CN102883879A

CN102883879A - Process for producing laminate, and laminate

Info

Publication number: CN102883879A
Application number: CN2011800233928A
Authority: CN
Inventors: 江畑研一
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2010-05-11
Filing date: 2011-04-28
Publication date: 2013-01-16
Anticipated expiration: 2031-04-28
Also published as: CN104085168A; TWI505933B; JP5835214B2; JPWO2011142280A1; TW201202030A; CN102883879B; WO2011142280A1; KR20130097069A

Abstract

Provided is a process for producing a laminate which comprises a substrate, a support plate, and a resin layer interposed therebetween, the process comprising the step of forming the resin layer on the support plate and the step of bringing the resin layer into close contact with the substrate so that the substrate is separable from the resin layer. The process may include, before the contact step, a step in which at least one of the surfaces of the substrate and resin layer that are to be close contacted with each other is treated beforehand with a silicone oil or a silane coupling agent. Alternatively, the resin layer is formed from a resin which contains a silicone oil or silane coupling agent in the step of resin layer formation and, thereafter, the substrate and the resin layer are superposed and close contacted in the contact step.

Description

The manufacture method of duplexer and duplexer

Technical field

The present invention relates to manufacture method and the duplexer of duplexer.

Background technology

In recent years, carry out slimming, the lightweight of the devices (electronic equipment) such as solar cell (PV), liquid crystal panel (LCD), organic EL panel (OLED), carrying out the thin plate for the substrate of these devices.On the other hand, when causing the undercapacity of substrate because of thin plate, in the manufacturing process of device, the treatability of substrate can reduce.

Therefore, all the time, extensively adopt following methods: after the substrate formation device thicker than final thickness is with member (for example, thin film transistor (TFT)), utilize chemical etching to process the substrate thin plate.Yet in the method, for example, by the 0.7mm thin plate during to 0.2mm or 0.1mm, the more than half etched liquid of the material of original substrate is pruned, and from the viewpoint of productivity ratio, raw-material service efficiency, is not preferred therefore with the thickness of 1 plate base.

In addition, in the thin plate method of above-mentioned substrate based on chemical etching, when there is fine scar in substrate surface, sometimes because of etch processes take the scar pit fine as starting point forms (etch pit), become optic defective.

Recently, in order to tackle above-mentioned problem, following methods has been proposed: prepare to be laminated with the duplexer of substrate and reinforcement plate, the substrate of duplexer form device with member after, from strippable substrate reinforcement plate (for example, with reference to patent documentation 1).Reinforcement plate has glass plate and the resin bed that is fixed on this glass plate, and resin bed and substrate fit tightly with strippable form.Reinforcement plate can be stacked with new substrate behind strippable substrate, thereby recycle as duplexer.

The prior art document

Patent documentation

Patent documentation 1: international disclosing No. 07/018028

Summary of the invention

The problem that invention will solve

Yet for the duplexer of above-mentioned existing structure, with reinforcement plate during from strippable substrate, the resin bed of reinforcement plate can cohesion failure sometimes, causes the part of resin bed to be attached on the substrate as the product side.Think that this is because the condition of processing because of heat treated, chemical liquid in the manufacturing process of device, cause that resin bed is deteriorated sometimes, resin bed and substrate fits tightly the intensity rising sometimes.

The present invention carries out in view of above-mentioned problem, and its purpose is, manufacture method and the duplexer that can suppress the duplexer of resin bed cohesion failure when peeling off resin bed and substrate are provided.

For the scheme of dealing with problems

To achieve these goals, the manufacture method of duplexer of the present invention is the manufacture method of following duplexer:

It is for making the method that has substrate and gripper shoe and be present in the duplexer of the resin bed between them, has following operation: the aforementioned resin layer is formed on the operation on the aforementioned gripper shoe and makes the aforementioned resin layer fit tightly operation in aforesaid base plate with strippable form

Wherein, be included in the operation that the aforementioned operation that fits tightly is processed with silicone oil or silane coupler in advance to the aforesaid base plate that will fit tightly at least one party surperficial and aforementioned resin layer surface before, perhaps,

In the operation that forms the aforementioned resin layer, form the aforementioned resin layer by the resin that comprises silicone oil or silane coupler, then, in the aforementioned operation that fits tightly, make aforesaid base plate and aforementioned resin ply and fit tightly.

In the manufacture method of duplexer of the present invention, preferably, at least one party on the aforesaid base plate that will fit tightly surface and aforementioned resin layer surface be coated with silicone oil or silane coupler operation and

Coating makes the operation of the processing of silane coupler reaction when silicone oil being carried out the operation of low-molecular-weight processing and silane-coating coupling agent during silicone oil,

In the aforementioned operation that fit tightly, make aforesaid base plate and aforementioned resin ply and fit tightly thereafter.In addition, preferably, surface treatment has been implemented with silicone oil or silane coupler in the aforesaid base plate surface that fit tightly, and the water contact angle that has applied the substrate surface of aforementioned processing is more than 90 °.

In the manufacture method of duplexer of the present invention, preferably, in the operation that the aforementioned resin layer is formed on the aforementioned gripper shoe, form cured resin composition layer on aforementioned gripper shoe surface, then make this hardening resin composition be solidified to form the aforementioned resin layer.

In addition, in the manufacture method of duplexer of the present invention, preferably, the aforementioned resin layer is formed by silicones.

And then in the manufacture method of duplexer of the present invention, preferably, the aforementioned resin layer is that the reaction solidfied material by olefinic organic based polysiloxane and organic hydrogen polysiloxanes forms.

In addition, duplexer of the present invention is following duplexer:

It has substrate and gripper shoe and is present in resin bed between them, aforementioned resin layer and aforesaid base plate fit tightly with strippable form, the aforementioned resin layer is being fixed in the mode of the peel strength between them greater than the peel strength between aforementioned resin layer and the aforesaid base plate on the aforementioned gripper shoe

The aforesaid base plate surface that fits tightly and at least one party on aforementioned resin layer surface are formed by the surface of processing with silicone oil or silane coupler in advance, and perhaps, the aforementioned resin layer is the resin bed that is formed by the resin that comprises silicone oil or silane coupler.

In duplexer of the present invention, preferably, fitting tightly in the substrate surface on aforementioned resin layer surface is to use silicone oil or silane coupler to implement the surface-treated surface.In addition, preferably, the aforementioned water contact angle of having implemented the surface-treated substrate surface is more than 90 °.

In addition, in duplexer of the present invention, preferably, the aforementioned resin layer is formed by silicones.

And then in duplexer of the present invention, preferably, the aforementioned resin layer is that the reaction solidfied material by olefinic organic based polysiloxane and organic hydrogen polysiloxanes forms.

The effect of invention

According to the present invention, can provide manufacture method and the duplexer that can when peeling off resin bed and substrate, suppress the duplexer of resin bed cohesion failure.

Description of drawings

Fig. 1 is the partial side view of an example of duplexer of the present invention.

The specific embodiment

Below, describe being used for implementing embodiments of the present invention with reference to accompanying drawing, but the present invention is not subjected to the restriction of following embodiment, can apply various distortion and displacement to following embodiment within not exceeding scope of the present invention.

Need to prove that in the present invention, resin bed is fixed on the peel strength that refers on the gripper shoe between resin bed and the gripper shoe greater than the state of the peel strength between resin bed and the substrate.

(the first embodiment)

Fig. 1 is the partial side view of an example of duplexer of the present invention.As shown in Figure 1, duplexer 10 is for existing the duplexer of substrate 20 and gripper shoe 31 and the resin bed between them 32.Resin bed 32 is fixed on the gripper shoe 31, and fits tightly the first interarea 201 in substrate 20 with strippable form.Gripper shoe 31 and resin bed 32 work as the reinforcement plate 30 that strengthens substrate 20 in the operation of making the devices (electronic equipment) such as liquid crystal panel.

Use this duplexer 10 until the device manufacturing process midway.That is, use this duplexer 10 until at device members such as substrate 20 formation thin film transistor (TFT)s.Thereafter, reinforcement plate 30 is peeled off from substrate 20, can not become the member of constituent apparatus.Can be stacked with new substrate 20 from the reinforcement plate 30 that substrate 20 is peeled off, thus recycle as duplexer 10.Below, each formation is elaborated.

At first, substrate 20 is described.

Substrate 20 forms device with member and constituent apparatus at the second interarea 202.Herein, device refers to the member of at least a portion of constituent apparatus with member.As the object lesson of device with member, can list thin film transistor (TFT) (TFT), colour filter (CF).As device, but illustration sunny can battery (PV), liquid crystal panel (LCD), organic EL panel (OLED) etc.

The kind of substrate 20 can be common substrate, for example, can be the metal substrates such as silicon wafer, glass substrate, resin substrate or stainless steel (SUS) substrate, copper base.Among them, the preferred glass substrate.This is chemical proofing, anti-excellent moisture permeability because of glass substrate, and percent thermal shrinkage is low.As the index of percent thermal shrinkage, use the linear expansion coefficient of stipulating among the JIS R 3102-1995.

When the linear expansion coefficient of substrate 20 is large, because the most heat tracing of the manufacturing process of device is processed, therefore produce easily various unfavorable conditions.For example, when substrate 20 forms TFT, if under heating, the substrate 20 that is formed with TFT is cooled off, the excessive worry of position deviation that causes TFT because of the thermal contraction of substrate 20 is arranged then.

Glass substrate is with the frit melting and be configured as melten glass tabular and obtain.This manufacturing process can be usual way, such as using float glass process, fusion method, slot draw method, Fourcault process (Fourcault process), Lu Baifa (Lubbers process) etc.In addition, especially the glass substrate of thinner thickness by the following method (horizontal sheet process) be shaped and obtain: will temporarily be configured as tabular glass heats to the temperature that can be shaped, with the stretching of the means such as extension and make its thinning.

Glass to glass substrate is not particularly limited, preferred alkali-free glass, Pyrex, soda-lime glass, high silica glass, chemically reinforced glass, other the oxide based glass take silica as main component.As oxide based glass, the content of the silica that preferably converts take oxide is the glass of 40 ~ 90 quality %.

As the glass of glass substrate, adopt to be suitable for the kind of device, the glass of its manufacturing process.For example, because the stripping of alkali metal component impacts liquid crystal easily, so the glass substrate that liquid crystal panel is used is to be formed by the glass that is substantially free of alkali metal component (alkali-free glass).Like this, the glass of glass substrate is suitably selected with its manufacturing process based on the kind of applied device.

Thickness to glass substrate is not particularly limited, and slimming and/or light-weighted viewpoint from glass substrate are usually less than 0.8mm, are preferably below the 0.3mm, more preferably below the 0.15mm.When 0.8mm is above, can't satisfy slimming and/or the light-weighted requirement of glass substrate.And when 0.3mm is following, can give good flexibility to glass substrate.When 0.15mm is following, glass substrate can be coiled into tubular.In addition, from being easy to make glass substrate, being easy to process the reasons such as glass substrate, the thickness of glass substrate is preferably more than the 0.03mm.

Kind to the resin of resin substrate is not particularly limited.Particularly, can pet resin, polycarbonate resin, polyimide resin, fluororesin, polyamide, Nomex resin, polyethersulfone resin, polyether ketone resin, polyether-ether-ketone resin, PEN resin, polyacrylic acid resinoid, various liquid crystal polymer resin, cyclic olefin resins, silicones etc. be shown example.Wherein, resin substrate can be transparent, also can be opaque.In addition, resin substrate can also be that the surface is formed with the resin substrate that the functional layers such as protective layer form.

Need to prove that substrate 20 can be by forming more than 2 layers, in this case, the material that forms each layer can be same material, also can be same material not.In addition, in this case, " thickness of substrate 20 " means the gross thickness of all layers in the substrate.From slimming and/or the light-weighted viewpoint of substrate, the thickness of substrate 20 is usually less than 1.0mm, is preferably below the 0.5mm, more preferably below the 0.3mm.In addition, from being easy to make substrate and being easy to the reason for the treatment of substrate etc., be preferably more than the 0.01mm.

Then, gripper shoe 31 is described.

Gripper shoe 31 and resin bed 32 actings in conjunction support and also strengthen substrate 20, prevent the distortion, damage, breakage of substrate 20 etc. in the manufacturing process of device.In addition, one of purpose of using gripper shoe 31 also is,, make the duplexer 10 identical with the thickness of existing substrate, thereby in the manufacturing process of device, can use manufacturing technology, the manufacturing equipment of the substrate that is suitable for existing thickness during than the thin substrate 20 of existing substrate at used thickness.

As gripper shoe 31, such as using metallic plates such as glass plate, resin plate or stainless steel (SUS) plate etc.Manufacturing process at device follows in the heat treated situation, and gripper shoe 31 is preferably used with the little material of the difference of the linear expansion coefficient of substrate 20 and formed, and more preferably uses the material identical with substrate 20 to form.When substrate 20 was glass substrate, gripper shoe 31 was preferably glass plate.The glass plate that the glass material of particularly preferably serving as reasons identical with glass substrate forms.

The thickness of gripper shoe 31 can be thicker than substrate 20, also can be thinner than substrate 20.Preferably, select the thickness of gripper shoe 31 according to the thickness of the thickness of the thickness of substrate 20, resin bed 32 and duplexer 10.For example, the manufacturing process of existing device is that the mode of processing the substrate of thickness 0.5mm designs, and when the thickness sum of the thickness of substrate 20 and resin bed 32 is 0.1mm, the thickness of gripper shoe 31 is made as 0.4mm.The thickness of gripper shoe 31 is preferably 0.08 ~ 5.0mm under normal conditions, more preferably 0.2 ~ 5.0mm, more preferably 0.2 ~ 1.0mm.

When gripper shoe 31 was glass plate, from the reason that is easy to process, be difficult to break etc., the thickness of glass plate was preferably more than the 0.08mm.In addition, have the appropriateness flexibility and the reason of such rigidity of not breaking after device forms with member when hope is peeled off, the thickness of glass plate is preferably below the 1.0mm.

Substrate 20 and gripper shoe 31 are preferably 500 * 10 in the difference of the average coefficient of linear expansion under 25 ~ 300 ℃ (below, referred to as " average coefficient of linear expansion ") ^-7/ ℃ below, more preferably 300 * 10 ^-7/ ℃ below, more preferably 200 * 10 ^-7/ ℃ below.When poor excessive, have following possibility: when carrying out heating and cooling in the manufacturing process of device, duplexer 10 violent warpages or substrate 20 are peeled off with reinforcement plate 30.When the material of the material of substrate 20 and gripper shoe 31 is identical, can suppress the generation of this problem.

Then, resin bed 32 is described.

Resin bed 32 is fixed on the gripper shoe 31, in addition, fits tightly in substrate 20 with strippable form.Resin bed 32 prevents until carry out the position deviation of the substrate 20 till the strip operation, and easily peels off from substrate 20 by strip operation, prevents substrate 20 grades because strip operation and breakage.

Size to resin bed 32 is not particularly limited.The size of resin bed 32 can be larger than substrate 20, gripper shoe 31, also can be less than it.

Preferably, below the surperficial 321(of the base material side of resin bed 32, be also referred to as " fitting tightly face 321 ") be attached at below the surperficial 201(of substrate 20 by resulting from the power of the intermolecular Van der Waals force of solid, be also referred to as " fitting tightly face 201 "), rather than the bonding force attaching by having such as common adhesive.This is because can easily peel off.Among the present invention, the character that can easily peel off of this resin layer surface is called fissility.

On the other hand, the adhesion on the surface of 32 pairs of gripper shoes 31 of resin bed is relatively higher than the adhesion on the surface 201 of 32 pairs of substrates 20 of resin bed.Therefore, the peel strength between resin bed 32 and the gripper shoe 31 is higher than the peel strength between resin bed 32 and the substrate 20.Among the present invention, resin layer surface is called the combination of substrate surface fits tightly, will be called the combination on gripper shoe surface fixing.Preferably carry out combination with bonding force, bonding force between resin bed 32 and the gripper shoe 31.But be not limited to these modes, as long as it is relatively higher to fit tightly the adhesion of face 201 than 32 pairs of resin beds, then also can be by resulting from the power attaching of above-mentioned Van der Waals force between resin bed 32 and the gripper shoe 31.

Thickness to resin bed 32 is not particularly limited, and is preferably 1 ~ 100 μ m, more preferably 5 ~ 30 μ m, more preferably 7 ~ 20 μ m.This is because when the thickness of resin bed 32 was this scope, resin bed 32 became abundant with fitting tightly of substrate 20.In addition, this be because, even entrained air bubbles, foreign matter between resin bed 32 and the substrate 20 also can suppress substrate 20 generation deformation defects.In addition, when the thickness of resin bed 32 is blocked up, needing time and materials in order to form resin bed, is uneconomic therefore.

Need to prove that resin bed 32 can be by forming more than 2 layers.In this case, " thickness of resin bed 32 " means the gross thickness of all layers in the resin bed.

In addition, resin bed 32 is when forming more than 2 layers, and the kind that forms the resin of each layer can be different.

Resin bed 32 preferably is lower than room temperature (about 25 ℃) or is not had the material of glass transition point to form by glass transition point.This is because of becoming non-fusible resin bed, more easily peel off with substrate 20, also becoming abundant with fitting tightly of substrate 20 simultaneously.

In addition, resin bed 32 carries out heat treated mostly in the manufacturing process of device, therefore preferably has heat resistance.

In addition, when the elastic modelling quantity of resin bed 32 is too high, the tendency of the fitting tightly property step-down of existence and substrate 20.On the other hand, the elastic modelling quantity of resin bed 32 is crossed when hanging down, and fissility can step-down.

Kind to the resin that forms resin bed 32 is not particularly limited.For example, can list acrylic resin, vistanex, polyurethane resin and silicones.Also several mixed with resin can be used.Preferred silicones wherein.This is heat resistance, fissility excellence because of silicones.In addition also because gripper shoe 31 is when be glass plate, be easy to fix at glass plate by the condensation reaction with the silanol base of glass pane surface.Silicone layer is under the state between gripper shoe 31 and the substrate 20, even for example processed about 1 hour with about 200 ℃ in atmosphere, fissility substantially can be not deteriorated yet, is preferred from this point yet.

Resin bed 32 is preferably formed by the silicones (solidfied material) of using for peeling paper in the silicones.Make to form peeling paper and have excellent fissility with the resin bed 32 that the hardening resin composition of silicones forms at the surface cure of gripper shoe 31, so be preferred.In addition, because flexibility is high, even therefore foreign matters such as entrained air bubbles, dust between resin bed 32 and the substrate 20 also can suppress the generation of the deformation defect of substrate 20.

Form the curable silicone of such peeling paper usefulness silicones according to its curing mechanism, can be divided into condensation reaction type organosilicon, addition reaction-type organosilicon, ultraviolet hardening organosilicon and electron ray curing type organosilicon, any all can use.Preferred addition reaction-type organosilicon among these.This is that heat resistance is also high because the degree of the easy degree of curing reaction, the fissility when forming resin bed 32 is good.

The addition reaction-type organosilicon is the solidification compound that comprises host and crosslinking agent, solidifies in the presence of the catalyst such as platinum group catalyst.The organosilyl curing of addition reaction-type is promoted by heat treated.The organosilyl host of addition reaction-type is to be formed by the straight chain shape organopolysiloxane with the thiazolinyl (vinyl etc.) that is bonded on the silicon atom (that is, the olefinic organic based polysiloxane), and vinyl etc. become crosslinking points.The organosilyl crosslinking agent of addition reaction-type is to be formed by the straight chain shape organopolysiloxane (that is, organic hydrogen polysiloxanes) with the hydrogen atom (silicon hydrogen base) that is bonded on the silicon atom, and silicon hydrogen base etc. becomes crosslinking points.

In addition, the formation peeling paper has solvent-borne type, emulsion-type and no-solvent type with the curable silicone of silicones in view of form, and arbitrary type all can use.Preferred no-solvent type among these.This is because the aspect of productivity ratio, security, environmental characteristics is excellent.In addition, also because be not heating and curing, producing the solvent of foaming when ultraviolet curing or electron ray curing when not being included in curing when forming resin bed 32, so bubble is difficult in resin bed 32 residual.

In addition, as forming the curable silicone of peeling paper with silicones, particularly, can list commercially available trade name or model is KNS-320A, KS-847(is organosilicon company of SHIN-ETSU HANTOTAI and makes), organosilicon company of TPR6700(GE Toshiba makes), the combination of vinyl organosilicon " 8500 " (Arakawa Chemical Industries, Ltd.'s manufacturing) and hydrogenated methyl polysiloxanes " 12031 " (Arakawa Chemical Industries, Ltd.'s manufacturing), the combination of vinyl organosilicon " 11364 " (Arakawa Chemical Industries, Ltd.'s manufacturing) and hydrogenated methyl polysiloxanes " 12031 " (Arakawa Chemical Industries, Ltd.'s manufacturing), the combination of vinyl organosilicon " 11365 " (Arakawa Chemical Industries, Ltd.'s manufacturing) and hydrogenated methyl polysiloxanes " 12031 " (Arakawa Chemical Industries, Ltd.'s manufacturing) etc.

Wherein, KNS-320A, KS-847 and TPR6700 are the curable silicones that contains in advance host and crosslinking agent.

In addition, the composition that the silicones of formation resin bed 32 preferably has in the silicone layer is difficult to the character of substrate 20 migrations, i.e. low organosilicon animal migration.

The method that resin bed 32 is fixed on the gripper shoe 31 is not particularly limited, for example can lists the lip-deep method that the resin of film-form is fixed on gripper shoe 31.Particularly, can list: in order to give the high bed knife (high-peeling strength) on the surface of film and to carrying out surface modification treatment (prime treatment) in the surface of gripper shoe 31, resin bed 32 is fixed on method on the gripper shoe 31.For example, the chemical method (prime treatment) of the lifting chemistry bed knife as silane coupler can routine be shown, the physical method of the increase surface active groups as flame (frame) is processed, the roughness that blasting treatment is such passes through to increase the surface increase the mechanical processing method that adheres to etc.

In addition, the layer of hardening resin composition that also can be by for example becoming resin bed 32 on gripper shoe 31 surfaces then is solidified to form this hardening resin composition the method for resin bed 32, forms thus the resin bed 32 that is fixed on the gripper shoe 31.As the method for the layer that forms hardening resin composition on gripper shoe 31 surfaces, for example can list hardening resin composition is coated on method on the gripper shoe 31.As coating process, can list spraying process, mould and be coated with method, spin-coating method, dip coating, rolling method, rod and be coated with method, silk screen print method, intaglio plate rubbing method.Can from these methods, suitably select according to the kind of resin combination.

In addition, when being coated on the hardening resin composition that forms resin bed 32 on the gripper shoe 31, its coating weight is preferably 1 ~ 100g/m ², 5 ~ 20g/m more preferably ²

When for example forming resin bed 32 by the organosilyl hardening resin composition of addition reaction-type, the hardening resin composition that will be formed by the mixture of olefinic organic based polysiloxane, organic hydrogen polysiloxanes and catalyst is coated on the gripper shoe 31 by the above-mentioned known methods such as spraying process, and it is heating and curing.The condition that is heating and curing is according to the compounding amount of catalyst and difference, for example, in total amount 100 mass parts with respect to olefinic organic based polysiloxane and organic hydrogen polysiloxanes, compounding during 2 mass parts platinum group catalyst, in atmosphere with 50 ℃ ~ 250 ℃, preferably react with 100 ℃ ~ 200 ℃.In addition, the reaction time of this moment is made as 5 ~ 60 minutes, preferably is made as 10 ~ 30 minutes.

By hardening resin composition is heating and curing, silicones and gripper shoe 31 are carried out chemical bond during curing reaction, and/or make silicone layer and gripper shoe 31 combinations by anchor effect (anchor effect).By their effect, silicone layer firmly is fixed on the gripper shoe 31.Need to prove, when being formed the resin bed that is formed by the resin beyond the silicones by hardening resin composition, also can form the resin bed that is fixed on the gripper shoe with method same as described above.

The method that resin bed 32 is fitted tightly on substrate 20 take strippable form can be as known method.For example, can list under the atmospheric pressure environment behind the overlapping substrate 20 in the fissility surface of resin bed 32, use the method for roller, press crimping resin bed 32 and substrate 20.By carrying out crimping with roller, press, resin bed 32 and substrate 20 fit tightly more, are preferred therefore.In addition, by utilizing the crimping of roller or press, can remove relatively easily the bubble that is blended between resin bed 32 and the substrate 20, be preferred therefore.

If utilize vacuum layer platen press, Vacuum Pressure method for making to carry out crimping, that then can more preferably suppress bubble sneaks into, guarantees well driving fit, thereby is preferred.Under vacuum, carry out crimping and also have following advantage: even also can owing to heating is grown up, not be difficult for causing the deformation defect of substrate 20 at the situation bubble of remaining small bubble.

When making resin bed 32 fit tightly on substrate 20 with strippable form, preferably, washing resin layer 32 and substrate 20 are in contact with one another the surface of a side fully, carry out stacked under the high environment of cleanliness factor.Even sneak into foreign matter between resin bed 32 and the substrate 20, because resin bed 32 can distortion therefore can the flatness on the surface of substrate 20 not impacted, but higher its flatness of cleanliness factor is better, is preferred therefore.

Need to prove, to resin bed 32 being fixed on the operation on the gripper shoe 31 and resin bed 32 being not particularly limited with the order that strippable form fits tightly the operation on substrate 20, for example can carry out approximately simultaneously.

Among the present invention, fit tightly face 201 and process with silicone oil or silane coupler in advance with at least one party who fits tightly face 321, perhaps, resin bed 32 is formed by the resin that comprises silicone oil or silane coupler.The first embodiment is wherein the former surface treatment.By before fitting tightly, carrying out surface treatment with silicone oil or silane coupler to fitting tightly face 201 in advance with at least one party who fits tightly face 321, can suitably regulate thus the density of the polar group that exists in the face of fitting tightly 201,321.Wherein, in the present embodiment, can be in advance the face that fits tightly 201 of substrate 20 sides be carried out surface treatment, also can be in advance the face that fits tightly 321 of resin bed 32 sides be carried out surface treatment, can also be in advance the face that fits tightly 201,321 of both sides be carried out surface treatment.In addition, by by resin-shaped resin layer 32(the second embodiment that comprises silicone oil or silane coupler), the density that also can similarly suitably regulate the polar group that exists in the face of fitting tightly 321.

Herein, the polar group that exists as the surface of glass substrate is such as listing hydroxyl (OH) etc.In addition, the polar group that exists as the surface of resin bed, (CO), carboxyl is (COOH) etc. such as listing carbonyl.These polar groups are hydrophilic radical.

Can judge whether the density of the polar group that exists in the face that fits tightly 201,321 of substrate 20 and resin bed 32 is appropriate by before fitting tightly, measuring the water contact angle become the face of fitting tightly 201,321 surface.Usually there is the density of the surperficial hydrophilic polar group that exists higher, the tendency that water contact angle becomes less.Herein, water contact angle refers to the contact angle stipulated among the JIS R 3257-1999.

Carried out surface-treated and fit tightly the water contact angle of face 201,321 before fitting tightly and be preferably more than 90 °, more preferably 90 ~ 120 °, more preferably 90 ~ 110 °.Both water contact angle of the face that fits tightly 201,321 before fitting tightly are during all less than 90 °, and the density of the polar group that the surface of substrate 20, resin bed 32 exists is too high.Therefore, in the manufacturing process of device, when the temperature of duplexer 10 surpassed 250 ℃, substrate 20 was promoted substrate 20 and resin bed 32(reinforcement plate 30 with the chemical bond of resin bed 32) becoming is difficult to separate.

Water contact angle before fitting tightly is the face that fits tightly 201 that the surface more than 90 ° is preferably substrate 20.If fitting tightly the water contact angle of face 201 is more than 90 °, be lower than 90 ° even then fit tightly the water contact angle of face 321 before fitting tightly, as long as the hydrophily of resin is not high especially, can easily peel off resin bed 32 and substrate 20.When particularly resin bed 32 is the hydrophobic resins such as silicones, be lower than 90 ° even fit tightly the water contact angle of face 321 before fitting tightly, also can easily peel off.

Can be pre-formed trickle concaveconvex structure by the face that fits tightly 201 at substrate 20 by the surface treatment before fitting tightly.In this case, by the anchor effect of concaveconvex structure, the face that fits tightly 201 of substrate 20 and the face that fits tightly 321 of resin bed 32 are fitted tightly with sufficient adhesion, can easily process duplexer 10.Wherein, when forming fine concaveconvex structure by surface treatment, there is the tendency that increases in water contact angle, and water contact angle can be above 120 ° sometimes.

Carry out the surface-treated surface and be preferably the face of abundant cleaning, be preferably the face after the firm washing.Cleanliness factor (activity degree) is crossed when hanging down, and can't carry out uniform surface treatment.As washing methods, can use the usual way for the washing of glass surface, resin surface.

It is desirable to, protect in advance with protective films such as masks and do not carry out the surface-treated surface.This is because the face that mistake is attached with the surface-treated material is difficult to form the device member in the manufacturing process of device.

Silicone oil, silane coupler as the surface-treated material may be used singly or in combin.When being used in combination, can carry out surface treatment with silane coupler after recycle silicon oil carry out surface treatment, also can carry out surface treatment with silicone oil after recycle silicon alkane coupling agent carry out surface treatment.

Kind to silicone oil is not particularly limited, can the straight chain silicone oil (straight silicone oil) such as dimethicone, methyl phenyl silicone oil, methyl hydrogen silicone oil be shown example, side chain or the terminal modified silicon oil that has imported alkyl, hydrogen base, epoxy radicals, amino, carboxyl, polyether-based, halogen group etc.As object lesson, can list hydrogenated methyl polysiloxanes, dimethyl polysiloxane, methyl phenyl silicone, diphenyl siloxane etc., heat resistance increases according to the order of above-mentioned record, and what heat resistance was the highest is diphenyl siloxane.These silicone oil are generally used for glass substrate, carried out the water-proofing treatment on surface of the substrates such as metal substrate of prime treatment.

Surface treatment method based on silicone oil can be usual way.For the processing that only merely is coated with silicone oil, owing to have the combination degree on silicone oil and processed surface low, can't give full play to the worry for the treatment of effect, therefore preferably be combined in processed lip-deep processing being coated with the after-applied silicone oil that makes of silicone oil.Think that making silicone oil be combined in processed lip-deep processing is processing as the strand that cuts off silicone oil, the part that cuts off is combined in (the following low-molecular-weight that this processing is called silicone oil) on the processed surface.

As the surface treatment method based on silicone oil, preferably, silicone oil is coated on the face that fits tightly 321 of the face that fits tightly 201, resin bed 32 of substrate 20, and carries out the method for low-molecular-weight.By the coating weight of regulating silicone oil, the treatment conditions of low-molecular-weight etc., the density optimization of the polar group that the face that fits tightly 321 of the face that fits tightly 201 of substrate 20, resin bed 32 can be existed.Thus, the cohesion failure of resin bed 32 in the time of can suppressing to peel off resin bed 32 and substrate 20.

The coating process of silicone oil can be usual way.For example, can be according to the kind of silicone oil, coating weight etc., be coated with method, spin-coating method, dip coating, rolling method, rod from spraying process, mould and be coated with method, silk screen print method, the intaglio plate rubbing method etc. and suitably select.As coating fluid, it is desirable to, use with hexane, heptane, dimethylbenzene equal solvent silicone oil is diluted to solution below the 1 quality %.When surpassing 1 quality %, the processing time of low-molecular-weight is long.In addition, it is desirable to, use to be diluted to the above solution of 0.01 quality %.When being lower than 0.01 quality %, it is insufficient that the optimization of the density of polar group can become.

The method of silicone oil low-molecular-weight can be used usual way, for example have by light decomposition, thermal decomposition and cut off the method for the siloxane bond of silicone oil.Utilize during light decomposes from the ultraviolet ray of the irradiations such as low pressure mercury lamp, xenon arc lamp, also the ozone that produces is shone in use capable of being combined by the ultraviolet ray in the atmosphere.Thermal decomposition can be carried out with batch furnace, conveyor furnace etc., also can utilize plasma, arc discharge etc.With batch furnace, when conveyor furnace carries out thermal decomposition, although according to the kind of the silicone oil of above-mentioned coating fluid, concentration and different, it is desirable to, under 250 ℃ ~ 400 ℃, process.When being lower than 250 ℃, organosilyl low-molecular-weight becomes insufficient, and when surpassing 400 ℃, organosilyl silication becomes significantly, and processing becomes insufficient as low-molecular-weight.

If the siloxane bond of silicone oil is cut off, then the density of the hydrophobic functional groups such as methyl uprises, and the density of the hydrophily polar group that exists in the face that fits tightly 201 of substrate 20, the face that fits tightly 321 of resin bed 32 reduces.Wherein, if the siloxane bond of silicone oil is excessively cut off, the tendency that then has the density of hydrophily polar group again to increase.

Kind to silane coupler is not particularly limited, for example, can preferably use and be selected from the following compound more than one: HMDS (HMDS), APTES, N-(2-amino-ethyl)-3-TSL 8330, N-{N-(2-amino-ethyl)-the 2-amino-ethyl }-the amino silane class such as 3-TSL 8330,3-anilino-propyl trimethoxy silicane; 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl) the epoxy radicals silicone hydride class such as ethyl trimethoxy silane; The chlorosilane class of 3-r-chloropropyl trimethoxyl silane and so on, silicon fluoride class; The hydrosulphonyl silanes such as 3-sulfydryl trimethoxy silane; Vinyltrimethoxy silane, N-2-(N-vinyl benzyl-2-amino-ethyl)-the vinyl silanes classes such as 3-TSL 8330; The silicon Acrylote alkanes such as 3-methacryloxypropyl trimethoxy silane.

Surface treatment method based on silane coupler can be usual way.For example, the face that fits tightly 321 of the face that fits tightly 201 of substrate 20, resin bed 32 is exposed in the atmosphere that comprises the gas that is formed by the silane coupler gasification, and the hydrophily polar group that exists in the face that fits tightly 321 with the face that fits tightly 201 of substrate 20, resin bed 32 is replaced as the method for the hydrophobic functional groups such as methyl etc.Concentration by regulating the silane coupler in the atmosphere, temperature, processing time etc., the density optimization of the polar group that exists in can the face that fits tightly 321 with the face that fits tightly 201 of substrate 20, resin bed 32.Thus, the cohesion failure of resin bed 32 in the time of can suppressing to peel off resin bed 32 and substrate 20.

In addition, fit tightly face 201,321 midway after mutually the peeling off of manufacturing process of device, can return to by the processing of regulation the state before the surface treatment.The surface-treated face based on silicone oil or silane coupler of for example applying can decompose by light, thermal decomposition returns to the state before the surface treatment.Thus, if for example the surface 201 of substrate 20 returns to the front state of surface treatment, the attaching intensity in the time of then can improving to surperficial 201 optical film adhered (for example, polarizing film).In addition, if pay attention to re-workability, then also can be with the state after the surface treatment directly to surface 201 optical film adhered of substrate 20.

(the second embodiment)

Formation and Fig. 1 of the duplexer of present embodiment are roughly the same, therefore omit diagram.

In the present embodiment, resin bed 32 is formed by the resin that comprises silicone oil or silane coupler.Preferably, resin bed 32 is by being solidified to form the hardening resin composition that comprises silicone oil or silane coupler.Hardening resin composition is not particularly limited, for example can uses to form the hardening resin composition that peeling paper is used silicones.Wherein, for the face that fits tightly 201,321 of substrate 20 and resin bed 32, before fitting tightly, also can not apply above-mentioned surface treatment.

Silicone oil, silane coupler can be used singly or in combination, preferred silicone oil, the silane coupler that does not have with the functional group of the composition reaction of hardening resin composition that use respectively.For example, when forming resin bed 32 by the organosilyl hardening resin composition of aforementioned addition reaction-type, as silicone oil, silane coupler, use the silicone oil, the silane coupler that do not have the functional group's (for example, vinyl, silicon hydrogen base) that becomes crosslinking points.In addition, when forming resin bed 32 by the organosilyl hardening resin composition of condensation reaction type, but use does not have the silicone oil of functional group's (hydrolization group, silanol base etc.) of cocondensation.

In this resin bed 32, silicone oil is also uncrosslinked when the curing of above-mentioned hardening resin composition, but comprises wherein dispersedly.In addition, silane coupler is condensation when the curing of above-mentioned hardening resin composition usually, and is included in the resin that has solidified with the form of the condensation product of silane coupler.Therefore, the condensation product that comprises dispersedly silicone oil or silane coupler in the face that fits tightly 321 of resin bed 32.

For example, when comprising silicone oil in the face that fits tightly 321 of resin bed 32, in the manufacturing process of device, if the temperature of duplexer 10 uprises, then silicone oil can low-molecular-weight.Its result, two density that fit tightly the hydrophily polar group that exists in the face 201,321 reduce, and the density of the hydrophobic functional groups such as methyl increases.

In addition, when comprising the silane coupler condensation product in the face that fits tightly 321 of resin bed 32, two fit tightly the hydrophily polar group that exists in the face 201,321 and are replaced by hydrophobic functional groups such as methyl.

Therefore, become the silicone oil that comprises in the hardening resin composition of resin bed 32 or content, the kind of silane coupler by adjusting, can be with two density optimizations that fit tightly the polar group that exists in the face 201,321.

Therefore, in the present embodiment, the cohesion failure of resin bed 32 in the time of also can similarly suppressing to peel off resin bed 32 and substrate 20 with the first embodiment.In addition, because the operation of silicone oil low-molecular-weight is carried out with the operation merging for other purposes, in addition, owing to not with the operation of silane coupler gasification, therefore can reduce process number.

It is desirable to, the silicone oil that comprises in the hardening resin composition of formation resin bed 32 and the content of silane coupler are 0.1 ~ 5 quality % with respect to the solid constituent of the hardening resin composition that comprises them.When being lower than 0.1 quality %, can't obtain sufficient effect.On the other hand, when surpassing 5 quality %, the heat resistance of resin bed 32 became low.

In the situation of the second embodiment, the face that fits tightly 201 of substrate 20 also can not apply the surface treatment in aforementioned the first embodiment.When substrate 20 is glass substrate, because its surface is the high surface of hydrophily, so fits tightly face 201 and also can before fitting tightly, apply in advance surface treatment in aforementioned the first embodiment.

Embodiment

Below, further specifically describe the present invention by embodiment etc., but the present invention is not subjected to the restriction of these examples.

[embodiment 1]

Substrate and gripper shoe are all used the glass plate (Asahi Glass Co., Ltd makes, AN100, alkali-free glass) of the long 720mm that obtains by float glass process * wide 600mm.Wherein, the thickness of substrate is made as 0.4mm, the thickness of gripper shoe is made as 0.3mm.The average coefficient of linear expansion of substrate and gripper shoe is respectively 38 * 10 ^-7/ ℃.

(making of reinforcement plate)

Gripper shoe is carried out pure water washing, UV washing, make the surface cleaning of gripper shoe.Utilize serigraphy at the single face of gripper shoe be coated with hardening resin composition (coating weight 30g/m thereafter, ²).

Hardening resin composition uses the solvent-free addition reaction-type organosilicon of 100 mass parts, and (organosilicon company of SHIN-ETSU HANTOTAI makes, and KNS-320A) (organosilicon company of SHIN-ETSU HANTOTAI makes, mixture CAT-PL-56) with 2 mass parts platinum group catalysts.

Above-mentioned solvent-free addition reaction-type organosilicon comprises the straight chain shape olefinic organic based polysiloxane (host) with the vinyl that is bonded on the silicon atom and methyl and has the hydrogen atom that is bonded on the silicon atom and the straight chain shape organic hydrogen polysiloxanes (crosslinking agent) of methyl.

In atmosphere, with 180 ℃ of heating it is solidified in the mixture that is coated on the gripper shoe, thereby the centre on gripper shoe form and the silicone layer of fixed length 705mm * wide 595mm * thickness 20 μ m.

(surface treatment of substrate)

Substrate is carried out pure water washing, UV washing, make the surface cleaning of substrate.Thereafter, apply on the basis of mask at the second interarea as the single face of substrate, the sprayed silicon oil content is the n-heptane solution of 0.5 quality % and dry on the first interarea of opposition side.Silicone oil uses dimethyl polysiloxane, and (Dow Corning Toray Co., Ltd. makes, SH200).Then, in order to carry out the low-molecular-weight of silicone oil, and in air, carry out 2 minutes based on the UV treatment of low pressure mercury lamp.

Thereafter, using contact angle instrument (KRUSS company makes, DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2), measure the water contact angle of the first interarea of substrate, is 100 °.

(making of duplexer)

After the UV treatment, the overlapping silicone layer of the first interarea to substrate at room temperature fits tightly substrate and silicone layer by vacuum pressing, thereby obtains the duplexer that formed by substrate and reinforcement plate.

(heat resistant test of duplexer)

With this duplexer in the oxysome volume concentrations is nitrogen atmosphere below the 1000ppm, 350 ℃ of lower heat treated 1 hour.Thereafter, after being cooled to room temperature, peel off cutter to inserting between substrate and the silicone layer, the limit keeps substrate-side smooth, and the limit makes the silicone layer side near the successively deflection deformation insertion position, thereby peels off substrate and silicone layer.

According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing thing from silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 100 °.

[embodiment 2]

Substrate and gripper shoe are used respectively the glass plate identical with embodiment 1.

(making of reinforcement plate)

Among the embodiment 2, as hardening resin composition, use two ends to have the straight chain shape olefinic organic based polysiloxane (vinyl organosilicon of vinyl, Arakawa Chemical Industries, Ltd. makes, 8500) polymethyl hydrogen siloxane (Arakawa Chemical Industries, Ltd. makes, 12031) and platinum group catalyst (Arakawa Chemical Industries, Ltd.'s manufacturing that, have silicon hydrogen base in the molecule, CAT 12070) mixture, in addition, reinforcement plate is made in similarly to Example 1 operation.

, regulate the mixing ratio of straight chain shape olefinic organic based polysiloxane and hydrogenated methyl polysiloxanes herein, making the mol ratio of vinyl and silicon hydrogen base is 1:1.In addition, total amount 100 mass parts with respect to straight chain shape olefinic organic based polysiloxane and hydrogenated methyl polysiloxanes are made as 5 mass parts with platinum group catalyst.

(surface treatment of substrate)

Among the embodiment 2, for the low-molecular-weight of silicone oil, carry out the Cement Composite Treated by Plasma based on normal pressure remote plasma body device (Sekisui Fine Chemical Co., Ltd. makes, RT series), in addition, the surface treatment of substrate is carried out in operation similarly to Example 1.

Herein, the treatment conditions with Cement Composite Treated by Plasma are made as: exported 3kw, nitrogen/air mass flow ratio=600slm/750sccm, transporting velocity 5m/ minute.The surface temperature of the substrate during the irradiation plasma is below 50 ℃.The water contact angle of the first interarea of the substrate after the surface treatment is 95 °.

(making of duplexer)

After the surface treatment, operation obtains the duplexer that is formed by substrate and reinforcement plate similarly to Example 1.

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, peel off similarly to Example 1 substrate and silicone layer.According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing thing from silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 100 °.

[embodiment 3]

(making of reinforcement plate)

Among the embodiment 3, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Among the embodiment 3, for the low-molecular-weight of silicone oil, carried out 10 minutes heat treated with 400 ℃ in atmosphere, in addition, the surface treatment of substrate is carried out in operation similarly to Example 1.The water contact angle of the first interarea of the substrate after the surface treatment is 105 °.

(making of duplexer)

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, peel off similarly to Example 1 substrate and silicone layer.According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing thing from silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 105 °.

[embodiment 4]

(making of reinforcement plate)

Among the embodiment 4, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Among the embodiment 4, for the low-molecular-weight of silicone oil, be the n-heptane solution of 0.1 quality % and make its drying to the first interarea sprayed silicon oil content of substrate, in atmosphere, carry out 10 minutes heat treated with 250 ℃, in addition, carry out similarly to Example 1 the surface treatment of substrate.The water contact angle of the first interarea of the substrate after the surface treatment is 98 °.

(making of duplexer)

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, peel off similarly to Example 1 substrate and silicone layer.According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing thing from silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 98 °.

[embodiment 5]

Substrate and gripper shoe are used respectively the glass plate (Asahi Glass Co., Ltd makes, AS, soda-lime glass) of the long 720mm that obtains by float glass process * wide 600mm.Wherein, the thickness of substrate is made as 0.4mm, the thickness of gripper shoe is made as 0.3mm.The average coefficient of linear expansion of substrate and gripper shoe is respectively 85 * 10 ^-7/ ℃.

(making of reinforcement plate)

Among the embodiment 5, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Among the embodiment 5, for the low-molecular-weight of silicone oil, the sprayed silicon oil content is the n-heptane solution of 0.5 quality % and dry on the first interarea of substrate, carries out 10 minutes heat treated in atmosphere, under 350 ℃, in addition, carry out similarly to Example 1 the surface treatment of substrate.The water contact angle of the first interarea of the substrate after the surface treatment is 102 °.

(making of duplexer)

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, peel off similarly to Example 1 substrate and silicone layer.According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing thing from silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 102 °.

[embodiment 6]

Substrate and gripper shoe are used respectively except chemical enhanced the glass plate identical with embodiment 5.

(making of reinforcement plate)

Among the embodiment 6, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Among the embodiment 6, for the low-molecular-weight of silicone oil, carry out similarly to Example 5 the surface treatment of substrate.The water contact angle of the first interarea of the substrate after the surface treatment is 102 °.

(making of duplexer)

After the surface treatment, obtain similarly to Example 1 the duplexer that is formed by substrate and reinforcement plate.

(heat resistant test of duplexer)

[embodiment 7]

(making of reinforcement plate)

Gripper shoe is carried out pure water washing, UV washing, make the surface cleaning of gripper shoe.Utilize serigraphy at the single face coating 99.5 mass parts hardening resin compositions of gripper shoe and mixture (the coating weight 30g/m of 0.5 mass parts silicone oil thereafter, ²).Herein, hardening resin composition uses the composition identical with embodiment 2, silicone oil use dimethyl polysiloxane (Dow Corning Toray Co., the Ltd. manufacturing, SH200).

Be coated on mixture on the gripper shoe in atmosphere, 180 ℃ of lower heating made it solidify in 30 minutes, thereby the centre on gripper shoe forms and the silicone layer of fixed length 705mm * wide 595mm * thickness 20 μ m.

(making of duplexer)

After making reinforcement plate, the surperficial stacked silicone layer after the washing of substrate at room temperature fits tightly substrate and silicone layer by vacuum pressing, thereby obtains the duplexer that formed by substrate and reinforcement plate.

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, peel off similarly to Example 1 substrate and silicone layer.According to the observation of light microscope, cohesion failure appears in the silicone layer that has no after peeling off, and has no substrate after peeling off and transfer printing from the resin of silicone layer occurs.In addition, the water contact angle of the first interarea of the substrate after peeling off is 102 °.

[embodiment 8]

Substrate and gripper shoe are used respectively the polyimide resin plate (Du Pont-Toray Co., Ltd. makes, Kapton 200HV) of long 720mm * wide 600mm.Wherein, the thickness of substrate is made as 0.05mm, the thickness of gripper shoe is made as 0.5mm.

(making of reinforcement plate)

Among the embodiment 8, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Among the embodiment 8, the surface treatment of substrate is carried out in operation similarly to Example 2.The water contact angle of the first interarea of the substrate after the surface treatment is 100 °.

(making of duplexer)

After the surface treatment, the overlapping silicone layer of the first interarea to substrate at room temperature fits tightly substrate and silicone layer by vacuum pressing, thereby obtains the duplexer that formed by substrate and reinforcement plate.

(heat resistant test of duplexer)

[embodiment 9]

(making of reinforcement plate)

Among the embodiment 9, reinforcement plate is made in similarly to Example 2 operation.

(surface treatment of substrate)

Substrate is carried out pure water washing, UV washing, make the surface cleaning of substrate.Thereafter, after the second interarea as the single face of substrate applies mask, with the first interarea of opposition side make silane coupler (Dow Corning Toray Co., Ltd. makes, Z6040) gas that forms of gasification is maintained in the atmosphere of saturation state and exposes 10 minutes.The surface temperature of the substrate during exposure is 25 ℃.The water contact angle of the first interarea of the substrate after the exposure is 100 °.

(making of duplexer)

After the surface treatment based on silane coupler, the overlapping silicone layer of the first interarea to substrate at room temperature fits tightly substrate and silicone layer by vacuum pressing, thereby obtains the duplexer that formed by substrate and reinforcement plate.

(heat resistant test of duplexer)

[comparative example 1]

(making of duplexer)

In the comparative example 1, similarly to Example 2 operation, make reinforcement plate, the first interarea of substrate carried out that pure water washing and UV wash and after the cleaningization, overlapping silicone layer on the first interarea of substrate, at room temperature by vacuum pressing substrate and silicone layer are fitted tightly, thereby obtain the duplexer that formed by substrate and reinforcement plate.In addition, the water contact angle before the fitting tightly of the face that fits tightly of substrate (the first interarea) is 7 °.

(heat resistant test of duplexer)

After this duplexer carried out heat treated similarly to Example 1, when peeling off similarly to Example 1 substrate and silicone layer, cohesion failure appearred in silicone layer, and the part of silicone layer is attached to substrate-side.

[comparative example 2]

(making of reinforcement plate)

In the comparative example 2, reinforcement plate is made in similarly to Example 2 operation.

(making of duplexer)

Make similarly to Example 2 reinforcement plate, the first interarea of substrate carried out the pure water washing and after the cleaningization, the overlapping silicone layer of the first interarea to substrate at room temperature fits tightly substrate and silicone layer by vacuum pressing, thereby obtains the duplexer that formed by substrate and reinforcement plate.In addition, the water contact angle before the fitting tightly of the first interarea of substrate is 40 °.

(heat resistant test of duplexer)

Understand in detail the present invention with reference to specific embodiment, but under the premise without departing from the spirit and scope of the present invention, can apply various corrections, change, this is apparent to those skilled in the art.

That the application applied for based on May 11st, 2010, Japanese patent application 2010-108952 are incorporated herein its content as reference.

Description of reference numerals

10 duplexers

20 substrates

201 fit tightly face (the first interarea)

202 second interareas

30 reinforcement plates

31 gripper shoes

32 resin beds

321 fit tightly face

Claims

1. the manufacture method of a duplexer, it is for making the method that has substrate and gripper shoe and be present in the duplexer of the resin bed between them, the method has following operation: described resin bed is formed on the operation on the described gripper shoe and makes described resin bed fit tightly operation in described substrate with strippable form

Wherein, be included in before the described operation that fits tightly the operation that at least one party to the described substrate surface that will fit tightly and described resin layer surface processes with silicone oil or silane coupler in advance, perhaps,

In forming the operation of described resin bed, form described resin bed by the resin that comprises silicone oil or silane coupler, then, in the described operation that fits tightly, make described substrate and described resin bed overlapping and fit tightly.

2. the manufacture method of duplexer according to claim 1, it has following operation:

To at least one party of the described substrate surface that will fit tightly and described resin layer surface be coated with silicone oil or silane coupler operation and

Make the operation of the processing of described silane coupler reaction when operation, silane-coating coupling agent that coating is carried out the low-molecular-weight processing to described silicone oil during silicone oil,

In the described operation that fit tightly make described substrate and described resin bed overlapping and fit tightly thereafter.

3. the manufacture method of duplexer according to claim 2, wherein, the described substrate surface that fit tightly has been implemented surface treatment with silicone oil or silane coupler, and the water contact angle that has applied the substrate surface of described processing is more than 90 °.

4. the manufacture method of each described duplexer according to claim 1 ~ 3, wherein, in the operation that described resin bed is formed on the described gripper shoe, form cured resin composition layer on described gripper shoe surface, then make this hardening resin composition be solidified to form described resin bed.

5. the manufacture method of each described duplexer according to claim 1 ~ 4, wherein, described resin bed is formed by silicones.

6. the manufacture method of each described duplexer according to claim 1 ~ 5, wherein, described resin bed is that the reaction solidfied material by olefinic organic based polysiloxane and organic hydrogen polysiloxanes forms.

7. duplexer, it has substrate and gripper shoe and is present in resin bed between them, described resin bed and described substrate fit tightly with strippable form, described resin bed is being fixed in the mode of the peel strength between them greater than the peel strength between described resin bed and the described substrate on the described gripper shoe

The described substrate surface that fits tightly and at least one party of described resin layer surface are formed by the surface of processing with silicone oil or silane coupler in advance, perhaps,

Described resin bed is the resin bed that is formed by the resin that comprises silicone oil or silane coupler.

8. duplexer according to claim 7, wherein, fitting tightly in the substrate surface of described resin layer surface is to have implemented the surface-treated surface with silicone oil or silane coupler.

9. duplexer according to claim 8, wherein, the described water contact angle of having implemented the surface-treated substrate surface is more than 90 °.

10. each described duplexer according to claim 7 ~ 9, wherein, described resin bed is formed by silicones.

11. each described duplexer according to claim 7 ~ 10, wherein, described resin bed is that the reaction solidfied material by olefinic organic based polysiloxane and organic hydrogen polysiloxanes forms.