-use circuit) used in the electronic unit such as semiconductor wafer etc. of circuit on surface.

Such as, as component used for solar batteries, when silicon type, the transparency electrodes such as the tin oxide of positive pole can be enumerated, with the metal etc. of the silicon layer that p layer/i layer/n layer represents and negative pole, other can enumerate the various components etc. corresponding to compound type, dye sensitization type, quantum point type etc.

In addition, as thin-film secondary battery component, when type lithium ion, can enumerate transparency electrode, the lithium compound of dielectric substrate, the metal of current collection layer, the resin etc. as sealant of the metal or metal oxide etc. of positive pole and negative pole, other can enumerate the various components etc. corresponding to ni-mh type, polymer-type, ceramic electrolyte type etc.

In addition, as electronic component-use circuit, when CCD or CMOS, the metal of conductive part can be enumerated, the silica, silicon nitride etc. of insulation division, other can enumerate the various components etc. corresponding to the various sensor such as pressure sensor, acceleration transducer or rigidity printed base plate, flexible printed board, hard and soft printed base plate etc.

(flow process of operation)

The above-mentioned manufacture method with the duplexer 22 of component used for electronic device is not particularly limited, according to the kind of the member of formation of component used for electronic device, known method is utilized to form component 20 used for electronic device on the surface at the 2nd interarea 16b of the glass substrate 16 of glass laminate 10.

It should be noted that, component 20 used for electronic device can not be whole (hereinafter referred to as " the whole components ") of the final component formed on the 2nd interarea 16b of glass substrate 16, and can be a part (hereinafter referred to as " partial component ") for whole component.Also the glass substrate with partial component peeled off from silicone layer 14 can be made in operation afterwards the glass substrate (being equivalent to electronic device described later) with whole component.

In addition, for the glass substrate with whole component peeled off from silicone layer 14, also can at other component used for electronic device of the upper formation of its release surface (the 1st interarea 16a).In addition, also can have the duplexer assembling of whole component, then support base material 12 be peeled off from the duplexer with whole component, thus manufacture electronic device.In addition, two duplexers with whole component also can be used to assemble, afterwards two support base materials 12 be peeled off from the duplexer with whole component, thus manufacture the glass substrate with component with two glass substrates.

Such as, if for the situation manufacturing OLED, in order to the glass substrate 16 in glass laminate 10 with the surface of silicone layer 14 side opposite side (be equivalent to the 2nd interarea 16b of glass substrate 16) form organic EL structure, carry out following various layer to be formed and process: form transparency electrode, and then on the face being formed with transparency electrode evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer etc., form backplate, use sealing plate to seal, etc.Formed and process as above-mentioned layer, specifically can enumerate the binder-treatment etc. of such as film forming process, vapor deposition treatment, sealing plate.

In addition, such as when manufacturing TFT-LCD, there is following various operation: TFT formation process, on the 2nd interarea 16b of the glass substrate 16 of glass laminate 10, use anti-corrosion liquid, the metal film formed by the conventional membrane formation process such as CVD and sputtering method and metal oxide film etc. carry out pattern formation, thus forms thin film transistor (TFT) (TFT); CF formation process, on the 2nd interarea 16b of the glass substrate 16 of another glass laminate 10, uses anti-corrosion liquid to form colour filter (CF) in the patterning; And bonding process, by stacked for the duplexer with CF obtained in the duplexer with TFT obtained in TFT formation process and CF formation process; Etc..

In TFT formation process, CF formation process, use well-known photoetching (photolithography) technology, etching technique etc., the 2nd interarea 16b of glass substrate 16 forms TFT or CF.Now, as the coating fluid that pattern is formed, anti-corrosion liquid can be used.

It should be noted that, before formation TFT, CF, also can clean the 2nd interarea 16b of glass substrate 16 as required.As cleaning method, well-known dry clean or wet-cleaned can be used.

In bonding process, the thin film transistor (TFT) forming surface making the duplexer with TFT is facing with the colour filter forming surface of the duplexer with CF, uses sealant (such as box (cell) formation ultraviolet hardening sealant) to fit.Afterwards, in the box formed by the duplexer with TFT and the duplexer with CF, liquid crystal material is injected.As the method injecting liquid crystal material, such as, there is decompression injection method, drip injection method.

(separation circuit)

As shown in Fig. 2 (D), separation circuit is using the interface of silicone layer 14 and glass substrate 16 as release surface, isolate the glass substrate 16 (there is the glass substrate of component) and the support base material 12 that are laminated with component 20 used for electronic device from the duplexer 22 with component used for electronic device obtained by above-mentioned component formation process, obtain the operation of the glass substrate 24 with component comprising component 20 used for electronic device and glass substrate 16.

Component used for electronic device 20 during stripping on glass substrate 16 is the parts of the component forming required whole formation, also can form remaining member of formation after isolation on glass substrate 16.

The method that glass substrate 16 and support base material 12 are peeled off is not particularly limited.Specifically, such as, can insert sharp blade-like object at glass substrate 16 and the interface of silicone layer 14, provide the starting point of stripping, then jet water and compressed-air actuated fluid-mixing, peel off thus.Be preferably, by the duplexer 22 with component used for electronic device according to support base material 12 be upside, component used for electronic device 20 side is that the mode of downside is arranged on platform, make component 20 side used for electronic device vacuum suction on platform (two-sided be laminated with support base material sequentially carry out), in this condition, cutter is first made to invade glass substrate 16-silicone layer 14 interface.And, afterwards with multiple vacuum suction pad adsorbent support base material 12 side, from inserting the near sites of cutter, promote vacuum suction pad successively.Thus, forms air layer at silicone layer 14 and the interface of glass substrate 16, the cohesion failure mechanics of silicone layer 14, this air layer to interface, condense whole expansion of failure mechanics, can easily support base material 12 be peeled off.

In addition, support base material 12 can be stacked with new glass substrate, thus manufacture glass laminate 10 of the present invention.

It should be noted that, when there is the glass substrate 24 of component from duplexer 22 separation with component used for electronic device, by utilizing winding-up and the controlled humidity of ion generator (Ionizer), can suppress the fragment Electrostatic Absorption of silicone layer 14 further on the glass substrate 24 with component.

The above-mentioned manufacture method with the glass substrate 24 of component is applicable to being manufactured on the compact display apparatus used in mobile phone, PDA and so on mobile terminal.Display unit is LCD or OLED mainly, comprises TN type, STN type, FE type, TFT type, mim type, IPS type, VA type etc. as LCD.Substantially, can be applied in the situation of any one display unit in passive driving types, active-drive.

As the glass substrate 24 with component manufactured by said method, can enumerate: the display unit panel with glass substrate and display device component, the solar cell with glass substrate and component used for solar batteries, there is the thin-film secondary battery of glass substrate and thin-film secondary battery component, there is the electronic unit etc. of glass substrate and component used for electronic device.As display unit panel, comprise liquid crystal panel, organic EL panel, plasma display device, field emission panel etc.

Embodiment

Below, by embodiment etc., the present invention is specifically described, but the invention is not restricted to these examples.

In following examples 1 ~ 5, comparative example 1 ~ 2, as glass substrate, use by the glass plate formed without alkali borosilicate glass (vertical 200mm, horizontal 200mm, thickness of slab 0.2mm, linear expansion coefficient 38 × 10 ^-7/ DEG C, Asahi Glass Inc. trade name " AN100 ").In addition, as support base material, use by the same glass plate (vertical 240mm, horizontal 240mm, thickness of slab 0.5mm, the linear expansion coefficient 38 × 10 that form without alkali borosilicate glass ^-7/ DEG C, Asahi Glass Inc. trade name " AN100 ").

< embodiment 1 >

First, after pure water cleaning is carried out to the support base material of thickness of slab 0.5mm, and then carry out UV cleaning, make it to clean.

Then, will there is at two ends the olefinic organic based polysiloxane (vinyl organosilicon, Huang Chuan chemical industrial company system, 8500) of vinyl and there is methylhydrogenpolysi,oxane (Huang Chuan chemical industrial company system, the 12031) mixture of hydrogen silicyl in molecule.1:1 is set to the mol ratio of the hydrogen atom of silicon atom bonding in total vinyl in olefinic organic based polysiloxane and methylhydrogenpolysi,oxane.Relative to resinous principle 100 mass parts, add the platinum class catalyst (Huang Chuan chemical industrial company system, CAT12070) of 5 weight portions.In addition, add methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), heptane, make the solution comprising bridging property organopolysiloxane.Utilize spin coater (rotating speed 300rpm, 15 seconds) to be coated on the 1st interarea of support base material by this solution, thus arrange on support base material and comprise uncured bridging property organopolysiloxane and layer (the coating weight 20g/m of silicone oil ²).

It should be noted that, relative to total quality 100 mass parts of olefinic organic based polysiloxane and methylhydrogenpolysi,oxane, the use amount of methyl phenyl silicone oil is set to 8 mass parts.In addition, relative to total quality 100 mass parts of olefinic organic based polysiloxane and methylhydrogenpolysi,oxane, the use amount of heptane is set to 100 mass parts.It should be noted that, the containing ratio of the phenyl contained in methyl phenyl silicone oil is relative to being 5 % by mole with whole organic groups of silicon atom bonding in silicone oil.

Then, be heating and curing at 230 DEG C 10 minutes in an atmosphere, the 1st interarea of support base material is formed the silicone layer of thickness 10 μm.It should be noted that, in this approach, the silicones of silicone layer does not have aromatic series base, and the methyl phenyl silicone oil as silicone oil has aromatic series base (phenyl).In addition, silicone layer is transparent.

Afterwards, at room temperature fitted by the silicones aspect of vacuum pressing by glass substrate and support base material, obtain glass laminate A.

In the glass laminate A obtained, support base material and glass substrate are with not producing bubble not closely sealed with silicone layer, do not strain shape defect yet, and flatness is also good.

Then, carry out heating for 60 minutes, be cooled to room temperature under blanket of nitrogen at 350 DEG C to glass laminate A, result does not observe the apparent changes such as being separated of support base material and glass substrate in glass laminate A, the foaming of silicone layer or albefaction.

Thereafter, glass laminate A everywhere in a bight, place, the stainless steel cutter of inserting thickness 0.1mm in the interface of glass substrate and support silicone layer, form the starting point portion of peeling off, make vacuum suction pad be adsorbed on the face in glass substrate and support base material non-peel-away face separately simultaneously, apply external force along the direction that glass substrate and support base material are separated from each other, glass substrate is separated without breakage with support base material.Herein, while jetting except electronic fluids by ion generator (Keyemce Inc.) to this interface, carry out the insertion of cutter.Specifically, continue winding-up except electronic fluids by ion generator to formed space, while promote vacuum suction pad.

It should be noted that, silicone layer is separated from glass substrate together by with support base material, by this results verification to peel strength (y) higher than the interface of silicone layer and glass substrate of, the peel strength (x) at the layer of support base material and the interface of silicone layer.In addition, the glass baseplate surface after stripping is transparent.

< embodiment 2 >

Use methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 3000cp) to replace methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), obtain glass laminate B with method similarly to Example 1 in addition.

It should be noted that, the containing ratio of the phenyl contained in the methyl phenyl silicone oil used is relative to being 5 % by mole with whole organic groups of silicon atom bonding in silicone oil.

In addition, the outward appearance of silicone layer is also transparent after just manufacturing, and is also transparent thereon after laminated glass substrate.

In the glass laminate B obtained, support base material and glass substrate are with not producing bubble not closely sealed with silicone layer, do not strain shape defect yet, and flatness is also good.

Then, to the heating that glass laminate B carries out similarly to Example 1, result does not observe the apparent change such as foaming or albefaction of being separated of support base material and glass substrate in glass laminate B, silicone layer.

Thereafter, for glass laminate B, carry out being separated of support base material and glass substrate with method similarly to Example 1, glass substrate is separated without breakage with support base material by result.It should be noted that, silicone layer is separated from glass substrate together by with support base material.By this results verification to peel strength (y) higher than the interface of silicone layer and glass substrate of, the peel strength (x) at the layer of support base material and the interface of silicone layer.In addition, the glass baseplate surface after stripping is transparent.

< embodiment 3 >

Use methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-54, viscosity 400cp) to replace methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), obtain glass laminate C with method similarly to Example 1 in addition.

It should be noted that, the containing ratio of the phenyl contained in the methyl phenyl silicone oil used is relative to being 25 % by mole with whole organic groups of silicon atom bonding in silicone oil.

In addition, the outward appearance of silicone layer omits gonorrhoea, thereon bleach after laminated glass substrate after just manufacturing.

In the glass laminate C obtained, support base material and glass substrate are with not producing bubble not closely sealed with silicone layer, do not strain shape defect yet, and flatness is also good.

Then, to the heating that glass laminate C carries out similarly to Example 1, result does not observe the apparent change such as foaming or albefaction of being separated of support base material and glass substrate in glass laminate C, silicone layer.

Then, for glass laminate C, carry out being separated of support base material and glass substrate with method similarly to Example 1, glass substrate is separated without breakage with support base material by result.It should be noted that, silicone layer is separated from glass substrate together by with support base material.By this results verification to peel strength (y) higher than the interface of silicone layer and glass substrate of, the peel strength (x) at the layer of support base material and the interface of silicone layer.It should be noted that, the glass baseplate surface after stripping is gonorrhoea slightly.

< embodiment 4 >

Methyl phenyl silicone oil (Dong Li Dow Corning Corporation system, SH550, viscosity 125cp) is used to replace methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), in addition, glass laminate D is obtained with method similarly to Example 1.

In the glass laminate D obtained, support base material and glass substrate are with not producing bubble not closely sealed with silicone layer, do not strain shape defect yet, and flatness is also good.

Then, to the heating that glass laminate E carries out similarly to Example 1, result does not observe the apparent change such as foaming or albefaction of being separated of support base material and glass substrate in glass laminate D, silicone layer.

Then, for glass laminate D, carry out being separated of support base material and glass substrate with method similarly to Example 1, glass substrate is separated without breakage with support base material by result.It should be noted that, silicone layer is separated from glass substrate together by with support base material.By this results verification to peel strength (y) higher than the interface of silicone layer and glass substrate of, the peel strength (x) at the layer of support base material and the interface of silicone layer.It should be noted that, the glass baseplate surface after stripping is gonorrhoea slightly.

< embodiment 5 >

Methyl phenyl silicone oil (contract Inc. of Mo Mendifu functional material Japan, TSF433, viscosity 450cp) is used to replace methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), in addition, glass laminate E is obtained with method similarly to Example 1.

In the glass laminate E obtained, support base material and glass substrate are with not producing bubble not closely sealed with silicone layer, do not strain shape defect yet, and flatness is also good.

Then, to the heating that glass laminate E carries out similarly to Example 1, result does not observe the apparent change such as foaming or albefaction of being separated of support base material and glass substrate in glass laminate E, silicone layer.

Then, for glass laminate E, carry out being separated of support base material and glass substrate with method similarly to Example 1, glass substrate is separated without breakage with support base material by result.It should be noted that, silicone layer is separated from glass substrate together by with support base material.By this results verification to peel strength (y) higher than the interface of silicone layer and glass substrate of, the peel strength (x) at the layer of support base material and the interface of silicone layer.It should be noted that, the glass baseplate surface after stripping is gonorrhoea slightly.

In addition, the silicon oil viscosity illustrating and use in embodiment 1 ~ 5 and phenyl containing ratio is gathered below.

Table 1

	Silicon oil viscosity	Phenyl containing ratio
			Embodiment 1	100cP	5 % by mole
Embodiment 2	3000cP	5 % by mole
			Embodiment 3	400cP	25 % by mole
Embodiment 4	125cP	25 % by mole
			Embodiment 5	450cP	25 % by mole

< comparative example 1 >

Except not using methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), obtain glass laminate X with method similarly to Example 1.

For obtained glass laminate X, carry out being separated of support base material and glass substrate with method similarly to Example 1, result silicone layer and glass substrate are difficult to peel off, and glass substrate also has and breaks.

< comparative example 2 >

Use methyl-silicone oil (Dong Li Dow Corning Corporation system, SH200, viscosity 200cP) 0.5 weight portion to replace methyl phenyl silicone oil (chemical industrial company of SHIN-ETSU HANTOTAI system, KF-50, viscosity 100cP), obtain glass laminate Y with method similarly to Example 1 in addition.It should be noted that, the manner is equivalent to the mode of embodiment 7 in existing document (WO2011/142280 pamphlet), does not all contain aromatic series base in silicones and silicone oil.

For obtained glass laminate Y, carry out being separated of support base material and glass substrate with method similarly to Example 1, result silicone layer and glass substrate are difficult to peel off, and glass substrate also has and breaks.

When embodiment 1 ~ 5, even if after enforcement high-temperature heating treatment, also can easily glass substrate thin for thickness be peeled off.It should be noted that, in embodiment 1 and 2, the surface (release surface) of the glass substrate after stripping keeps transparent, on the other hand, omits gonorrhoea in embodiment 3 ~ 5.Infer this is because, in embodiment 3 ~ 5, the part oozing out into the silicone oil on silicone layer surface is transferred on glass substrate.Confirm according to the above results, under the silicon oil condition used in embodiment 1 and 2, the spatter property of the glass baseplate surface after stripping is more excellent.

On the other hand, do not using the comparative example 1 of silicone oil and all do not containing in silicones and silicone oil in the comparative example 2 of aromatic series base, fissility is poor.

< embodiment 6 >

In this example, the glass laminate A obtained in embodiment 1 is used to manufacture OLED.

First, by the 2nd interarea of the glass substrate of plasma CVD method in glass laminate A successively film forming go out silicon nitride, silica, non-crystalline silicon.Then, utilize ion doping apparatus in amorphous silicon layer, inject the boron of low concentration, carry out the heating of 450 DEG C, 60 minutes under nitrogen atmosphere to carry out Dehydroepiandrosterone derivative.Then, laser anneal device is utilized to carry out the crystallization process of amorphous silicon layer.Then, by utilizing photolithographic etching and ion doping apparatus, in amorphous silicon layer, injecting the phosphorus of low concentration, forming the TFT zone of N-type and P type.Then, go out silicon oxide film by plasma CVD method in the 2nd interarea side film forming of glass substrate and form gate insulating film, then going out molybdenum by sputtering film-forming, utilizing and use photolithographic etching to form gate electrode.Then, utilize photoetching process and ion doping apparatus, inject boron and the phosphorus of high concentration in N-type, P type desired region separately, form source area and drain region.Then, on the 2nd interarea side of glass substrate, by utilizing the silica film forming of plasma CVD method to form interlayer dielectric, sputtering method is utilized to form the film forming of aluminium, and by using photolithographic etching to form TFT electrode.Then, the heating of 450 DEG C, 60 minutes is carried out under a hydrogen atmosphere to carry out hydrogenation treatment, then by utilizing the silicon nitride film forming of plasma CVD method to form passivation layer.Then, at the 2nd interarea side coated UV line curable resin of glass substrate, lithographically planarization layer and contact hole is formed.Then, go out tin indium oxide by sputtering film-forming, utilize and use photolithographic etching to form pixel electrode.

Then, by vapour deposition method on the 2nd interarea side of glass substrate successively film forming go out as hole injection layer 4,4 '; 4 "-three (3-methylphenylphenyl amino) triphenylamine, as two [(N-naphthyl)-N-phenyl] benzidine of hole transmission layer, be mixed with 2 of 40 volume % as luminescent layer, oxine aluminium complex (the Alq of two [4-[N-(4-methoxyphenyl)-N-phenyl] aminostyryl] naphthalene-1, the 5-dimethoxy nitrile (BSN-BCN) of 6- ₃), as the Alq of electron transfer layer ₃.Then, go out aluminium by sputtering film-forming, utilize and use photolithographic etching to form opposite electrode.Then, the 2nd interarea side of glass substrate seals across the tack coat of ultraviolet hardening another sheet glass substrate of fitting.Organic EL structure is formed on the glass substrate by above-mentioned flow process.The glass laminate A (hereinafter referred to as panel A) on the glass substrate with organic EL structure is the duplexer (having the display unit panel of support base material) with component used for electronic device of the present invention.

Next, make the sealing side vacuum suction of panel A in platform, the stainless steel cutter of the interface inserting thickness 0.1mm of the glass substrate then in the bight of panel A and silicone layer, the starting point of stripping is provided in the interface of glass substrate and silicone layer.Then, with the support base material surface of vacuum suction pad absorption panel A, absorption layer is then made to increase.Herein, while jetting except electronic fluids by ion generator (Keyemce Inc.) to this interface, carry out the insertion of cutter.Then, continue to be jetted except electronic fluids to formed space by ion generator, while promote vacuum suction pad.Its result, platform only remains the glass substrate being formed with organic EL structure, and the support base material can with silicone layer is peeled off.

Next, the release surface of the glass substrate be separated with method is similarly to Example 1 cleaned, laser cutter or line sliver (Scribe & Break) method is used to cut the glass substrate after separation, after being divided into multiple box (cell), the glass substrate and counter substrate that are formed with organic EL structure are assembled, implements module generation operation and make OLED.The OLED so obtained can not have problems in performance.

< embodiment 7 >

In this example, the glass laminate A obtained in embodiment 1 is used to manufacture LCD.

First, prepare two panels glass laminate A, by the 2nd interarea of the glass substrate in plasma CVD method glass laminate A1 one of wherein successively film forming go out silicon nitride, silica, non-crystalline silicon.Then, utilize ion doping apparatus in amorphous silicon layer, inject the boron of low concentration, carry out the heating of 450 DEG C, 60 minutes under nitrogen atmosphere to carry out Dehydroepiandrosterone derivative.Then, laser anneal device is utilized to carry out the crystallization process of amorphous silicon layer.Then, by utilizing photolithographic etching and ion doping apparatus, in amorphous silicon layer, injecting the phosphorus of low concentration, forming the TFT zone of N-type and P type.Then, go out silicon oxide film by plasma CVD method in the 2nd interarea side film forming of glass substrate and form gate insulating film, then going out molybdenum by sputtering film-forming, utilizing and use photolithographic etching to form gate electrode.Then, utilize photoetching process and ion doping apparatus, inject boron and the phosphorus of high concentration in N-type, P type desired region separately, form source area and drain region.Then, in the 2nd interarea side of glass substrate, by utilizing the silica film forming of plasma CVD method to form interlayer dielectric, by the film forming utilizing sputtering method to form aluminium, and by using photolithographic etching to form TFT electrode.Then, the heating of 450 DEG C, 60 minutes is carried out under a hydrogen atmosphere to carry out hydrogenation treatment, then by utilizing the silicon nitride film forming of plasma CVD method to form passivation layer.Then, at the 2nd interarea side coated UV line curable resin of glass substrate, lithographically planarization layer and contact hole is formed.Then, go out tin indium oxide by sputtering film-forming, utilize and use photolithographic etching to form pixel electrode.

Then, another glass laminate A2 is carried out to the heating of 450 DEG C, 60 minutes under air atmosphere.Then, go out chromium by film forming on the 2nd interarea of the glass substrate of sputtering method in glass laminate A, utilize and use photolithographic etching to form light shield layer.Then, be coated with the 2nd interarea side coating chromatic photoresist (color resist) of method at glass substrate by mould, lithographically form colour filter with heat cure.Then, go out tin indium oxide by sputtering film-forming, form opposite electrode.Then, be coated with the 2nd interarea side coated UV line cured resin liquid of method at glass substrate by mould, lithographically form column spacing body (spacer) with heat cure.Then, by rolling method coating polyimide resin liquid, form oriented layer by heat cure, carry out rub (rubbing).

Then, by dispensing method (dispenser method), sealing resin liquid is depicted as frame-shaped, after dripping liquid crystal by dispensing method in frame, use the glass laminate A1 being above formed with pixel electrode, fitted each other in 2nd interarea side of the glass substrate of two panels glass laminate A, obtain LCD by ultraviolet curing and heat cure.

Next, make the 2nd interarea vacuum suction of glass laminate A1 in platform, the stainless steel cutter of the interface inserting thickness 0.1mm of the glass substrate in the bight of glass laminate A2 and silicone layer, provides the starting point of the stripping between the 1st interarea of glass substrate and the fissility surface of silicone layer.Herein, while jetting except electronic fluids by ion generator (Keyemce Inc.) to this interface, carry out the insertion of cutter.Then, continue to be jetted except electronic fluids to formed space by ion generator, while promote vacuum suction pad.Then, after the 2nd interarea with the support base material of vacuum suction pad absorption glass laminate A2, absorption layer is made to increase.Its result, platform only remains the LCD sylphon with the support base material of glass laminate A1, and the support base material can with silicone layer is peeled off.

Then, make the 2nd interarea vacuum suction being formed with the glass substrate of colour filter on the 1st interarea in platform, the stainless steel cutter of the interface inserting thickness 0.1mm of the glass substrate in the bight of glass laminate A1 and silicone layer, provides the starting point of the stripping on the 1st interarea of glass substrate and the fissility surface of silicone layer.Then, after the 2nd interarea with the support base material of vacuum suction pad absorption glass laminate A1, absorption layer is made to increase.Its result, platform only remains LCD box (cell), and the support base material that can be fixed with silicone layer is peeled off.Thus, the multiple LCD boxes be made up of the glass substrate of thickness 0.1mm can be obtained.

Next, multiple LCD box is divided into by cutting action.Implement the operation each LCD box in the completed attaching polarizer, next, implement module generation operation and obtain LCD.The LCD obtained thus can not have problems in performance.

< embodiment 8 >

First, go out molybdenum by film forming on the 2nd interarea of the glass substrate of sputtering method in glass laminate A, utilize and use photolithographic etching to form gate electrode.Then, go out silicon nitride by plasma CVD method in the 2nd further film forming in interarea side of glass substrate and form gate insulating film, next going out indium oxide gallium zinc by sputtering film-forming, utilizing and use photolithographic etching to form oxide semiconductor layer.Then, go out silicon nitride to form channel protective layer by plasma CVD method in the 2nd further film forming in interarea side of glass substrate, next go out molybdenum by sputtering film-forming, utilize and use photolithographic etching to form source electrode and drain electrode.Then, carry out in an atmosphere heating for 60 minutes at 450 DEG C.Then, go out silicon nitride to form passivation layer by plasma CVD method in the 2nd further film forming in interarea side of glass substrate, next go out tin indium oxide by sputtering film-forming, utilize and use photolithographic etching to form pixel electrode.

Then, as hole injection layer 4 are gone out in the 2nd interarea side of glass substrate successively film forming by vapour deposition method, 4 '; 4 "-three (3-methylphenylphenyl amino) triphenylamine, as two [(N-naphthyl)-N-phenyl] benzidine of hole transmission layer, be mixed with 40 volume %2 as luminescent layer, oxine aluminium complex (the Alq of two [4-[N-(4-methoxyphenyl)-N-phenyl] aminostyryl] naphthalene-1, the 5-dimethoxy nitrile (BSN-BCN) of 6- ₃), as the Alq of electron transfer layer ₃.Then, go out aluminium by sputtering film-forming, utilize and use photolithographic etching to form opposite electrode.Then, the 2nd interarea side of glass substrate seals across the tack coat of ultraviolet hardening another sheet glass substrate of fitting.Organic EL structure is formed on the glass substrate by above-mentioned flow process.The glass laminate A (hereinafter referred to as panel A) on the glass substrate with organic EL structure is the duplexer (having the display unit panel of support base material) with component used for electronic device of the present invention.

Next, the release surface of the glass substrate be separated with method is similarly to Example 1 cleaned, laser cutter or line sliver method is used to cut the glass substrate after separation, after being divided into multiple box (cell), the glass substrate and counter substrate that are formed with organic EL structure are assembled, implements module generation operation and make OLED.The OLED obtained thus can not have problems in performance.

The application is based on the Japanese patent application 2012-230092 applied on October 17th, 2012, and the content of this application is incorporated in this description with the form of reference.

Symbol description

10 glass laminate

12 support base materials

14 silicone layers

1st interarea of 14a silicone layer

16 glass substrates

1st interarea of 16a glass substrate

2nd interarea of 16b glass substrate

18 support base materials with silicone layer

20 components used for electronic device

22 duplexers with component used for electronic device

24 glass substrates with component

Claims

1. a glass laminate, possesses the layer of the layer of support base material, silicone layer and glass substrate successively, the peel strength at the layer of described support base material and the interface of described silicone layer higher than the peel strength at the interface of described silicone layer and described glass substrate, wherein

The silicones of described silicone layer is the cross-linking agent of bridging property organopolysiloxane,

Described silicone layer contains silicone oil,

One in the silicones contained in described silicone layer and described silicone oil has aromatic series base, and another one does not have aromatic series base in fact.

2. glass laminate as claimed in claim 1, wherein,

Described silicone oil has phenyl,

It is 5 ~ 50 % by mole with the containing ratio of phenyl in whole organic groups of silicon atom bonding in described silicone oil.

3. glass laminate as claimed in claim 1 or 2, wherein,

The content of silicone oil described in described silicone layer is 6 ~ 20 mass parts relative to described silicones 100 mass parts.

4. the glass laminate according to any one of claims 1 to 3, wherein,

Described silicone oil is 100 ~ 6000cP the viscosity of 25 DEG C.

5. the glass laminate according to any one of Claims 1 to 4, wherein,

The thickness of described silicone layer is 2 ~ 100 μm.

6. the glass laminate according to any one of Claims 1 to 5, wherein,

Described support base material is glass plate.

7. manufacture a method for the glass laminate according to any one of claim 1 ~ 6, wherein,

Form at the one side of support base material the layer comprising bridging property organopolysiloxane and silicone oil, described support base material face make described bridging property organopolysiloxane crosslinked thus form silicone layer, then at the superficial layer laminated glass substrate of described silicone layer.

8. there is a support base material for silicone layer, there is support base material and be arranged on the silicone layer with fissility surface on described support base material face, wherein,

Described silicone layer contains silicone oil,

9. there is the support base material of silicone layer as claimed in claim 8, wherein,

Described silicone oil has phenyl,

It is 5 ~ 50 % by mole with the phenyl containing ratio in whole organic groups of silicon atom bonding in described silicone oil.

10. there is the support base material of silicone layer as claimed in claim 9, wherein,

It is 5 ~ 30 % by mole with the containing ratio of phenyl in whole organic groups of silicon atom bonding in described silicone oil.

11. support base materials with silicone layer according to any one of claim 8 ~ 10, wherein,

12. support base materials with silicone layer according to any one of claim 8 ~ 11, wherein,

Described silicone oil is 100 ~ 6000cP the viscosity of 25 DEG C.