CN104736340B - Glass laminate and its manufacture method and the supporting base material with silicone layer - Google Patents
Glass laminate and its manufacture method and the supporting base material with silicone layer Download PDFInfo
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- CN104736340B CN104736340B CN201380054462.5A CN201380054462A CN104736340B CN 104736340 B CN104736340 B CN 104736340B CN 201380054462 A CN201380054462 A CN 201380054462A CN 104736340 B CN104736340 B CN 104736340B
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- glass substrate
- silicone resin
- silicone
- layer
- resin layer
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Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 134
- 239000005340 laminated glass Substances 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title description 71
- 239000000758 substrate Substances 0.000 claims abstract description 352
- 239000011521 glass Substances 0.000 claims abstract description 332
- 229920002545 silicone oil Polymers 0.000 claims abstract description 89
- 125000003118 aryl group Chemical group 0.000 claims abstract description 40
- 229920002050 silicone resin Polymers 0.000 claims description 241
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 125000000962 organic group Chemical group 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 299
- 239000002585 base Substances 0.000 description 113
- 238000010438 heat treatment Methods 0.000 description 33
- 238000000206 photolithography Methods 0.000 description 23
- 238000005530 etching Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 19
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 19
- 238000001723 curing Methods 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 238000004544 sputter deposition Methods 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 14
- 238000010030 laminating Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- -1 siloxane unit Chemical group 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000007607 die coating method Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005224 laser annealing Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WNDSQRGJJHSKCQ-UHFFFAOYSA-N naphthalene-1,5-dicarbonitrile Chemical compound C1=CC=C2C(C#N)=CC=CC2=C1C#N WNDSQRGJJHSKCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
Landscapes
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
The present invention relates to a kind of glass laminate, the glass laminate possesses the layer of the layer, silicone layer and glass substrate of supporting base material successively, the peel strength at the layer of supporting base material and the interface of silicone layer is higher than silicone layer and the peel strength at the interface of glass substrate, the silicones of silicone layer is the cross-linking agent of bridging property organopolysiloxane, silicone layer contains silicone oil, one of silicones and silicone oil for containing in silicone layer have aromatic series base, and another one does not have aromatic series base substantially.
Description
Technical Field
The present invention relates to a glass laminate and a method for producing the same, and more particularly to a glass laminate having a silicone resin layer containing silicone oil and a method for producing the same.
In addition, the present invention relates to a support substrate having a silicone layer, and more particularly, to a support substrate having a silicone layer on a surface of which a glass substrate is to be peelably laminated, and a method for manufacturing the same.
Background
In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and glass substrates used for these devices have been made thinner. If the strength of the glass substrate is insufficient due to thinning, the handling property of the glass substrate in the device manufacturing process is degraded.
Therefore, the following methods have been widely adopted in the past: after a device member (for example, a thin film transistor) is formed on a glass substrate having a thickness larger than the final thickness, the glass substrate is thinned by a chemical etching treatment.
However, in this method, for example, when the thickness of 1 glass substrate is thinned from 0.7mm to 0.2mm or 0.1mm, most of the material of the original glass substrate is removed by the etching solution, which is not preferable from the viewpoint of productivity and efficiency of use of the raw material. In the method of making a glass substrate into a thin plate by chemical etching, when a fine flaw is present on the surface of the glass substrate, a fine pit (etching pit) may be formed from the flaw as a starting point by the etching treatment, resulting in an optical defect.
Recently, in order to solve the above problems, the following methods have been proposed: a glass laminate in which a thin plate glass substrate and a reinforcing plate are laminated is prepared, a member for an electronic device such as a display device is formed on the thin plate glass substrate of the glass laminate, and then the support plate is separated from the thin plate glass substrate (see, for example, patent document 1 or patent document 2). The reinforcing plate has a support plate and a silicone resin layer fixed to the support plate, and the silicone resin layer and the thin glass substrate are bonded in a peelable manner. The interface between the silicone resin layer of the glass laminate and the thin plate glass substrate is peeled off, and the reinforcing plate separated from the thin plate glass substrate can be laminated with a new thin plate glass substrate, and can be reused as a glass laminate.
Patent document 2 (particularly, example 7) specifically discloses the use of a silicone resin layer containing dimethylpolysiloxane as a silicone oil.
Documents of the prior art
Patent document
Patent document 1: WO 2007/018028 No. 2
Patent document 2: WO2011/142280 No. 2
Disclosure of Invention
Problems to be solved by the invention
In recent years, higher heat resistance has been required for the glass laminates described in patent documents 1 and 2. With the advancement and complication of the functions of the electronic device member formed on the glass substrate of the glass laminate, the temperature at the time of forming the electronic device member is further increased, and the time required for exposure to the high temperature is also long. Further, the glass substrate to be used is also further thinned, and the handling property thereof becomes difficult.
The glass laminates described in patent documents 1 and 2 can withstand treatment in the atmosphere at 300 ℃ for 1 hour. However, according to the studies of the present inventors, referring to patent documents 1 and 2, when a glass laminate using a glass substrate having a smaller thickness is subjected to a treatment at 350 ℃ for 1 hour, when the glass substrate is peeled from the surface of the silicone resin layer, the glass substrate may not be peeled from the surface of the resin layer and a part of the glass substrate may be broken, or a part of the resin layer may remain on the glass substrate, which may result in a decrease in the productivity of the electronic device.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a glass laminate in which an increase in peel strength between a glass substrate and a silicone resin layer is suppressed even after a high-temperature heat treatment condition, and the glass substrate can be easily peeled, and a method for manufacturing the same.
The present invention also relates to a support base material having a silicone resin layer used for producing the glass laminate.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention.
That is, a first aspect of the present invention is a glass laminate comprising a layer of a support base, a silicone resin layer, and a layer of a glass substrate in this order, wherein the peel strength at the interface between the layer of the support base and the silicone resin layer is higher than the peel strength at the interface between the silicone resin layer and the glass substrate, wherein the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, the silicone resin layer contains a silicone oil, and one of the silicone resin and the silicone oil contained in the silicone resin layer has an aromatic group and the other has substantially no aromatic group.
In the first aspect, the silicone oil preferably has a phenyl group, and the content of phenyl groups in all organic groups bonded to silicon atoms in the silicone oil is preferably 5 to 50 mol%.
In the first aspect, the content of the silicone oil in the silicone resin layer is preferably 6 to 20 parts by mass with respect to 100 parts by mass of the silicone resin.
In the first embodiment, the viscosity of the silicone oil at 25 ℃ is preferably 100 to 6000 cP.
In the first embodiment, the thickness of the silicone resin layer is preferably 2 to 100 μm.
In the first mode, the support substrate is preferably a glass plate.
A second aspect of the present invention is a method for producing a glass laminate according to the first aspect, characterized in that a layer containing a crosslinkable organopolysiloxane and a silicone oil is formed on one surface of a support base, the crosslinkable organopolysiloxane is crosslinked on the surface of the support base to form a silicone resin layer, and then a glass substrate is laminated on the surface of the silicone resin layer.
A third aspect of the present invention is a support substrate having a silicone layer, comprising a support substrate and a silicone layer having a releasable surface provided on a surface of the support substrate, wherein the silicone resin of the silicone layer is a crosslinked product of a crosslinkable organopolysiloxane, the silicone layer contains a silicone oil, one of the silicone resin and the silicone oil contained in the silicone layer has an aromatic group, and the other has substantially no aromatic group.
In the third embodiment, the silicone oil preferably has a phenyl group, and the content of phenyl groups in all organic groups bonded to silicon atoms in the silicone oil is preferably 5 to 50 mol%, and more preferably 5 to 30 mol%.
In the third aspect, the content of the silicone oil in the silicone resin layer is preferably 6 to 20 parts by mass with respect to 100 parts by mass of the silicone resin.
In the third embodiment, the viscosity of the silicone oil at 25 ℃ is preferably 100 to 6000 cP.
Effects of the invention
According to the present invention, it is possible to provide a glass laminate in which an increase in peel strength between a glass substrate and a silicone resin layer is suppressed even after a high-temperature heat treatment condition, and the glass substrate can be easily peeled, and a method for manufacturing the same.
In addition, according to the present invention, a support substrate having a silicone resin layer used in the production of the glass laminate can be provided.
Drawings
FIG. 1 is a schematic cross-sectional view of one embodiment of a glass laminate of the present invention.
Fig. 2(a) to 2(D) are schematic cross-sectional views showing an embodiment of the method for manufacturing a glass substrate with a member according to the present invention in the order of steps.
Detailed Description
The present invention is not limited to the following embodiments, and various modifications and substitutions may be made thereto without departing from the scope of the present invention.
The glass laminate of the present invention comprises a layer supporting a substrate, a silicone resin layer, and a glass substrate in this order. That is, since the silicone resin layer is provided between the layer of the support base and the layer of the glass substrate, one side of the silicone resin layer is in contact with the layer of the support base and the other side is in contact with the layer of the glass substrate.
One of the characteristics of the glass laminate of the present invention is as follows: the silicone resin layer contains silicone oil, and only one of the silicone resin and the silicone oil in the silicone resin layer has an aromatic group, and the other has substantially no aromatic group. By introducing an aromatic group into only one of the silicone resin and the silicone oil, the compatibility between the two is reduced. As a result, the silicone oil is likely to exude to the surface of the silicone resin layer in a short time, and even if the time from the formation of the silicone resin layer to the lamination of the glass substrate is short, the silicone resin layer exhibiting good releasability from the glass substrate is likely to be obtained, and as a result, an increase in the peel strength between the glass substrate and the silicone resin layer can be suppressed even after heating at a high temperature. As described later, when a predetermined silicone oil is used, the transparency of the surface of the silicone resin layer is further ensured, and the transparency of the surface of the glass substrate to be peeled is also more excellent.
Further, the silicone resin layer of the present invention exhibits good releasability, and therefore has a feature that even if the thickness of the glass substrate is reduced, the glass substrate is less likely to break at the time of peeling after heating at a high temperature.
FIG. 1 is a schematic cross-sectional view of one example of a glass laminate of the present invention.
As shown in fig. 1, the glass laminate 10 is a laminate including a layer supporting a base material 12, a layer of a glass substrate 16, and a silicone resin layer 14 therebetween. One surface of the silicone resin layer 14 is in contact with the layer of the support base 12, and the other surface thereof is in contact with the 1 st main surface 16a of the glass substrate 16. In other words, the silicone resin layer 14 is in contact with the 1 st main surface 16a of the glass substrate 16.
The double-layer portion composed of the layer supporting the base material 12 and the silicone resin layer 14 reinforces the glass substrate 16 in the member forming step of manufacturing a member for an electronic device such as a liquid crystal panel. The double-layer portion composed of the layer of the support base 12 and the silicone resin layer 14, which is previously manufactured for manufacturing the glass laminate 10, is referred to as a support base 18 having a silicone resin layer.
The glass laminate 10 is used until a member forming step described later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the 2 nd main surface 16b of the glass substrate 16. Thereafter, the glass laminate on which the electronic device member is formed is separated into the support base 18 having the silicone layer and the glass substrate having the member, and the support base 18 having the silicone layer does not become a portion constituting the electronic device. A new glass substrate 16 can be stacked on the support base 18 having the silicone resin layer and reused as a new glass laminate 10.
The interface between the support base 12 and the silicone resin layer 14 has a peel strength (x), and when a peel-direction stress exceeding the peel strength (x) is applied to the interface between the support base 12 and the silicone resin layer 14, peeling occurs at the interface between the support base 12 and the silicone resin layer 14. The interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y), and when a peel-direction stress exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, peeling occurs at the interface between the silicone resin layer 14 and the glass substrate 16.
In the glass laminate 10 (also referred to as a laminate having an electronic device member described later), the peel strength (x) is higher than the peel strength (y). Therefore, when a stress in a direction in which the support base 12 and the glass substrate 16 are peeled off is applied to the glass laminate 10, the glass laminate 10 of the present invention is peeled off at the interface between the silicone layer 14 and the glass substrate 16, and is separated into the glass substrate 16 and the support base 18 having the silicone layer.
The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone layer 14 to the support base 12 can be increased, and relatively higher adhesion than that of the glass substrate 16 can be maintained after the heat treatment.
In order to improve the adhesion of the silicone resin layer 14 to the supporting base 12, as described later, it is preferable to form the silicone resin layer 14 by cross-linking and curing a cross-linkable organopolysiloxane on the supporting base 12. The silicone resin layer 14 bonded to the support substrate 12 with high bonding force can be formed by utilizing the bonding force at the time of crosslinking curing.
On the other hand, the bonding force of the cured product of the crosslinkable organopolysiloxane after crosslinking and curing to the glass substrate 16 is generally lower than the bonding force generated during crosslinking and curing. Therefore, it is preferable to produce the glass laminate 10 by forming the silicone resin layer 14 by cross-linking and curing the cross-linkable organopolysiloxane on the support base 12, and then laminating the glass substrate 16 on the surface of the silicone resin layer 14.
Next, the respective layers (the support base 12, the glass substrate 16, and the silicone resin layer 14) constituting the glass laminate 10 will be described in detail first, and then the glass laminate and the method for manufacturing the glass substrate having the member will be described in detail.
[ supporting base Material ]
The support base material 12 supports the glass substrate 16 for reinforcement, and prevents the glass substrate 16 from being deformed, damaged, or broken during the production of the electronic component member in a member forming step (step of producing the electronic component member) to be described later.
As the support base material 12, for example, a glass plate, a plastic plate, a metal plate such as SUS plate, or the like can be used. In general, since the member forming step is accompanied by heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16, more preferably the same material as the glass substrate 16, and the support base 12 is preferably a glass plate. In particular, the support base material 12 is preferably a glass plate made of the same glass material as the glass substrate 16.
The support substrate 12 may be thicker or thinner than the glass substrate 16. The thickness of the support base 12 is preferably selected based on the thickness of the glass substrate 16, the thickness of the silicone layer 14, and the thickness of the glass laminate 10, and for example, the thickness of the support base 12 is set to 0.4mm when the sum of the thickness of the glass substrate 16 and the thickness of the silicone layer 14 is 0.1mm, in the current member forming process, which is designed to process a substrate having a thickness of 0.5 mm. The thickness of the supporting substrate 12 is preferably 0.2 to 5.0mm in a usual case.
When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08mm or more for the reasons of easy handling, difficulty in breaking, and the like. Further, the thickness of the glass plate is preferably 1.0mm or less for the reason that the glass plate is desired to have rigidity that does not crack and can be appropriately flexed when peeled off after the electronic device member is formed.
The difference between the average linear expansion coefficients of the supporting base material 12 and the glass substrate 16 at 25 to 300 ℃ is preferably 500 × 10-7Less than/DEG C, more preferably 300 × 10-7Less than or equal to 200/DEG C, more preferably 200 × 10-7Below/° c. If the difference is too large, the glass laminate 10 may be severely warped or the supporting base material 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming step. In the case where the material of the support base material 12 is the same as that of the glass substrate 16, the occurrence of such a problem can be suppressed.
[ glass substrate ]
The glass substrate 16 has a1 st main surface 16a in contact with the silicone resin layer 14, and an electronic component member is provided on a2 nd main surface 16b on the side opposite to the silicone resin layer 14 side.
The glass substrate 16 may be of a conventional type, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 16 is excellent in chemical resistance and moisture permeation resistance, and has a low thermal shrinkage rate. As an index of the thermal shrinkage, a linear expansion coefficient specified in JIS R3102 (revised 1995) was used.
When the linear expansion coefficient of the glass substrate 16 is large, various defects are likely to occur because the member forming process is often accompanied by heat treatment. For example, in the case where TFTs are formed on the glass substrate 16, when the glass substrate 16 on which the TFTs are formed is cooled after heating, the TFTs may be excessively displaced due to thermal shrinkage of the glass substrate 16.
The glass substrate 16 can be obtained by melting a glass raw material and forming the molten glass into a plate shape. Such a forming method may be a conventional method, and for example, a float method, a melt method, a flow-down drawing method, a Fourccault method, a Lubbers method, or the like can be used. In particular, the glass substrate 16 having a small thickness can be obtained by molding a glass that has been temporarily molded into a sheet shape by a method (redraw method) in which the glass is heated to a temperature at which the glass can be molded and is drawn by a stretching or the like to be thin.
The type of glass of the glass substrate 16 is not particularly limited, but alkali-free borosilicate glass, soda-lime glass, high silica glass, and other oxide glass containing silicon oxide as a main component are preferable. The oxide glass is preferably a glass having a silicon oxide content of 40 to 90 mass% in terms of oxide.
As the glass of the glass substrate 16, glass suitable for the type of the member for electronic devices or the manufacturing process thereof is used. For example, since elution of an alkali metal component easily affects liquid crystal, a glass substrate for a liquid crystal panel is made of glass (alkali-free glass) substantially free of an alkali metal component (but usually contains an alkaline earth metal component). Thus, the glass of the glass substrate 16 is appropriately selected based on the kind of the device to be used and the manufacturing process thereof.
From the viewpoint of reduction in thickness and/or weight of the glass substrate 16, the thickness of the glass substrate 16 is preferably 0.3mm or less, more preferably 0.15mm or less, and still more preferably 0.10mm or less. When the thickness is 0.3mm or less, good flexibility can be imparted to the glass substrate 16. When the thickness is 0.15mm or less, the glass substrate 16 can be wound into a roll.
The thickness of the glass substrate 16 is preferably 0.03mm or more for the reasons of easy manufacturing of the glass substrate 16, easy handling of the glass substrate 16, and the like.
The glass substrate 16 may be formed of two or more layers, and in this case, the materials forming the respective layers may be the same type of material or different types of materials. In this case, the "thickness of the glass substrate 16" refers to the total thickness of all the layers.
[ Silicone layer ]
The silicone resin layer 14 prevents the glass substrate 16 from being displaced and prevents the glass substrate 16 and the like from being damaged by the separating operation until the operation of separating the glass substrate 16 from the support base 12 is performed. The surface (the 1 st main surface of the silicone resin layer) 14a of the silicone resin layer 14 in contact with the glass substrate 16 is in releasable contact with the 1 st main surface 16a of the glass substrate 16. The silicone resin layer 14 is bonded to the 1 st main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) at the interface is lower than the peel strength (x) at the interface between the silicone resin layer 14 and the support base 12.
That is, when the glass substrate 16 and the support base 12 are separated from each other, peeling occurs at the interface between the 1 st main surface 16a of the glass substrate 16 and the silicone resin layer 14, and peeling hardly occurs at the interface between the support base 12 and the silicone resin layer 14. Therefore, the silicone resin layer 14 has surface characteristics that it adheres to the 1 st main surface 16a of the glass substrate 16 but can easily peel off the glass substrate 16. That is, the silicone resin layer 14 is bonded to the 1 st main surface 16a of the glass substrate 16 with a certain degree of bonding force to prevent the glass substrate 16 from being displaced, and is bonded with a bonding force to such an extent that the glass substrate 16 is not broken and can be easily peeled when the glass substrate 16 is peeled. In the present invention, such a property of the silicone resin layer 14 surface that can be easily peeled is referred to as peelability. On the other hand, the first main surface 1 of the support base 12 and the silicone resin layer 14 are bonded to each other with a bonding force that is relatively difficult to peel.
Before and after the electronic device member is formed on the surface (the 2 nd main surface 16b) of the glass substrate 16 of the glass laminate 10, the bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may be changed (that is, the peel strength (x) and the peel strength (y) may be changed). However, even after the electronic device member is formed, the peel strength (y) is lower than the peel strength (x).
The silicone layer 14 and the glass substrate 16 are considered to be bonded together with weak adhesive force, i.e., a bonding force due to van der waals force. When the glass substrate 16 is laminated on the surface of the silicone resin layer 14 after the silicone resin layer 14 is formed, it is considered that the silicone resin of the silicone resin layer 14 is bonded with a bonding force due to van der waals force when the silicone resin is sufficiently crosslinked to such an extent that the bonding force is not exhibited. However, the silicone resin of the silicone resin layer 14 rarely has a weak adhesive force to some extent. Even when the adhesiveness is extremely low, when a member for an electronic device is formed on the glass laminate 10 after the production thereof, it is considered that the silicone resin of the silicone resin layer 14 adheres to the surface of the glass substrate 16 by a heating operation or the like, and the bonding force between the silicone resin layer 14 and the layer of the glass substrate 16 increases.
Optionally, the surface of the silicone resin layer 14 before lamination and the 1 st main surface 16a of the glass substrate 16 before lamination may be subjected to a treatment for weakening the bonding force therebetween before lamination. By laminating the surfaces to be laminated after performing a non-adhesive treatment or the like, the bonding force at the interface between the silicone resin layer 14 and the layer of the glass substrate 16 can be weakened, and the peel strength (y) can be reduced.
The silicone resin layer 14 is bonded to the surface of the supporting base material 12 with a strong bonding force such as an adhesive force or an adhesive force. For example, as described above, by crosslinking and curing the crosslinkable organopolysiloxane on the surface of the supporting base material 12, a silicone resin as a crosslinked product can be bonded to the surface of the supporting base material 12 to obtain a high bonding force. In addition, a treatment (for example, a treatment using a coupling agent) that generates a strong bonding force between the surface of the support substrate 12 and the silicone resin layer 14 may be performed to improve the bonding force between the surface of the support substrate 12 and the silicone resin layer 14.
The silicone resin layer 14 and the layer supporting the substrate 12 are bonded with a high bonding force, meaning that the peel strength (x) at the interface between the two is high.
The thickness of the silicone resin layer 14 is not particularly limited, but is preferably 2 to 100 μm, more preferably 3 to 50 μm, and still more preferably 7 to 20 μm. When the thickness of the silicone resin layer 14 is within this range, strain defects in the glass substrate 16 can be suppressed even if air bubbles or foreign matter are present between the silicone resin layer 14 and the glass substrate 16. In addition, when the thickness of the silicone resin layer 14 is too thick, it takes time and material to form it, which is not economical, and heat resistance may be lowered. If the thickness of the silicone resin layer 14 is too small, the adhesion between the silicone resin layer 14 and the glass substrate 16 may be reduced.
The silicone resin layer 14 may be formed of two or more layers. In this case, the "thickness of the silicone resin layer 14" refers to the total thickness of all layers.
In addition, in the case where the silicone resin layer 14 is composed of two or more layers, the resins forming each layer may be composed of different crosslinked silicone resins.
The silicone resin contained in the silicone resin layer 14 is a crosslinked product of a crosslinkable organopolysiloxane, and the silicone resin forms a three-dimensional network structure.
The type of the crosslinkable organopolysiloxane is not particularly limited, and the structure thereof is not particularly limited as long as it is crosslinked and cured by a predetermined crosslinking reaction to form a crosslinked material (cured product) constituting the silicone resin, and it is sufficient if it has a predetermined crosslinkability. The form of crosslinking is not particularly limited, and any known form may be adopted as appropriate depending on the kind of crosslinkable group contained in the crosslinkable organopolysiloxane. Examples thereof include hydrosilylation reactions; condensation reaction; or a radical reaction using a heat treatment, a high-energy ray treatment or a radical polymerization initiator; and so on.
More specifically, when the crosslinkable organopolysiloxane has radical-reactive groups such as alkenyl groups or alkynyl groups, the radical-reactive groups react with each other via the radical reaction to crosslink the organopolysiloxane to form a cured product (crosslinked silicone resin).
When the crosslinkable organopolysiloxane has silanol groups, the silanol groups are crosslinked by a condensation reaction with each other to form a cured product.
When the crosslinkable organopolysiloxane contains an organopolysiloxane (i.e., an organoalkenylpolysiloxane) having an alkenyl group (e.g., a vinyl group) bonded to a silicon atom and an organopolysiloxane (i.e., an organohydrogenpolysiloxane) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom, the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (e.g., a platinum-based catalyst), thereby forming a cured product.
Among them, from the viewpoint of easy formation of the silicone resin layer 14 and more excellent releasability of the glass substrate, a preferable embodiment is one in which the crosslinkable organopolysiloxane includes an organopolysiloxane having an alkenyl group at both terminals and/or in a side chain (hereinafter also referred to as organopolysiloxane a) and an organopolysiloxane having a hydrosilyl group at both terminals and/or in a side chain (hereinafter also referred to as organopolysiloxane B).
The alkenyl group is not particularly limited, but examples thereof include a vinyl group (vinyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferable because of excellent heat resistance.
Examples of the group other than the alkenyl group contained in the organopolysiloxane a and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly, an alkyl group having 4 or less carbon atoms).
The position of the alkenyl group in the organopolysiloxane a is not particularly limited, and when the organopolysiloxane a is linear, the alkenyl group may be present in either one of the M unit and the D unit shown below, or both of the M unit and the D unit. From the viewpoint of curing speed, it is preferably present at least in the M unit, preferably in both of the two M units.
The M unit and the D unit are examples of basic structural units of an organopolysiloxane, the M unit is a monofunctional siloxane unit to which three organic groups are bonded, and the D unit is a difunctional siloxane unit to which two organic groups are bonded. In the siloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded via one oxygen atom, whereby the number of oxygen atoms per silicon atom in the siloxane bond is considered to be 1/2, and the expression O is represented in the formula1/2。
The number of alkenyl groups in the organopolysiloxane a is not particularly limited, and is preferably 1 to 3, more preferably 2 per molecule.
The position of the hydrosilyl group in the organopolysiloxane B is not particularly limited, and when the organopolysiloxane a is linear, the hydrosilyl group may be present in either the M unit or the D unit, or both the M unit and the D unit. From the viewpoint of curing speed, it is preferably present at least in the D unit.
The number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, and preferably has at least 3, more preferably 3 in one molecule.
The mixing ratio of the organopolysiloxane a and the organopolysiloxane B is not particularly limited, but is preferably adjusted so that the molar ratio of the hydrogen atoms bonded to the silicon atoms in the organopolysiloxane B to the total alkenyl groups in the organopolysiloxane a (hydrogen atoms/alkenyl groups) is 0.7 to 1.05. Among them, the mixing ratio is preferably adjusted to 0.8 to 1.0.
As the hydrosilylation catalyst, a platinum group metal-based catalyst is preferably used. The platinum group metal catalyst includes platinum-based, palladium-based, rhodium-based catalysts, and the like, and the platinum-based catalyst is particularly preferably used from the viewpoint of economy and reactivity. As the platinum group metal catalyst, a known platinum group metal catalyst can be used. Specifically, platinum fine powder; platinum black; chloroplatinic acids such as tetrachloroplatinic acid and hexachloroplatinic acid; platinum tetrachloride; alcohol compounds, aldehyde compounds of chloroplatinic acid; or an olefin complex, alkenylsiloxane complex, carbonyl complex of platinum; and so on.
The amount of the hydrosilylation catalyst is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the organopolysiloxane a and the organopolysiloxane B.
The weight average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, and is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000 in terms of polystyrene as measured by GPC (gel permeation chromatography) from the viewpoints of excellent handling properties and film-forming properties, and further suppressing decomposition of the silicone resin under high-temperature processing conditions.
The viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPas, more preferably 15 to 3000 mPas. The viscosity value described in the present specification is a value measured at 25 ℃ unless otherwise specified.
Specific commercially available trade names and types of the crosslinkable organopolysiloxane include KNS-320A, KS-847 (all manufactured by shin-Etsu Silicone Co., Ltd.), TPR6700 (manufactured by Momentive Performance Materials, Japan contract Co., Ltd.), a combination of vinyl silicone "8500" (manufactured by Mitsuka chemical industries) and methylhydrogenpolysiloxane "12031" (manufactured by Mitsuka chemical industries), a combination of vinyl silicone "11364" (manufactured by Mitsuka chemical industries) and methylhydrogenpolysiloxane "12031" (manufactured by Mitsuka chemical industries), a combination of vinyl silicone "11365" (manufactured by Mitsuka chemical industries) and methylhydrogenpolysiloxane "12031" (manufactured by Mitsuka chemical industries), and the like.
The silicone resin layer 14 contains silicone oil. The silicone oil is a non-crosslinkable (non-reactive) organopolysiloxane which is different from the crosslinkable organopolysiloxane and does not react with the crosslinkable organopolysiloxane and which does not have crosslinkability.
The type of silicone oil is not particularly limited, and examples thereof include: pure silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane and the like; modified silicone oils obtained by introducing a polyether group, a halogen group, or the like into the side chain or the terminal of pure silicone oils.
Specific commercially available trade names and types of silicone oils include KTSF433 (manufactured by Momontevif functional materials, Japan contract Co., Ltd.), KF-50, KF-53, KF-54 (manufactured by shin-Etsu chemical Co., Ltd.), SH550 (manufactured by Toto Corning Co., Ltd.), and the like.
Examples of the silicone oil having no aromatic group include SH200 (manufactured by Torredo Corning Co., Ltd.), KNS-330 (manufactured by shin-Etsu chemical Co., Ltd.).
The viscosity of the silicone oil is not particularly limited, but is preferably 100 to 6000cP, more preferably 100 to 3000cP, and still more preferably 125 to 1000cP, in terms of easy bleeding to the surface of the silicone resin layer 14 and further excellent releasability of the glass substrate 16, and in terms of further excellent transparency of the glass substrate 16 after release.
The content of the silicone oil in the silicone resin layer 14 is not particularly limited, and is preferably 6 to 20 parts by mass, more preferably 6 to 15 parts by mass, and even more preferably 8 to 15 parts by mass, per 100 parts by mass of the silicone resin, in view of excellent releasability of the glass substrate 16 and further excellent transparency of the peeled glass substrate.
One of the silicone resin constituting the silicone resin layer 14 and the silicone oil contained in the silicone resin layer 14 has an aromatic group, and the other has substantially no aromatic group. In other words, only one of the silicone resin and the silicone oil has an aromatic group. As described above, in this method, the silicone resin has poor compatibility with the silicone oil, and as a result, the silicone oil easily bleeds out to the surface of the silicone resin layer 14, and the glass substrate 16 is easily peeled off even after the high-temperature heat treatment.
The fact that the silicone resin or silicone oil has substantially no aromatic group means that the silicone resin or silicone oil may have an aromatic group within a range not affecting the effect of the present invention, and more specifically, means that the content of the aromatic group in all the organic groups bonded to the silicon atom in the silicone resin or silicone oil is less than 1 mol%.
The silicone resin or silicone oil having an aromatic group means that the aromatic group is contained at a content of the aromatic group or more.
The type of the aromatic group is not particularly limited, and monovalent aromatic groups (for example, aromatic hydrocarbon groups or aromatic heterocyclic groups) and the like can be mentioned. Among these, aromatic hydrocarbon groups are preferable, and phenyl groups are particularly preferable, from the viewpoint of ease of preparation of silicone resin or silicone oil.
As the above-described mode, more specifically, there are the following two modes: the case where the silicone oil has an aromatic group and the silicone resin does not substantially have an aromatic group (mode a); the case where the silicone resin has an aromatic group and the silicone oil has substantially no aromatic group (mode B). Among them, the embodiment a is preferable in that the silicone resin layer 14 can be more easily produced and the glass substrate 16 is more excellent in releasability.
In the case of the embodiment a, the aromatic group contained in the silicone oil is preferably a phenyl group, and the content of the aromatic group (particularly, phenyl group) in all the organic groups bonded to the silicon atom in the silicone oil is preferably 5 to 50 mol%, more preferably 5 to 30 mol%, and further preferably 10 to 30 mol%, from the viewpoint that the glass substrate 16 after the high-temperature heat treatment is more excellent in releasability and the glass substrate 16 after the release is more excellent in transparency.
In the case of the embodiment a, the bonding position of the aromatic group in the silicone oil is not particularly limited, and both terminals and/or side chains may be mentioned. Examples of the group other than the phenyl group contained in the silicone oil include an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.).
On the other hand, in the case of the embodiment B, the aromatic group contained in the silicone resin is preferably a phenyl group, and the content of the aromatic group (particularly, phenyl group) in all the organic groups bonded to the silicon atom in the silicone resin is preferably 5 to 90 mol%, more preferably 30 to 90 mol%, from the viewpoint of more excellent releasability of the glass substrate 16 after the high-temperature heat treatment. In the case of the embodiment B, examples of the group other than the phenyl group contained in the silicone resin include an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.).
The silicone oil having an aromatic group is preferably a methylphenyl silicone oil, for example, because it is excellent in compatibility with the silicone resin.
Examples of the aromatic group-containing silicone resin include a silicone resin obtained by crosslinking a crosslinkable organopolysiloxane having a phenyl group.
[ glass laminate and Process for producing the same ]
As described above, the glass laminate 10 of the present invention is a laminate including the support base 12, the glass substrate 16, and the silicone resin layer 14 therebetween.
The method for producing the glass laminate 10 of the present invention is not particularly limited, and in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), it is preferable to form the silicone resin layer 14 by crosslinking and curing a predetermined crosslinkable organopolysiloxane on the surface of the supporting base 12. Namely the following method: the glass laminate 10 is produced by forming a layer containing a crosslinkable organopolysiloxane and silicone oil on the surface of the support base 12, crosslinking the crosslinkable organopolysiloxane on the surface of the support base 12 to form a silicone resin layer 14 (crosslinked silicone resin), and then laminating a glass substrate 16 on the silicone resin layer of the silicone resin layer 14.
It is considered that when the crosslinkable organopolysiloxane is cured on the surface of the supporting base 12, adhesion is caused by interaction with the surface of the supporting base 12 during the curing reaction, and the peel strength of the silicone resin from the surface of the supporting base 12 is improved. Therefore, even if the glass substrate 16 and the supporting base 12 are made of the same material, a difference in peel strength can be provided between the silicone resin layer 14 and the both.
Hereinafter, a step of forming a layer containing a crosslinkable organopolysiloxane and silicone oil on the surface of the support base 12 and forming the silicone resin layer 14 by crosslinking the crosslinkable organopolysiloxane on the surface of the support base 12 is referred to as a resin layer forming step, and a step of laminating the glass substrate 16 on the silicone resin layer of the silicone resin layer 14 to form the glass laminate 10 is referred to as a laminating step, and the flow of each step will be described in detail.
(resin layer Forming step)
In the resin layer forming step, a layer containing a crosslinkable organopolysiloxane and silicone oil is formed on the surface of the supporting base 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the supporting base 12 to form the silicone resin layer 14.
In order to form a layer containing the crosslinkable organopolysiloxane and the silicone oil on the supporting base 12, it is preferable to use a coating composition in which the crosslinkable organopolysiloxane and the silicone oil are dissolved in a solvent, coat the composition on the supporting base 12 to form a layer of the solution, and then remove the solvent to form a layer containing the crosslinkable organopolysiloxane and the silicone oil. The thickness of the layer containing the crosslinkable organopolysiloxane and the silicone oil can be controlled by adjusting the concentrations of the crosslinkable organopolysiloxane and the silicone oil in the composition, and the like.
The solvent is not particularly limited as long as it can easily dissolve the crosslinkable organopolysiloxane and the silicone oil in the working environment and can be easily volatilized and removed. Specific examples thereof include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like.
The method for applying the composition containing the crosslinkable organopolysiloxane and the silicone oil on the surface of the supporting base 12 is not particularly limited, and a known method can be used. Examples thereof include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method.
Thereafter, if necessary, a drying treatment for removing the solvent may be performed. The method of drying treatment is not particularly limited, and examples thereof include a method of removing the solvent under reduced pressure, a method of heating at a temperature at which the crosslinkable organopolysiloxane does not cure, and the like.
Next, the crosslinkable organopolysiloxane on the support base 12 is crosslinked to form the silicone resin layer 14. More specifically, as shown in fig. 2(a), the silicone resin layer 14 is formed on at least one surface of the supporting base 12 in this process.
As described above, the method of curing (crosslinking) is appropriately selected depending on the crosslinking form of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment. Among them, in the case where the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, the silicone resin layer 14 is preferably produced by heat curing from the viewpoint that a silicone resin excellent in adhesion to the glass substrate 16 and heat resistance can be obtained.
Next, the manner of heat curing is described in detail.
The temperature condition for thermally curing the crosslinkable organopolysiloxane is not particularly limited as long as it is within a range that can improve the heat resistance of the silicone resin layer 14 and can control the peel strength (y) after lamination with the glass substrate 16 as described above, and is preferably 150 to 300 ℃, more preferably 180 to 250 ℃. The heating time is preferably 10 to 120 minutes, and more preferably 30 to 60 minutes. When the temperature for heat curing is too low, heat resistance and flatness of the silicone resin layer 14 are lowered, while when the temperature is too high, the peel strength (y) is too low, and adhesion between the glass substrate 16 and the silicone resin layer 14 may be impaired.
The crosslinkable organopolysiloxane can be cured by precuring (precuring) and then post curing (main curing). By performing the pre-curing, the silicone resin layer 14 having more excellent heat resistance can be obtained. In this case, the step of forming a layer containing the crosslinkable organopolysiloxane and the silicone oil by removing the solvent from the layer and the step of performing the precuring are not particularly distinguished.
(laminating step)
The laminating step is a step of laminating the glass substrate 16 on the silicone surface of the silicone resin layer 14 obtained in the resin layer forming step to obtain the glass laminate 10 including the layer supporting the base material 12, the silicone resin layer 14, and the glass substrate 16 in this order. More specifically, as shown in fig. 2B, the glass laminate 10 is obtained by laminating the silicone resin layer 14 and the glass substrate 16 with the surface (the 1 st main surface of the silicone resin layer) 14a of the silicone resin layer 14 on the side opposite to the support base 12 side and the 1 st main surface 16a of the glass substrate 16 having the 1 st main surface 16a and the 2 nd main surface 16B as lamination surfaces.
The method of laminating the glass substrate 16 on the silicone resin layer 14 is not particularly limited, and a known method can be employed.
For example, a method of laminating the glass substrate 16 on the surface of the silicone resin layer 14 in a normal pressure atmosphere is given. After the glass substrate 16 is laminated on the surface of the silicone resin layer 14, the glass substrate 16 may be pressed to the silicone resin layer 14 using a roller or press (press) as needed. It is preferable that the air bubbles mixed between the silicone resin layer 14 and the layer of the glass substrate 16 be relatively easily removed by pressing with a roller or a press.
When the pressure bonding is performed by the vacuum lamination method or the vacuum pressing method, bubble inclusion is suppressed and good adhesion is secured, which is more preferable. By carrying out the pressing under vacuum, the following advantages are obtained: even when the fine bubbles remain, the bubbles do not grow by heating, and strain defects of the glass substrate 16 are hardly caused.
When laminating the glass substrate 16, it is preferable to sufficiently clean the surface of the glass substrate 16 in contact with the silicone resin layer 14 and laminate the glass substrate in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 16, and is therefore preferable.
After the glass substrates 16 are laminated, a pre-annealing treatment (heat treatment) may be performed as necessary. By performing this pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 can be improved, an appropriate peel strength (y) can be obtained, positional displacement of the electronic component member and the like are less likely to occur in the member forming step described later, and the productivity of the electronic component can be improved.
The conditions of the pre-annealing treatment are appropriately selected according to the type of the silicone resin layer 14 to be used, and the heat treatment is preferably performed at 300 ℃ or higher (preferably 300 to 400 ℃) for 5 minutes or longer (preferably 5 to 30 minutes) in order to more appropriately set the peel strength (y) between the glass substrate 16 and the silicone resin layer 14.
The formation of the silicone resin layer 14 is not limited to the above method.
For example, in the case of using the support base 12 made of a material having higher adhesion to the silicone surface than the glass substrate 16, a film of silicone resin can be produced by curing a crosslinkable organopolysiloxane on a releasable surface, and laminated while interposing the film between the glass substrate 16 and the support base 12.
In addition, when the adhesion obtained by curing the crosslinkable organopolysiloxane is sufficiently low for the glass substrate 16 and sufficiently high for the support base 12, the crosslinkable organopolysiloxane may be cured between the glass substrate 16 and the support base 12 to form the silicone resin layer 14.
Even when the support base 12 is made of the same glass material as the glass substrate 16, the adhesion of the surface of the support base 12 can be improved to improve the peel strength with respect to the silicone resin layer 14. Examples are: a chemical method (undercoating treatment) such as a silane coupling agent which chemically improves the fixing force; physical methods of increasing surface active groups such as flame (flame) treatment; a mechanical treatment method such as sand blasting to increase the grip by increasing the surface roughness; and so on.
(glass laminate)
The glass laminate 10 of the present invention can be used in various applications, for example, applications for manufacturing electronic components such as a panel for a display device, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on a surface thereof, which will be described later. In this application, the glass laminate 10 is often exposed (for example, for 1 hour or more) to a high temperature (for example, 350 ℃ or more).
Here, the panel for a display device includes: LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter (シャッター) panel, and the like.
[ glass substrate having Member and method for producing the same ]
In the present invention, a member-equipped glass substrate (a glass substrate having a member for an electronic device) including a glass substrate and a member for an electronic device is produced using the laminate.
The method for producing the glass substrate having a member is not particularly limited, and from the viewpoint of excellent productivity of electronic devices, the following method is preferred: the method for producing a laminate having a member for an electronic device, which comprises forming a member for an electronic device on a glass substrate in the above glass laminate, comprises separating the glass substrate having the member and the support base material having a silicone resin layer from the resulting laminate having the member for an electronic device, with the glass substrate-side interface of the silicone resin layer as a release surface.
Hereinafter, a step of forming an electronic component member on a glass substrate in the above glass laminate to produce a laminate having the electronic component member is referred to as a member forming step, and a step of separating the glass substrate having the member and the support base material having the silicone layer from the laminate having the electronic component member with a glass substrate side interface of the silicone layer as a release surface is referred to as a separating step.
Hereinafter, materials and flows used in the respective steps will be described in detail.
(Member-Forming step)
The member forming step is a step of forming a member for an electronic device on the glass substrate 16 in the glass laminate 10 obtained in the laminating step. More specifically, as shown in fig. 2C, the electronic component member 20 is formed on the 2 nd main surface 16b (exposed surface) of the glass substrate 16, and the laminate 22 having the electronic component member is obtained.
First, the electronic component member 20 used in the present step will be described in detail, and then the flow of the step will be described in detail.
(Member for electronic device (functional element))
The electronic device member 20 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of an electronic device. More specifically, examples of the electronic component member 20 include members used in electronic components such as a panel for a display device, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on a surface thereof (for example, a member for a display device, a member for a solar cell, a member for a thin film secondary battery, and a circuit for an electronic component).
For example, in the case of a silicon type solar cell member, a transparent electrode such as tin oxide for a positive electrode, a silicon layer represented by p layer/i layer/n layer, and a metal for a negative electrode are exemplified, and other members corresponding to a compound type, a dye-sensitized type, a quantum dot type, and the like are exemplified.
In the case of lithium ion type, examples of the member for a thin-film secondary battery include transparent electrodes of metals, metal oxides, and the like of the positive electrode and the negative electrode, lithium compounds of the electrolyte layer, metals of the current collecting layer, resins as the sealing layer, and the like, and other examples include various members corresponding to nickel hydride type, polymer type, ceramic electrolyte type, and the like.
In addition, in the case of a CCD or a CMOS, examples of the electronic component circuit include metals of a conductive portion, silicon oxide and silicon nitride of an insulating portion, and the like, and other examples of the electronic component circuit include various sensors such as a pressure sensor and an acceleration sensor, and various members such as a rigid printed board, a flexible printed board, and a rigid flexible printed board.
(flow of step)
The method for producing the laminate 22 having the electronic component member is not particularly limited, and the electronic component member 20 is formed on the surface of the 2 nd main surface 16b of the glass substrate 16 of the glass laminate 10 by a conventionally known method depending on the type of the constituent member of the electronic component member.
The electronic device member 20 may be not the entire member finally formed on the 2 nd main surface 16b of the glass substrate 16 (hereinafter referred to as "entire member"), but may be a part of the entire member (hereinafter referred to as "partial member"). The glass substrate having a partial member peeled from the silicone resin layer 14 may be formed into a glass substrate having an entire member (corresponding to an electronic device described later) in a subsequent step.
In addition, other electronic component members may be formed on the release surface (the 1 st main surface 16a) of the glass substrate having the entire member released from the silicone resin layer 14. Alternatively, the electronic device may be manufactured by assembling a laminate having the entire member and then peeling the support base material 12 from the laminate having the entire member. Further, it is also possible to manufacture a member-equipped glass substrate having two glass substrates by assembling two laminates having the entire member and then peeling off the two support base materials 12 from the laminates having the entire member.
For example, in the case of manufacturing an OLED, in order to form an organic EL structure on the surface of the glass substrate 16 of the glass laminate 10 opposite to the silicone resin layer 14 (corresponding to the 2 nd main surface 16b of the glass substrate 16), the following various layers are formed and treated: a transparent electrode is formed, and further a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like are vapor-deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed using a sealing plate, and the like. Examples of the layer formation and the treatment include a film formation treatment, a vapor deposition treatment, and a bonding treatment of a sealing plate.
In addition, for example, in the case of manufacturing a TFT-LCD, there are various steps as follows: a TFT forming step of forming a Thin Film Transistor (TFT) by patterning a metal film, a metal oxide film, or the like formed by a conventional film forming method such as a CVD method or a sputtering method, on the 2 nd main surface 16b of the glass substrate 16 of the glass laminate 10 using a resist solution; a CF forming step of forming a Color Filter (CF) on the 2 nd main surface 16b of the glass substrate 16 of the other glass laminate 10 by using a resist solution for patterning; and a bonding step of laminating the laminate having the TFT obtained in the TFT forming step and the laminate having the CF obtained in the CF forming step; and so on.
In the TFT forming step and the CF forming step, the TFT or the CF is formed on the 2 nd main surface 16b of the glass substrate 16 using a well-known photolithography (photolithography) technique, an etching technique, or the like. In this case, a resist solution may be used as the coating solution for pattern formation.
Before forming the TFTs and CF, the 2 nd main surface 16b of the glass substrate 16 may be cleaned as necessary. As the cleaning method, well-known dry cleaning or wet cleaning may be used.
In the bonding step, the thin film transistor-forming surface of the stacked body having the TFT and the color filter-forming surface of the stacked body having the CF are bonded to each other with a sealant (for example, an ultraviolet-curable sealant for cell formation). Then, a liquid crystal material is injected into a cell formed of a laminate having a TFT and a laminate having a CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a dropping injection method.
(separation Process)
As shown in fig. 2D, the separation step is a step of separating the glass substrate 16 (glass substrate with member) on which the electronic component member 20 is laminated and the support base 12 from the laminate 22 with the electronic component member obtained in the member forming step, with the interface between the silicone layer 14 and the glass substrate 16 as a release surface, to obtain a member-provided glass substrate 24 including the electronic component member 20 and the glass substrate 16.
When the electronic component member 20 on the glass substrate 16 is a part of the member forming the entire necessary configuration at the time of peeling, the remaining constituent members may be formed on the glass substrate 16 after separation.
The method for peeling the glass substrate 16 and the supporting base material 12 is not particularly limited. Specifically, for example, peeling may be performed by inserting a sharp blade-like object at the interface of the glass substrate 16 and the silicone layer 14, providing a starting point for peeling, and then blowing a mixed fluid of water and compressed air. Preferably, the laminate 22 having the electronic component member is placed on a stage so that the support base 12 is on the upper side and the electronic component member 20 is on the lower side, and the electronic component member 20 side is vacuum-sucked on the stage (sequentially in the case of double-sided lamination of the support base), and in this state, the cutter is first inserted into the interface between the glass substrate 16 and the silicone resin layer 14. Then, the side of the support base material 12 is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are lifted in order from the vicinity of the portion where the cutter is inserted. In this way, an air layer is formed at the interface between the silicone resin layer 14 and the glass substrate 16 and at the condensation-fractured surface of the silicone resin layer 14, and this air layer spreads over the interface and the condensation-fractured surface, and the support base 12 can be easily peeled off.
In addition, the support base material 12 may be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.
When the glass substrate 24 having the member is separated from the laminate 22 having the member for electronic devices, the fragments of the silicone resin layer 14 can be further suppressed from being electrostatically adsorbed on the glass substrate 24 having the member by blowing with an Ionizer (Ionizer) and controlling humidity.
The method for manufacturing the glass substrate 24 having the member is suitable for manufacturing a small display device used in a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, an MIM type, an IPS type, a VA type, and the like. Basically, the present invention can be applied to a display device of either a passive drive type or an active drive type.
Examples of the glass substrate 24 having a member manufactured by the above method include: a panel for a display device having a glass substrate and a member for a display device, a solar cell having a glass substrate and a member for a solar cell, a thin-film secondary cell having a glass substrate and a member for a thin-film secondary cell, an electronic component having a glass substrate and a member for an electronic device, and the like. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.
Examples
The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples.
In the following examples 1 to 5 and comparative examples 1 to 2, the glass substrate used was a glass substrateGlass plate made of alkali borosilicate glass (200 mm in length, 200mm in width, 0.2mm in plate thickness, linear expansion coefficient 38 × 10-7"AN 100" manufactured by Asahi glass company,. The glass plate made of the same alkali-free borosilicate glass (240 mm in vertical direction, 240mm in horizontal direction, 0.5mm in plate thickness, linear expansion coefficient 38 × 10, 10) was used as a supporting substrate-7"AN 100" manufactured by Asahi glass company,/° C).
< example 1 >
First, a support base having a thickness of 0.5mm was cleaned with pure water and then cleaned with UV.
Next, an organoalkenylpolysiloxane having vinyl groups at both ends (vinylsilicone, 8500, manufactured by Mitsuwa chemical industries, Ltd.) and a methylhydrogenpolysiloxane having hydrosilyl groups in the molecule (12031, manufactured by Mitsuwa chemical industries, Ltd.) were compounded. The molar ratio of the total vinyl groups in the organoalkenylpolysiloxane to the silicon-bonded hydrogen atoms in the methylhydrogenpolysiloxane was set to 1: 1. 5 parts by weight of a platinum catalyst (CAT 12070, manufactured by Mitsukawa chemical industries, Ltd.) was added to 100 parts by weight of the resin component. Furthermore, a solution containing a crosslinkable organopolysiloxane was prepared by adding methyl phenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.) and heptane. This solution was applied to the 1 st main surface of a support substrate by a spin coater (rotation speed 300rpm, 15 seconds), to provide a layer (coating weight 20 g/m) comprising an uncured crosslinkable organopolysiloxane and a silicone oil on the support substrate2)。
The amount of the methylphenyl silicone oil used was 8 parts by mass per 100 parts by mass of the total of the organoalkenylpolysiloxane and the methylhydrogenpolysiloxane. The amount of heptane used was 100 parts by mass per 100 parts by mass of the total of the organoalkenylpolysiloxane and the methylhydrogenpolysiloxane. The content of phenyl groups contained in the methylphenyl silicone oil was 5 mol% based on the total organic groups bonded to silicon atoms in the silicone oil.
Subsequently, the resultant was cured by heating at 230 ℃ for 10 minutes in the air to form a silicone resin layer having a thickness of 10 μm on the 1 st main surface of the support base. In this embodiment, the silicone resin of the silicone resin layer does not have an aromatic group, and the methylphenyl silicone oil as the silicone oil has an aromatic group (phenyl group). In addition, the silicone layer is transparent.
Then, the glass substrate and the silicone resin layer of the support base material were laminated by vacuum pressing at room temperature to obtain a glass laminate a.
In the resulting glass laminate a, the support base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and were free from strain defects and had good smoothness.
Next, the glass laminate a was subjected to a heating treatment at 350 ℃ for 60 minutes in a nitrogen atmosphere and cooled to room temperature, and as a result, no change in appearance such as separation of the support base material from the glass substrate and foaming or whitening of the silicone resin layer in the glass laminate a was observed.
Thereafter, a stainless steel blade having a thickness of 0.1mm was inserted into the interface between the glass substrate and the supporting silicone layer at one corner of the four positions of the glass laminate a to form a peeling starting point, and the glass substrate and the supporting base material were separated without damage by applying an external force in the direction in which the glass substrate and the supporting base material were separated from each other while the vacuum suction pad was attracted to the surface of the non-peeling surface of each of the glass substrate and the supporting base material. Here, the insertion of the tool was performed while blowing off the electric fluid to the interface by an ionizer (manufactured by keyence corporation). Specifically, the vacuum adsorption pad is lifted while the gap formed is continuously blown with the electrically-removing fluid by the ionizer.
From the results of the separation of the silicone layer from the glass substrate together with the support base, it was confirmed that the peel strength (x) at the interface between the layer of the support base and the silicone layer was higher than the peel strength (y) at the interface between the silicone layer and the glass substrate. The surface of the glass substrate after peeling was transparent.
< example 2 >
A glass laminate B was obtained in the same manner as in example 1 except that a methylphenyl silicone oil (KF-50, viscosity 3000cP, manufactured by shin-Etsu chemical Co., Ltd.) was used in place of the methylphenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.).
The content of phenyl groups contained in the methylphenyl silicone oil used was 5 mol% based on the total organic groups bonded to silicon atoms in the silicone oil.
The appearance of the silicone resin layer is transparent even immediately after production, and is also transparent even after a glass substrate is laminated thereon.
In the resulting glass laminate B, the support base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and the glass laminate B was free from strain defects and had good smoothness.
Next, the glass laminate B was subjected to the same heat treatment as in example 1, and as a result, no change in appearance such as separation of the support base material from the glass substrate and foaming or whitening of the silicone resin layer in the glass laminate B was observed.
Thereafter, the glass laminate B was separated from the glass substrate in the same manner as in example 1, and as a result, the glass substrate and the support substrate were separated without damage. The silicone resin layer is separated from the glass substrate together with the support base material. From the results, it was confirmed that the peel strength (x) at the interface between the layer of the support base and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate. The surface of the glass substrate after peeling was transparent.
< example 3 >
A glass laminate C was obtained in the same manner as in example 1 except that a methylphenyl silicone oil (KF-54, viscosity 400cP, manufactured by shin-Etsu chemical Co., Ltd.) was used in place of the methylphenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.).
The content of phenyl groups contained in the methylphenyl silicone oil used was 25 mol% based on the total organic groups bonded to silicon atoms in the silicone oil.
The appearance of the silicone resin layer was slightly cloudy immediately after production, and the glass substrate was laminated thereon to make it transparent.
In the resulting glass laminate C, the support base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and the glass laminate C had no strain-like defects and also had good smoothness.
Next, the glass laminate C was subjected to the same heat treatment as in example 1, and as a result, no change in appearance such as separation of the support base material from the glass substrate and foaming or whitening of the silicone resin layer was observed in the glass laminate C.
Then, the glass laminate C was separated from the glass substrate in the same manner as in example 1, and as a result, the glass substrate and the support substrate were separated without breakage. The silicone resin layer is separated from the glass substrate together with the support base material. From the results, it was confirmed that the peel strength (x) at the interface between the layer of the support base and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate. The surface of the glass substrate after peeling was slightly cloudy.
< example 4 >
A glass laminate D was obtained in the same manner as in example 1 except that a methylphenyl silicone oil (SH 550, viscosity 125cP, manufactured by Tolydo Corning Co., Ltd.) was used in place of the methylphenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.).
The content of phenyl groups contained in the methylphenyl silicone oil used was 25 mol% based on the total organic groups bonded to silicon atoms in the silicone oil.
The appearance of the silicone resin layer was slightly cloudy immediately after production, and the glass substrate was laminated thereon to make it transparent.
In the resulting glass laminate D, the support base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and the glass laminate D was free from strain defects and had good smoothness.
Next, the glass laminate E was subjected to the same heat treatment as in example 1, and as a result, no change in appearance such as separation of the support base material from the glass substrate and foaming or whitening of the silicone resin layer in the glass laminate D was observed.
Then, the glass laminate D was separated from the glass substrate in the same manner as in example 1, and as a result, the glass substrate and the support substrate were separated without breakage. The silicone resin layer is separated from the glass substrate together with the support base material. From the results, it was confirmed that the peel strength (x) at the interface between the layer of the support base and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate. The surface of the glass substrate after peeling was slightly cloudy.
< example 5 >
A glass laminate E was obtained in the same manner as in example 1 except that methylphenyl silicone oil (TSF 433, viscosity 450cP, manufactured by Morgate corporation) was used in place of the methylphenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.).
The content of phenyl groups contained in the methylphenyl silicone oil used was 25 mol% based on the total organic groups bonded to silicon atoms in the silicone oil.
The appearance of the silicone resin layer was slightly cloudy immediately after production, and the glass substrate was laminated thereon to make it transparent.
In the resulting glass laminate E, the support base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and the glass laminate E was free from strain defects and had good smoothness.
Next, the glass laminate E was subjected to the same heat treatment as in example 1, and as a result, no change in appearance such as separation of the support base material from the glass substrate and foaming or whitening of the silicone resin layer in the glass laminate E was observed.
Then, the glass laminate E was separated from the glass substrate in the same manner as in example 1, and as a result, the glass substrate and the support substrate were separated without breakage. The silicone resin layer is separated from the glass substrate together with the support base material. From the results, it was confirmed that the peel strength (x) at the interface between the layer of the support base and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate. The surface of the glass substrate after peeling was slightly cloudy.
The viscosity and phenyl content of the silicone oils used in examples 1 to 5 are summarized below.
TABLE 1
| Viscosity of Silicone oil | Content of phenyl group | |
| Example 1 | 100cP | 5 mol% |
| Example 2 | 3000cP | 5 mol% |
| Example 3 | 400cP | 25 mol% |
| Example 4 | 125cP | 25 mol% |
| Example 5 | 450cP | 25 mol% |
< comparative example 1 >
A glass laminate X was obtained in the same manner as in example 1, except that methyl phenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.) was not used.
In the glass laminate X obtained, the supporting base material and the glass substrate were separated in the same manner as in example 1, and as a result, the silicone resin layer and the glass substrate were less likely to be peeled off, and the glass substrate was also broken.
< comparative example 2 >
A glass laminate Y was obtained in the same manner as in example 1 except that 0.5 part by weight of methyl silicone oil (SH 200, viscosity 200cP, manufactured by Tolydo Corning Co., Ltd.) was used in place of the methyl phenyl silicone oil (KF-50, viscosity 100cP, manufactured by shin-Etsu chemical Co., Ltd.). This embodiment corresponds to the embodiment of example 7 in the conventional document (WO2011/142280 pamphlet), and neither the silicone resin nor the silicone oil contains an aromatic group.
In the glass laminate Y obtained, the supporting base and the glass substrate were separated in the same manner as in example 1, and as a result, the silicone resin layer and the glass substrate were less likely to be peeled off, and the glass substrate was also broken.
In the cases of examples 1 to 5, even after the high-temperature heat treatment, the thin glass substrate could be easily peeled. In examples 1 and 2, the surface (release surface) of the glass substrate after the release was transparent, but in examples 3 to 5, the surface was slightly cloudy. This is presumably because in examples 3 to 5, a part of the silicone oil exuded to the surface of the silicone resin layer was transferred onto the glass substrate. From the above results, it was confirmed that the silicone oils used in examples 1 and 2 were superior in the cleaning property of the surface of the glass substrate after peeling.
On the other hand, in comparative example 1 in which no silicone oil was used and comparative example 2 in which no aromatic group was contained in both the silicone resin and the silicone oil, the releasability was poor.
< example 6 >
In this example, an OLED was manufactured using the glass laminate a obtained in example 1.
First, silicon nitride, silicon oxide, and amorphous silicon were sequentially formed on the 2 nd main surface of the glass substrate in the glass laminate a by a plasma CVD method. Next, boron was implanted into the amorphous silicon layer at a low concentration by an ion doping apparatus, and heat treatment was performed at 450 ℃ for 60 minutes in a nitrogen atmosphere to perform dehydrogenation treatment. Next, crystallization treatment of the amorphous silicon layer was performed by a laser annealing apparatus. Next, by etching using photolithography and an ion doping apparatus, phosphorus is implanted at a low concentration into the amorphous silicon layer, thereby forming N-type and P-type TFT regions. Next, a silicon oxide film was formed on the 2 nd main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, molybdenum was formed by a sputtering method, and a gate electrode was formed by etching using a photolithography method. Next, a source region and a drain region are formed by implanting boron and phosphorus at high concentrations into desired regions of the N-type and the P-type, respectively, using photolithography and an ion doping apparatus. Next, on the 2 nd main surface side of the glass substrate, an interlayer insulating film is formed by silicon oxide film formation by a plasma CVD method, aluminum film formation is formed by a sputtering method, and a TFT electrode is formed by etching using a photolithography method. Then, a passivation layer was formed by performing a heat treatment at 450 ℃ for 60 minutes under a hydrogen atmosphere to perform a hydrogenation treatment, and then forming a silicon nitride film by a plasma CVD method. Next, an ultraviolet curable resin was applied to the 2 nd main surface side of the glass substrate, and a planarization layer and a contact hole were formed by photolithography. Next, indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.
Then, 4', 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl ] triphenylamine as a hole transport layer were sequentially formed on the 2 nd main surface side of the glass substrate by a vapor deposition method]Benzidine, and 2, 6-bis [4- [ N- (4-methoxyphenyl) -N-phenyl ] mixed with 40 vol% as a light-emitting layer]Aminostyryl radical]8-hydroxyquinoline aluminum complex (Alq) of naphthalene-1, 5-dicarbonitrile (BSN-BCN)3) Alq as an electron transport layer3. Next, aluminum was deposited by sputtering, and the counter electrode was formed by etching using photolithography. Next, another glass substrate was bonded to the 2 nd main surface side of the glass substrate via an ultraviolet-curable adhesive layer, and sealed. The organic EL structure was formed on the glass substrate by the above-described procedure. A glass laminate a (hereinafter referred to as a panel a) having an organic EL structure on a glass substrate is a laminate having a member for an electronic device (a panel for a display device having a supporting base material) of the present invention.
Next, the sealing body side of panel a was vacuum-sucked to the stage, and then a stainless steel cutter having a thickness of 0.1mm was inserted at the interface of the glass substrate and the silicone layer at the corner of panel a, providing a starting point of peeling at the interface of the glass substrate and the silicone layer. Then, the surface of the supporting substrate of the panel a is sucked by a vacuum suction pad, and then the suction pad is raised. Here, the insertion of the tool was performed while blowing off the electric fluid to the interface by an ionizer (manufactured by keyence corporation). Then, the vacuum adsorption pad is lifted while the electric fluid is continuously blown to the formed gap by the ionizer. As a result, only the glass substrate on which the organic EL structure is formed remains on the stage, and the supporting base material having the silicone resin layer can be peeled off.
Next, the peeled surface of the glass substrate separated in the same manner as in example 1 was cleaned, the separated glass substrate was cut by a laser cutter or a Scribe & Break (Scribe & Break) method, and divided into a plurality of cells, and then the glass substrate on which the organic EL structure was formed was assembled with a counter substrate, and a module forming step was performed to produce an OLED. The OLEDs thus obtained do not present problems in terms of performance.
< example 7 >
In this example, an LCD was produced using the glass laminate a obtained in example 1.
First, two glass laminates a were prepared, and silicon nitride, silicon oxide, and amorphous silicon were sequentially formed on the 2 nd main surface of the glass substrate in one of the glass laminates a1 by a plasma CVD method. Next, boron was implanted into the amorphous silicon layer at a low concentration by an ion doping apparatus, and heat treatment was performed at 450 ℃ for 60 minutes in a nitrogen atmosphere to perform dehydrogenation treatment. Next, crystallization treatment of the amorphous silicon layer was performed by a laser annealing apparatus. Next, by etching using photolithography and an ion doping apparatus, phosphorus is implanted at a low concentration into the amorphous silicon layer, thereby forming N-type and P-type TFT regions. Next, a silicon oxide film was formed on the 2 nd main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, molybdenum was formed by a sputtering method, and a gate electrode was formed by etching using a photolithography method. Next, a source region and a drain region are formed by implanting boron and phosphorus at high concentrations into desired regions of the N-type and the P-type, respectively, using photolithography and an ion doping apparatus. Next, on the 2 nd main surface side of the glass substrate, an interlayer insulating film is formed by silicon oxide film formation by a plasma CVD method, aluminum film formation is formed by a sputtering method, and a TFT electrode is formed by etching using a photolithography method. Next, a passivation layer was formed by performing a heat treatment at 450 ℃ for 60 minutes under a hydrogen atmosphere to perform a hydrogenation treatment, and then forming a silicon nitride film by a plasma CVD method. Next, an ultraviolet curable resin was applied to the 2 nd main surface side of the glass substrate, and a planarization layer and a contact hole were formed by photolithography. Next, indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.
Subsequently, the other glass laminate a2 was subjected to a heat treatment at 450 ℃ for 60 minutes in an atmospheric air atmosphere. Next, chromium was formed on the 2 nd main surface of the glass substrate in the glass laminate a by sputtering, and the light-shielding layer was formed by etching using photolithography. Next, a color resist (color resist) was applied to the 2 nd main surface side of the glass substrate by a die coating method, and a color filter layer was formed by photolithography and thermosetting. Next, indium tin oxide was deposited by sputtering to form a counter electrode. Next, an ultraviolet curable resin solution was applied to the 2 nd main surface side of the glass substrate by a die coating method, and a columnar spacer (spacer) was formed by photolithography and thermosetting. Next, a polyimide resin solution was applied by a roll coating method, and an alignment layer was formed by thermosetting, and rubbing was performed.
Next, the sealing resin liquid was drawn into a frame shape by a dispensing method (dispenser method), the liquid crystal was dropped into the frame by the dispensing method, and then the 2 nd principal surface sides of the glass substrates of the two glass laminates a were bonded to each other using the glass laminate a1 having the pixel electrode formed thereon, and the LCD panel was obtained by ultraviolet curing and heat curing.
Next, the 2 nd main surface of the glass laminate a1 was vacuum-sucked on the stage, and a stainless steel cutter having a thickness of 0.1mm was inserted into the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate a2, to provide a starting point of peeling between the 1 st main surface of the glass substrate and the releasable surface of the silicone resin layer. Here, the insertion of the tool was performed while blowing off the electric fluid to the interface by an ionizer (manufactured by keyence corporation). Then, the vacuum adsorption pad is lifted while the electric fluid is continuously blown to the formed gap by the ionizer. Then, the 2 nd main surface of the support substrate of the glass laminate a2 was sucked by a vacuum suction pad, and then the suction pad was raised. As a result, only the LCD empty box having the supporting substrate of the glass laminate a1 remained on the stage, and the supporting substrate having the silicone layer could be peeled off.
Next, the 2 nd main surface of the glass substrate having the color filter formed on the 1 st main surface was vacuum-sucked on a stage, and a stainless steel cutter having a thickness of 0.1mm was inserted into the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate a1, to provide a starting point of peeling of the 1 st main surface of the glass substrate from the releasable surface of the silicone resin layer. Then, the 2 nd main surface of the support substrate of the glass laminate a1 was sucked by a vacuum suction pad, and then the suction pad was raised. As a result, only the LCD cell (cell) remains on the stage, and the support substrate to which the silicone layer is fixed can be peeled off. Thus, a plurality of LCD cells each composed of a glass substrate having a thickness of 0.1mm were obtained.
Next, the LCD cells are divided into a plurality of LCD cells by a cutting process. After the completion of the process of attaching a polarizing plate to each LCD cell, a module forming process is performed to obtain an LCD. The resulting LCD does not cause problems in performance.
< example 8 >
In this example, an OLED was manufactured using the glass laminate a obtained in example 1.
First, molybdenum was formed on the 2 nd main surface of the glass substrate in the glass laminate a by a sputtering method, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride was further formed on the 2 nd main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, indium gallium zinc oxide was formed by a sputtering method, and an oxide semiconductor layer was formed by etching using a photolithography method. Next, silicon nitride was further formed on the 2 nd main surface side of the glass substrate by a plasma CVD method to form a channel protective layer, molybdenum was formed by a sputtering method, and a source electrode and a drain electrode were formed by etching using a photolithography method. Subsequently, the heating treatment was carried out at 450 ℃ for 60 minutes in the air. Next, a passivation layer was formed by further forming silicon nitride on the 2 nd main surface side of the glass substrate by a plasma CVD method, and then indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.
Then, 4', 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl ] as a hole transport layer were sequentially formed on the 2 nd principal surface side of the glass substrate by a vapor deposition method]Benzidine, a mixture of 40% by volume of 2, 6-bis [4- [ N- (4-methoxyphenyl) -N-phenyl ] as a light-emitting layer]Aminostyryl radical]8-hydroxyquinoline aluminum complex (Alq) of naphthalene-1, 5-dicarbonitrile (BSN-BCN)3) Alq as an electron transport layer3. Next, aluminum was deposited by sputtering, and the counter electrode was formed by etching using photolithography. Next, another glass substrate was bonded to the 2 nd main surface side of the glass substrate via an ultraviolet-curable adhesive layer, and sealed. The organic EL structure was formed on the glass substrate by the above-described procedure. A glass laminate a (hereinafter referred to as a panel a) having an organic EL structure on a glass substrate is a laminate having a member for an electronic device (a panel for a display device having a supporting base material) of the present invention.
Next, the sealing body side of panel a was vacuum-sucked to the stage, and then a stainless steel cutter having a thickness of 0.1mm was inserted at the interface of the glass substrate and the silicone layer at the corner of panel a, providing a starting point of peeling at the interface of the glass substrate and the silicone layer. Then, the surface of the supporting substrate of the panel a is sucked by a vacuum suction pad, and then the suction pad is raised. Here, the insertion of the tool was performed while blowing off the electric fluid to the interface by an ionizer (manufactured by keyence corporation). Then, the vacuum adsorption pad is lifted while the electric fluid is continuously blown to the formed gap by the ionizer. As a result, only the glass substrate on which the organic EL structure is formed remains on the stage, and the supporting base material having the silicone resin layer can be peeled off.
Next, the peeled surface of the glass substrate separated in the same manner as in example 1 was cleaned, the separated glass substrate was cut by a laser cutter or a scribing and breaking method, and divided into a plurality of cells (cells), and then the glass substrate on which the organic EL structure was formed was assembled with a counter substrate, and a module forming step was performed to produce an OLED. The resulting OLED does not pose a problem in performance.
The present application is based on japanese patent application 2012-230092, filed on day 17, 10/2012, the content of which is incorporated in the present description by reference.
Description of the symbols
10 glass laminate
12 support substrate
14 Silicone layer
14a the 1 st principal surface of the silicone resin layer
16 glass substrate
1 st principal surface of 16a glass substrate
16b the 2 nd principal surface of the glass substrate
18 support substrate having silicone layer
20 Member for electronic device
22 laminate having electronic component member
24 glass substrate with member
Claims (10)
1. A glass laminate comprising a layer of a support base material, a silicone resin layer and a glass substrate in this order, wherein the peel strength at the interface between the layer of the support base material and the silicone resin layer is higher than the peel strength at the interface between the silicone resin layer and the glass substrate, wherein
The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
the silicone resin layer contains silicone oil,
one of the silicone resin and the silicone oil contained in the silicone resin layer has an aromatic group, and the other has substantially no aromatic group, and
wherein the content of the silicone oil in the silicone resin layer is 6 to 20 parts by mass relative to 100 parts by mass of the silicone resin.
2. The glass laminate of claim 1,
the silicone oil has a phenyl group, and the silicone oil has a phenyl group,
the silicone oil has a phenyl group content of 5 to 50 mol% in all organic groups bonded to silicon atoms.
3. The glass laminate of claim 1 or 2,
the viscosity of the silicone oil at 25 ℃ is 100-6000 cP.
4. The glass laminate of claim 1 or 2,
the thickness of the silicone resin layer is 2-100 μm.
5. The glass laminate of claim 1 or 2,
the support substrate is a glass plate.
6. A method of making the glass laminate of any of claims 1 to 5,
a layer containing a crosslinkable organopolysiloxane and a silicone oil is formed on one surface of a support base, the crosslinkable organopolysiloxane is crosslinked on the support base surface to form a silicone resin layer, and then a glass substrate is laminated on the surface of the silicone resin layer.
7. A support substrate having a silicone layer, having a support substrate and a silicone layer having a releasable surface provided on a face of the support substrate,
the support base having a silicone layer can be used for producing a glass laminate comprising, in this order, a layer of a support base, a silicone layer, and a layer of a glass substrate, the peel strength of the interface between the layer of the support base and the silicone layer being higher than the peel strength of the interface between the silicone layer and the glass substrate,
wherein,
the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
the silicone resin layer contains silicone oil,
one of the silicone resin and the silicone oil contained in the silicone resin layer has an aromatic group, and the other has substantially no aromatic group, and
wherein the content of the silicone oil in the silicone resin layer is 6 to 20 parts by mass relative to 100 parts by mass of the silicone resin.
8. The support substrate having a silicone layer according to claim 7,
the silicone oil has a phenyl group, and the silicone oil has a phenyl group,
the silicone oil has a phenyl group content of 5 to 50 mol% in all organic groups bonded to silicon atoms.
9. The support substrate having a silicone layer according to claim 8,
the silicone oil has a phenyl group content of 5 to 30 mol% in all organic groups bonded to silicon atoms.
10. The support substrate having a silicone layer according to claim 7 or 8,
the viscosity of the silicone oil at 25 ℃ is 100-6000 cP.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-230092 | 2012-10-17 | ||
| JP2012230092 | 2012-10-17 | ||
| PCT/JP2013/077678 WO2014061565A1 (en) | 2012-10-17 | 2013-10-10 | Glass laminate and manufacturing method therefor, and support base with silicone resin layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104736340A CN104736340A (en) | 2015-06-24 |
| CN104736340B true CN104736340B (en) | 2017-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380054462.5A Active CN104736340B (en) | 2012-10-17 | 2013-10-10 | Glass laminate and its manufacture method and the supporting base material with silicone layer |
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| Country | Link |
|---|---|
| JP (1) | JP6194893B2 (en) |
| KR (1) | KR20150073976A (en) |
| CN (1) | CN104736340B (en) |
| TW (1) | TWI613073B (en) |
| WO (1) | WO2014061565A1 (en) |
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| CN106163798B (en) * | 2014-04-10 | 2019-05-10 | Ａｇｃ株式会社 | Glass laminate and its manufacturing method, the manufacturing method of electronic device |
| CN107107568A (en) * | 2014-12-26 | 2017-08-29 | 旭硝子株式会社 | Glass laminate, the manufacture method of electronic device, the manufacture method of glass laminate, glass plate packing body |
| WO2017175682A1 (en) * | 2016-04-05 | 2017-10-12 | 旭硝子株式会社 | Glass plate constituent |
| CN110313185B (en) * | 2017-02-23 | 2021-07-27 | Ａｇｃ株式会社 | Glass plate structure |
| GB201820275D0 (en) * | 2018-12-12 | 2019-01-30 | Heliac Aps | Improved coatings for glass |
| CN112174519B (en) * | 2020-09-10 | 2022-12-06 | 河北光兴半导体技术有限公司 | Composite glass plate and preparation method and application thereof |
| WO2024071351A1 (en) * | 2022-09-30 | 2024-04-04 | 日東電工株式会社 | Shaped objects |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101242951A (en) * | 2005-08-09 | 2008-08-13 | 旭硝子株式会社 | Thin sheet glass laminate and method for manufacturing display using thin sheet glass laminate |
| CN102482532A (en) * | 2008-07-30 | 2012-05-30 | 蓝星有机硅法国简易股份有限公司 | Silicone composition for coating a flexible support intended to form a crosslinked coating having increased attachment, mechanical strength and reactivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090037856A (en) * | 2006-07-12 | 2009-04-16 | 아사히 가라스 가부시키가이샤 | Glass substrate with protective glass, process for producing display using glass substrate with protective glass, and silicone for release paper |
| WO2011142280A1 (en) * | 2010-05-11 | 2011-11-17 | 旭硝子株式会社 | Process for producing laminate, and laminate |
| JP5796449B2 (en) * | 2011-10-12 | 2015-10-21 | 旭硝子株式会社 | Manufacturing method of electronic device, manufacturing method of carrier substrate with resin layer |
-
2013
- 2013-10-10 KR KR1020157009424A patent/KR20150073976A/en not_active Application Discontinuation
- 2013-10-10 CN CN201380054462.5A patent/CN104736340B/en active Active
- 2013-10-10 JP JP2014542095A patent/JP6194893B2/en active Active
- 2013-10-10 WO PCT/JP2013/077678 patent/WO2014061565A1/en active Application Filing
- 2013-10-16 TW TW102137303A patent/TWI613073B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101242951A (en) * | 2005-08-09 | 2008-08-13 | 旭硝子株式会社 | Thin sheet glass laminate and method for manufacturing display using thin sheet glass laminate |
| CN102482532A (en) * | 2008-07-30 | 2012-05-30 | 蓝星有机硅法国简易股份有限公司 | Silicone composition for coating a flexible support intended to form a crosslinked coating having increased attachment, mechanical strength and reactivity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6194893B2 (en) | 2017-09-13 |
| TW201429709A (en) | 2014-08-01 |
| TWI613073B (en) | 2018-02-01 |
| KR20150073976A (en) | 2015-07-01 |
| CN104736340A (en) | 2015-06-24 |
| WO2014061565A1 (en) | 2014-04-24 |
| JPWO2014061565A1 (en) | 2016-09-05 |
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Address after: Tokyo, Japan Patentee after: AGC Corporation Address before: Tokyo, Japan Patentee before: Asahi Glass Co., Ltd. |