CN111909623B - Adhesive tape for vacuum process - Google Patents
Adhesive tape for vacuum process Download PDFInfo
- Publication number
- CN111909623B CN111909623B CN202010373041.0A CN202010373041A CN111909623B CN 111909623 B CN111909623 B CN 111909623B CN 202010373041 A CN202010373041 A CN 202010373041A CN 111909623 B CN111909623 B CN 111909623B
- Authority
- CN
- China
- Prior art keywords
- adhesive tape
- film
- adhesive layer
- silicone resin
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 268
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000008569 process Effects 0.000 title claims abstract description 46
- 239000012790 adhesive layer Substances 0.000 claims abstract description 210
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 109
- 239000012298 atmosphere Substances 0.000 claims abstract description 63
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 238000003860 storage Methods 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims description 229
- 229920001296 polysiloxane Polymers 0.000 claims description 152
- 238000007259 addition reaction Methods 0.000 claims description 76
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 49
- 239000003431 cross linking reagent Substances 0.000 claims description 48
- -1 polysiloxane Polymers 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000011342 resin composition Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 3
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- 239000002210 silicon-based material Substances 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 abstract description 156
- 239000010408 film Substances 0.000 description 309
- 230000001070 adhesive effect Effects 0.000 description 81
- 239000000853 adhesive Substances 0.000 description 80
- 239000010409 thin film Substances 0.000 description 57
- 230000015572 biosynthetic process Effects 0.000 description 50
- 238000001035 drying Methods 0.000 description 49
- 239000011248 coating agent Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 33
- 239000011521 glass Substances 0.000 description 33
- 238000004544 sputter deposition Methods 0.000 description 29
- 239000000203 mixture Substances 0.000 description 26
- 239000004205 dimethyl polysiloxane Substances 0.000 description 25
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 25
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 21
- 238000004132 cross linking Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 19
- 239000006059 cover glass Substances 0.000 description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229920006267 polyester film Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 239000013464 silicone adhesive Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 125000006038 hexenyl group Chemical group 0.000 description 5
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- KBSDLBVPAHQCRY-UHFFFAOYSA-N 307496-19-1 Chemical group C1CC=CCC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 KBSDLBVPAHQCRY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013557 residual solvent Substances 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention provides an adhesive tape for a vacuum process. The invention provides an adhesive tape used in a vacuum film forming process, which reduces the generation of outgas which is a cause of poor appearance of a functional film after film forming. The adhesive tape for vacuum process comprises a silicone resin (G) and a silicone resin (R) in a mass ratio (G)/(R) =35/65-100/0, wherein the alkenyl group content is 1.0X10 ‑5 ～1.0×10 ‑3 The storage modulus at 200℃measured in a He atmosphere at mol/g was 1.0X10 5 ～1.0×10 7 Adhesive layer of Pa at a vacuum degree of 1.0X10 ‑4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated by the adhesive tape is 180mg/m 2 The following is given.
Description
Technical Field
The invention relates to an adhesive tape for vacuum process.
Background
In flat panel display devices such as smart phones, mobile phones, personal digital assistants PDA, and digital cameras, and touch panel display devices, a thin plate-shaped cover glass is disposed on the front surface of the display so as to be wider than the image display portion in order to protect the display and improve the appearance and design, and a chemically strengthened glass is used as the cover glass.
In recent years, in particular, in a smart phone or the like, a protective glass having a shape called 2.5D type, quasi-3D type, or the like, in which the front surface protrudes from the case and the end portion is curved, has been marketed. Since the cover glass has not only the flat portion but also the side portion at the outer periphery thereof exposed to the surface, the side portion also needs to be reinforced in the same manner as the flat portion. As a method for reinforcing the cover glass subjected to the curved surface processing, there is known a method in which an inorganic film is continuously laminated from the entire surface of a flat portion of the cover glass and a surface side to a back side of a side surface portion provided on the outer peripheral edge of the flat portion by a post-reaction sputtering method or a sputtering method accompanied by a pretreatment (see patent document 1).
However, as a sputtering apparatus for efficiently forming a functional thin film such as a reinforcing inorganic film or an antireflection film on the protective glass as described above, a carousel sputtering apparatus is known (see patent literature 2). The carousel-type sputtering apparatus is a rotary/intermittent-type sputtering apparatus having a structure in which a substrate holder (drum) having a polygonal prism shape is disposed in a chamber, and a magnetron holding a rectangular target is disposed inside a chamber wall. While rotating a substrate holder on which a substrate is mounted, power is supplied to a magnetron to generate plasma on the upper surface of a target, and a predetermined reaction gas is introduced into a chamber, thereby forming a film.
In this case, the protective glass is usually mounted on a plurality of fixtures to form a film, but recently, in order to form a film of a larger number of protective glass pieces by a batch process, and to reduce damage or the like occurring when the protective glass pieces are mounted on the fixtures or removed from the fixtures, a method has been studied in which a plurality of protective glass pieces are temporarily fixed to a carrier glass substrate or the like by an adhesive tape, the carrier glass substrate is mounted on the fixtures to form a film, and the adhesive tape is peeled off and removed after the film is formed. In the case of forming a film by this method, the fixing material does not directly contact the cover glass, and thus, for example, a functional thin film can be formed on the entire surface including the side surface portion of the 2.5D to 3D cover glass. The temperature of the cover glass at the time of film formation may be set to a high temperature of 150 to 200 ℃ from the viewpoint of improvement of the adhesiveness of the functional film. The film formation time is usually about 30 to 60 minutes, although it depends on the number of layers and the material of the functional thin film. The vacuum degree at the time of film formation is usually 1.0X10 -4 And Torr or below. Therefore, the adhesive tape requires (1) a temporary fixing force for protecting the glass from falling off in the sputtering step 2) The amount of outgas generation is controlled to a level that does not affect the appearance or characteristics of the functional thin film formed well, (3) after film formation, the protective glass can be peeled off from the carrier glass substrate without breakage or residual adhesive.
As tapes and laminates used under a vacuum atmosphere at high temperature, there are known: an adhesive tape for vacuum processing comprising a base material and an adhesive layer disposed on at least one side of the base material, wherein the adhesive layer is composed of an active energy ray-curable adhesive comprising a base polymer and a photopolymerization initiator, and wherein the photopolymerization initiator has a 5% weight loss temperature in TGA (thermogravimetric analysis) of 160 ℃ or higher (see patent document 3); a laminate comprising a substrate and an adhesive layer laminated on one surface of the substrate, wherein the adhesive layer is formed from a silicone adhesive composition comprising: a silicone resin composition comprising a silicone rubber containing an addition organopolysiloxane having a siloxane bond as a main skeleton and containing an alkenyl group as a constituent, 0.01 to 3 parts by mass of a platinum catalyst per 100 parts by mass of the silicone rubber, and 15 to 100 parts by mass of a silicone resin per 100 parts by mass of the silicone rubber, wherein the adhesive layer is heated in an air atmosphere at 5 ℃/min from 23 ℃ to 200 ℃ and the mass reduction ratio at 200 ℃ to 40 ℃ is 0.20% by mass or less (see patent document 4); etc.
In patent document 3, specifically, as an example of a vacuum process, a process of adhering an adhesive tape as an underfill material to a semiconductor chip is exemplified in which, in a state where the adhesive tape is disposed above the semiconductor chip (bump forming surface), airtight spaces are separated above and below the adhesive tape, both the above airtight space and the below airtight space are depressurized, and then only the above airtight space is returned to atmospheric pressure, thereby adhering the adhesive tape to an adherend by a pressure difference, in order to reinforce and protect bumps of the semiconductor chip at the time of flip chip mounting. The process of depressurizing both the upper airtight space and the lower airtight space corresponds to a vacuum process, and in the examples, the gas release amount from the adhesive sheet when left under a heated and depressurized environment (100 ℃,1000 pa=7.5 Torr) for 1 hour is in the range of 100 to 400 μg/1g of the adhesive sheet.
Patent document 4 describes that a light release sheet including an adhesive sheet having an adhesive layer formed of an organosilicon-based adhesive composition is peeled off, a surface of the adhesive layer is stuck to one main surface of a base material formed of an alkali-free glass substrate, then a heavy release sheet is peeled off, a laminate including the base material formed of an alkali-free glass substrate and the adhesive composition layer is produced, the laminate is put into an oven in which an air atmosphere having a temperature of 240 ℃ is maintained for 60 minutes, and then taken out from the oven, and an annealing treatment is performed in which the laminate is cooled to 23 ℃ in an air atmosphere having a relative humidity of 50% at 23 ℃ to impart mass reduction resistance.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-171556
Patent document 2: japanese patent laid-open No. 2006-265739
Patent document 3: japanese patent application laid-open No. 2017-214528
Patent document 4: japanese patent application laid-open No. 2014-195922
Disclosure of Invention
Problems to be solved by the invention
However, the adhesive tape described in patent document 3 is 1.0x10 -4 When the protective glass is used under a high vacuum of not more than Torr, outgas from the adhesive tape cannot be sufficiently suppressed, and for example, sputtering may adversely affect the appearance and properties of a functional thin film such as an inorganic film for reinforcing a protective glass or an antireflection film.
In patent document 4, after the production and preparation of a monolithic laminate, the laminate is put into an oven at 240 ℃ or higher, left in this atmosphere for 60 minutes, and then left to cool in an air atmosphere at 23 ℃ and a relative humidity of 50% for a long period of time, so that there is room for improvement in operability and productivity. In addition, when the silicone adhesive composition is subjected to an annealing treatment at 350 ℃ for 60 minutes or longer, for example, the adhesive may be modified or decomposed, and there is a concern that the adherend may have a residual adhesive (adhesive residue).
In order to form a functional thin film on a heat-resistant substrate such as a cover glass, it cannot be said that conventional adhesive tapes using an active energy ray-curable acrylic adhesive or a silicone adhesive are necessarily optimal in terms of performance and productivity, and there is still room for improvement in terms of performance and productivity.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an adhesive tape for vacuum process which can suppress the generation of outgas from the adhesive tape to a level that does not adversely affect the appearance and characteristics of the functional film when forming the functional film on a film substrate such as glass or film by a vacuum film forming process such as sputtering or vapor deposition, and which can be produced by a roll-to-roll method.
Means for solving the problems
The present inventors have made intensive studies on an adhesive layer of an adhesive tape for vacuum processing based on such an object, and as a result, have found that if the following adhesive composition is used as the adhesive layer, the adhesive composition is involved in the following manner: (1) The silicone gum (G) containing alkenyl groups bonded to silicon atoms and the silicone resin (R) containing no alkenyl groups bonded to silicon atoms are blended so that the mass ratio (G)/(R) is in the range of (G)/(R) =35/65 to 100/0, and the content of alkenyl groups bonded to silicon atoms is 1.0X10 -5 ～1.0×10 -3 An addition-reaction type silicone resin (2) having a molar ratio of mol/g as a main component is crosslinked with an organopolysiloxane having a hydrogen atom (SiH) bonded to a silicon atom and a platinum group metal catalyst to give a storage modulus of 1.0X10 at 200 ℃ measured under an He atmosphere 5 ～1.0×10 7 A range of Pa; and the adhesive tape having the adhesive layer was adjusted so as to have a vacuum of 1.0X10 -4 Heating from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under the atmosphere of Torr or lessThe total amount of outgas generated after the reaction was 180mg/m at 200℃for 30 minutes 2 In the following, when the adhesive tape is used as an adhesive tape for temporary fixation in forming a functional thin film on a heat-resistant substrate by a vacuum film forming process such as sputtering or vapor deposition, generation of outgas from the adhesive tape during the film forming process can be suppressed, and the obtained functional thin film is excellent in removability (no adhesive residue on a processed adherend, no breakage of the processed adherend during peeling) without adversely affecting the appearance or characteristics of the obtained functional thin film, and can be produced by a roll-to-roll method, thereby completing the present invention.
In a laminate using a conventional silicone adhesive composition which is less likely to generate outgas even in a high-temperature environment, a method of heating the laminate at 200 ℃ or higher for 60 minutes or higher by annealing treatment and removing volatile components (solvent, low-molecular silicone components) remaining in the adhesive layer of the laminate from the adhesive composition layer has been adopted. However, in this method, production by the roll-to-roll method is extremely difficult as in a usual adhesive tape, and operability is also poor. Further, there is a concern that the adhesive may be decomposed or deteriorated due to the processing temperature or the processing time, or the decomposed product which may be a cause of outgas may be increased in turn.
As a method for reducing the amount of air released from the adhesive tape, the present inventors have focused on the fact that the environment in which the adhesive tape is used is not in air but in a high vacuum, in addition to various studies on methods other than high-temperature and long-time annealing. That is, the use environment of the adhesive tape is not at a high temperature in air, but at a special high vacuum, that is, at a high temperature in a sealed state, the silicone gel in the silicone adhesive is hardly oxidized and decomposed, but on the other hand, when the interaction between the silicon atoms in the main chain skeleton and the oxygen atoms in other main chain skeletons strongly acts, a part of the main chain skeleton may undergo cracking (cracking), resulting in a reduction in molecular weight. In addition, the silicone resin is similarly difficult to oxidize and decompose, but in particular, in the case where silanol is present at the terminal, and in the case where the terminal silanol strongly interacts with the silicon atom and the oxygen atom in the same main chain skeleton to form a cyclic structure, a low molecular weight component such as linear low molecular weight siloxane or cyclic siloxane may be generated. As a result, when the adhesive tape is used under high vacuum and high temperature, it is considered that outgas is still easily generated from the adhesive layer. Thus, if the high crosslinking structure of the adhesive layer is achieved by optimizing the alkenyl group content of the silicone gum, the storage modulus of the silicone adhesive at high vacuum and high temperature is increased, and the movement of the molecular chains of the silicone gum and the silicone resin is restricted, the interaction between the main chain backbones and the interaction within the same backbone can be suppressed, and therefore even in the adhesive tape manufactured by the usual roll-to-roll method, the occurrence of new low molecular weight components as described above can be suppressed, and as a result, the occurrence of outgas from the adhesive in the vacuum film forming process is considered to be suppressed.
The present invention includes the following configurations. That is, the adhesive tape for vacuum process of the present invention is characterized in that:
comprises a substrate and an adhesive layer on at least one surface of the substrate,
the adhesive layer is formed of a resin composition containing an addition reaction type silicone resin as a main component, an organopolysiloxane having at least 2 or more hydrogen atoms (SiH) bonded to silicon atoms in 1 molecule as a crosslinking agent, and a platinum group metal catalyst as a catalyst,
the addition reaction type silicone resin is prepared by blending a silicone gum (G) formed from an organopolysiloxane containing an alkenyl group bonded to a silicon atom and a silicone resin (R) formed from an organopolysiloxane containing no alkenyl group bonded to a silicon atom in such a manner that the mass ratio thereof is in the range of (G)/(R) =35/65 to 100/0, and the content of alkenyl groups bonded to silicon atoms is 1.0X10 -5 ～1.0×10 -3 The range of the mol/g is that,
the adhesive layer has a storage modulus of 1.0X10 at 200℃measured under an atmosphere of He 5 ～1.0×10 7 In the range of Pa,
the adhesive tape has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 180mg/m 2 The following is given.
In the above aspect, the substrate is preferably a polyethylene terephthalate film.
The adhesive tape is suitable for use in a vacuum process for forming a functional film selected from the group consisting of an antireflection film, an antiglare film, an antifouling film, and a colored film on a heat-resistant substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive tape for vacuum process which can suppress outgas from the adhesive tape to a level that does not adversely affect the appearance and characteristics of the functional film when forming the functional film on a film substrate such as glass or film by a vacuum film forming process such as sputtering or vapor deposition, and which can be produced even in a roll-to-roll manner.
Drawings
Fig. 1 is a diagram showing an example of a structure to which the single-sided adhesive tape according to the present embodiment is applied.
Fig. 2 is a diagram showing an example of a structure to which the double-sided adhesive tape according to the present embodiment is applied.
Fig. 3 is a view showing an example of a state in which a plurality of film substrates are temporarily fixed to a carrier substrate in a vertically placed posture by applying the double-sided adhesive tape according to the present embodiment.
Fig. 4 is a view showing another example of a state in which a plurality of film substrates are temporarily fixed to a carrier substrate in a vertically placed posture by applying the double-sided adhesive tape of the present embodiment.
Fig. 5 is a diagram showing an example of a temporary fixing method of a film substrate to a carrier substrate by applying the single-sided adhesive tape according to the present embodiment.
Fig. 6 is a view showing another example of a temporary fixing method of a film substrate to a carrier substrate by applying the single-sided adhesive tape according to the present embodiment.
Fig. 7 is a diagram showing an example of a temporary fixing method of a film substrate to a carrier substrate by applying the double-sided adhesive tape according to the present embodiment.
Fig. 8 is a view showing another example of a temporary fixing method of a film substrate to a carrier substrate by applying the double-sided adhesive tape according to the present embodiment.
Symbol description
1: base material, 2, 3: adhesive layer, 10': single-sided adhesive tape, 11: carrier substrate, 12: film substrate, 20: double-sided adhesive tape, 30, 40: schematic diagrams of the vertical placement posture of the carrier substrate to which the film substrate is temporarily fixed, 50, 60, 70, 80: a schematic view of a carrier substrate to which a thin film substrate is temporarily fixed.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
(construction of adhesive tape)
Fig. 1 is a diagram showing a configuration of a single-sided adhesive tape 10 (hereinafter, may be simply referred to as an adhesive tape 10) as an example of an adhesive tape for vacuum process to which the present embodiment is applied. Fig. 2 is a diagram showing a configuration of a double-sided adhesive tape 20 (hereinafter, may be simply referred to as an adhesive tape 20) as another example of an adhesive tape for vacuum process to which the present embodiment is applied. Specifically, the adhesive tapes 10 and 20 of the present embodiment are used for temporarily fixing the singulated protective glass to a carrier substrate (glass, SUS, etc.) held in a vacuum apparatus in a vacuum process for forming an antireflection film on the surface of the protective glass, for example.
As shown in fig. 1, the adhesive tape 10 has a structure in which a single-sided adhesive tape is formed by laminating an adhesive layer 2, which is an example of an adhesive layer containing an addition reaction type silicone resin as a main component, on one side of a base material 1. As shown in fig. 2, the adhesive tape 20 has a double-sided adhesive tape in which an adhesive layer 2 and an adhesive layer 3 are laminated on both sides of a base material 1, respectively, as an example of an adhesive layer containing an addition reaction type silicone resin as a main component. Here, the adhesive layer 2 and the adhesive layer 3 may be the same or different.
Although not shown, the adhesive tapes 10 and 20 may have anchor coatings for improving the adhesion between the substrate 1 and the adhesive layer 2 and the adhesion between the substrate 1 and the adhesive layer 3, as required, between the substrate 1 and the adhesive layer 2 and between the substrate 1 and the adhesive layer 3. The pressure-sensitive adhesive layer 2 may have a release film on its surface (the surface opposite to the surface facing the substrate 1) and the pressure-sensitive adhesive layer 3 (the surface opposite to the surface facing the substrate 1). In the case of the single-sided adhesive tape 10, the surface of the substrate 1 (the surface opposite to the adhesive layer 2) may be subjected to a surface treatment such as a release improving treatment.
< substrate >
The substrate 1 of the present embodiment is not particularly limited, and for example, a resin film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially oriented polypropylene, polyimide, aliphatic polyimide (transparent polyimide), polycycloolefin, fluorine-based resin, or polyolefin resin can be used. For example, a composite film obtained by laminating polyethylene terephthalate and a polyolefin resin film, a composite film obtained by further laminating these composite films and a resin film, a resin film obtained by coextrusion to form a plurality of layers, or the like can be used as the base material 2 depending on the application. Among them, a material containing polyethylene terephthalate as a main component is preferably used as the base material 1 from the viewpoint of versatility. The thickness of the base material is preferably in the range of 12 to 200. Mu.m, more preferably in the range of 25 to 100. Mu.m.
< adhesive layer >)
The adhesive layers 2 and 3 of the present embodiment contain an addition reaction type silicone resin as a main component. Specifically, the addition reaction type silicone resin includes: a resin comprising a silicone material (G) comprising an organopolysiloxane having an alkenyl group bonded to a silicon atom and a silicone resin (R) comprising an organopolysiloxane having no alkenyl group bonded to a silicon atom, wherein the mass ratio (G)/(R) is in the range of 35/65 to 100/0.
The components constituting the adhesive layers 2 and 3 will be described in detail below.
[ addition reaction type Silicone-based resin ]
Addition ofThe reactive silicone resin comprises: a resin comprising a silicone material (G) comprising an organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom and a silicone resin (R) comprising an organopolysiloxane such as polydimethylsiloxane not having an alkenyl group bonded to a silicon atom, wherein the mass ratio (G)/(R) is in the range of 35/65 to 100/0. The addition reaction type silicone resin has a content of alkenyl groups bonded to silicon atoms of 1.0X10 -5 ～1.0×10 -3 The design is carried out in such a way that the mol/g is in the range.
If the content of the above alkenyl groups bonded to silicon atoms is less than 1.0X10 -5 The crosslinking and curing of the adhesive layers 2 and 3 tend to be insufficient and the crosslinking density tends to be low. As a result, the adhesive layers 2 and 3 have a low storage modulus at 200 ℃ in the He atmosphere, and thus the amount of outgas generated increases, and the appearance of the functional thin film formed well may be deteriorated. In addition, since the cohesive force of the adhesive layers 2 and 3 is also reduced, there is a concern that the film substrate may be left with adhesive residue when the adhesive tapes 10 and 20 are peeled off after film formation. On the other hand, if the content of the above alkenyl group bonded to silicon atom exceeds 1.0X10 -3 The crosslinking and curing of the adhesive layers 2 and 3 tend to proceed excessively at mol/g, and the crosslinking density also increases excessively. As a result, the adhesive force of the adhesive layers 2 and 3 is extremely reduced, and thus temporary fixing force of the thin film substrate becomes insufficient, and the thin film substrate may be peeled off during film formation.
The silicone material (G) composed of an organopolysiloxane such as polydimethylsiloxane containing an alkenyl group bonded to a silicon atom and the silicone resin (R) composed of an organopolysiloxane such as polydimethylsiloxane not containing an alkenyl group bonded to a silicon atom contained in the addition reaction type silicone resin will be described in further detail below.
In the following description, the silicone gum (G) formed of an organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom may be referred to as a silicone gum (G) having an alkenyl group bonded to a silicon atom, or simply as a silicone gum (G). Similarly, a silicone resin (R) formed of an organopolysiloxane such as polydimethylsiloxane which does not contain an alkenyl group bonded to a silicon atom may be referred to as a silicone resin (R) formed of an organopolysiloxane such as polydimethylsiloxane, or simply referred to as a silicone resin (R).
[ Silicone Material (G) comprising organopolysiloxane such as polydimethylsiloxane having alkenyl groups bonded to silicon atoms ]
The silicone gel (G) formed of an organopolysiloxane such as polydimethylsiloxane containing an alkenyl group bonded to a silicon atom in the present embodiment is not particularly limited as long as it is a material used for an addition-reaction type silicone-based adhesive or an addition-reaction type silicone-based release agent, that is, a material containing at least 2 alkenyl groups bonded to a silicon atom in 1 molecule on average. Specifically, as the above-mentioned silicone gum (G), a silicone gum having a content of alkenyl groups bonded to silicon atoms of 1.0X10 can be used -6 ～1.0×10 -1 The silicone gum in the range of mol/g is preferably used in an amount of 2.0X10 from the viewpoint of controlling the storage modulus of the adhesive layers 2 and 3 -6 ～1.0×10 -2 A silicone gum in the range of mol/g. The silicone gum (G) is such that the alkenyl group content in the addition reaction type silicone resin is 1.0X10 -5 ～1.0×10 -3 The molar ratio of the catalyst may be 1 kind alone or 2 or more kinds may be used in combination.
Examples of the molecular structure of the organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom include a linear structure in which a main chain portion is formed of a diorganosiloxane repeating unit, a structure in which a part of the molecular structure includes a branched chain, a branched structure, or a cyclic structure. Among them, organopolysiloxane having a linear structure is preferable in terms of physical properties such as mechanical strength of the adhesive.
The silicone gum (G) formed of the organopolysiloxane containing an alkenyl group bonded to a silicon atom may be oily or rubbery, and is preferably gel-like. In the case where the silicone gum (G) is oily, the viscosity of the silicone gum (G) formed from organopolysiloxane is preferably 1,000mpa·s or more at 25 ℃. When the viscosity is less than 1000mpa·s, the adhesive layers 2 and 3 may not exhibit desired adhesive properties and physical properties, and the adhesion between the adhesive layers 2 and 3 and the substrate 1 may be poor. In the case where the silicone gum (G) is a green gum, the viscosity of the silicone gum (G) formed from organopolysiloxane when dissolved in toluene so as to be 30 mass% concentration is preferably 100,000mpa·s or less at 25 ℃. If the viscosity exceeds 100,000mpa·s, stirring at the time of preparing the adhesive composition may be difficult, and uniform coating may be difficult. The viscosity may be measured using a BM-type rotational viscometer.
Examples of the silicone gum (G) formed from an organopolysiloxane containing an alkenyl group bonded to a silicon atom include, but are not limited to, silicone gum represented by the following general formula (1) or general formula (2).
[ chemical 1]
R 1 (3-a) X a SiO-(R 1 XSiO) m -(R 1 2 SiO) n -SiR 1 (3-a) X a General formula (1)
[ chemical 2]
R 1 2 (OH)SiO-(R 1 XSiO) m+2 -(R 1 2 SiO) n -SiR 1 2 (OH) general formula (2)
In the general formulae (1) and (2), R is 1 Each independently is a 1-valent hydrocarbon group having no aliphatic unsaturated bond, and X is an organic group containing an alkenyl group. a is an integer of 0 to 3, m is an integer of 0 or more, and n is an integer of 100 or more, but a and m are not both 0.m+n is a value at which the organopolysiloxane has a viscosity of 1,000 mPas or more at 25 ℃.
As R as above 1 The hydrocarbon group is preferably a 1-valent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, which does not have an aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl, ethyl, propyl and butyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl, and particularly preferably methyl or phenyl.
The above X is preferably an organic group containing an alkenyl group having 2 to 10 carbon atoms. Examples thereof include vinyl, allyl, hexenyl, octenyl, acryloxypropyl, acryloylmethyl, methacryloxypropyl, acryloxymethyl, methacryloxypropyl, methacryloxymethyl, cyclohexenylethyl, and vinyloxypropyl. Among them, lower alkenyl groups such as vinyl, allyl, and hexenyl are preferable, vinyl groups are particularly preferable from the industrial viewpoint, and hexenyl groups are particularly preferable from the viewpoint of crosslinkability. The binding position of the alkenyl group is not particularly limited, and may be a molecular chain end, a molecular chain side chain, or both a molecular chain end and a molecular chain side chain.
The number of alkenyl groups is not limited to a few, and is usually preferably in the range of 0.02 to 3.0 per 100 organopolysiloxane groups, for example, since the number of alkenyl groups varies in an appropriate range so as to be balanced with the content of the silicone resin (R) composed of an organopolysiloxane such as polydimethylsiloxane, the amount of the crosslinking agent to be added, and other additive components contained in the addition reaction type silicone adhesive. The molecular weight is preferably adjusted so as to be within the above viscosity range within the above ratio so that the number of alkenyl groups in the organopolysiloxane 1 molecule is at least 2 on average.
If the number of alkenyl groups is less than 0.02 per 100 organic groups of the organopolysiloxane, crosslinking and curing of the adhesive layers 2, 3 tend to be insufficient, and the crosslinking density also decreases. As a result, the adhesive layers 2 and 3 have a low storage modulus at 200 ℃ in the He atmosphere, and therefore the amount of outgas generated increases and the cohesive force decreases. In this case, there is a concern that the appearance of the functional film formed well is deteriorated, and there is a concern that the film substrate may be left with adhesive residue when the adhesive tapes 10, 20 are peeled off after the film formation. On the other hand, if the number of alkenyl groups exceeds 3.0 relative to 100 organic groups of the organopolysiloxane, crosslinking and curing of the adhesive layers 2, 3 proceed excessively, and the crosslinking density also becomes excessively high. As a result, the adhesive force of the adhesive layers 2 and 3 may be extremely reduced. In this case, the temporary fixing force of the thin film substrate may become insufficient, and the thin film substrate may be peeled off during film formation.
Specific examples of the above-mentioned silicone gum (G) containing an alkenyl group bonded to a silicon atom include a molecular chain both terminal dimethylvinylsiloxy-terminated dimethylpolysiloxane, a molecular chain both terminal dimethylvinylsiloxy-terminated dimethylsiloxane-methylvinylsiloxy copolymer, a molecular chain both terminal dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenyl siloxane copolymer, a molecular chain both terminal dimethylvinylsiloxy-terminated methylphenylpolysiloxane, a molecular chain both terminal trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer, a molecular chain both terminal trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, a molecular chain both terminal trimethylsiloxy-terminated dimethylsiloxane-methylhexenyl siloxane copolymer, a molecular chain both terminal dimethylvinylsiloxy-terminated dimethylsiloxane-methylhexenyl siloxane copolymer, a molecular chain both terminal dimethylhexenyl siloxy-terminated dimethylsiloxane copolymer, and the like.
[ Silicone resin (R) formed from organopolysiloxane such as polydimethylsiloxane ]
The silicone resin (R) formed of an organopolysiloxane such as polydimethylsiloxane in the present embodiment has R 2 3 SiO 0.5 Unit (M unit) and SiO 2 The organopolysiloxane of units (Q units) is called the so-called MQ resin. The silicone resin (R) formed of an organopolysiloxane such as polydimethylsiloxane has substantially no alkenyl group in the molecule, and conventionally known silicone resins can be used. R is R 2 Examples of the 1-valent hydrocarbon group having 1 to 10 carbon atoms include R as described above 1 The illustrated groups. The organopolysiloxane is preferably represented by R 2 3 SiO 0.5 unit/SiO 2 R is contained so that the molar ratio of the units is in the range of 0.5 to 1.7 2 3 SiO 0.5 Units and SiO 2 A unit. R is R 2 3 SiO 0.5 unit/SiO 2 If the molar ratio of the units is less than 0.5, the resulting adhesive layers 2 and 3 may have reduced adhesion and tackiness, and the temporary fixing force of the thin film substrate may be insufficient, resulting in falling off of the thin film substrate during film formation. On the other hand, if R 2 3 SiO 0.5 unit/SiO 2 If the molar ratio of the units exceeds 1.7, the adhesive force and the holding power of the adhesive layer 2 may be reduced, and the temporary fixing force of the thin film substrate may be insufficient, so that the thin film substrate may be peeled off during film formation. In addition, the organopolysiloxane may have an OH group, but in this case, the content of the OH group is preferably 4.0 mass% or less with respect to the total mass of the organopolysiloxane. If the OH group content exceeds 4.0 mass%, low molecular weight components such as low molecular weight silanol and cyclic siloxane are likely to be generated, and thus the amount of outgas generated increases, and the appearance of the functional thin film formed well may be deteriorated.
The silicone resin (R) formed of an organopolysiloxane such as polydimethylsiloxane may be used alone or in combination of 2 or more kinds. In addition, the organopolysiloxane may have R within a range that does not impair the characteristics of the present invention 2 SiO 1.5 Units (T units) and/or R 2 2 SiO units (D units).
The silicone resin (R) formed from the organopolysiloxane such as polydimethylsiloxane and the silicone material (G) formed from the organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom can be used by simply mixing them together. In addition, as the silicone gum (G) formed from an organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom, when the organopolysiloxane represented by the general formula (2) is contained, the silicone gum (G) formed from an organopolysiloxane such as polydimethylsiloxane having an alkenyl group bonded to a silicon atom and the silicone resin (R) formed from an organopolysiloxane such as polydimethylsiloxane may be used as a (partial) condensation reaction product obtained by reacting in advance the silicone gum (G) formed from an organopolysiloxane such as polydimethylsiloxane, as long as the characteristics of the present invention are not impaired.
[ mass ratio (G)/(R) of silicone resin (R) to silicone gel (G) contained in adhesive layer of the present embodiment ]
The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin contained in the adhesive layers 2 and 3 of the present embodiment is in the range of 35/65 to 100/0, preferably 50/50 to 70/30. Here, when 2 or more types of silicone gum (G) are used in combination, the total amount of the silicone gum is regarded as the mass of the silicone gum (G) in the addition reaction type silicone resin. Similarly, when 2 or more types of silicone resins (R) are used in combination, the total amount of the silicone resins is regarded as the mass of the silicone resin (R) in the addition reaction type silicone resin.
If the mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) contained in the adhesive layers 2, 3 of the present embodiment is smaller than the lower limit of the above range, that is, if the content ratio of the silicone gum (G) is small, crosslinking and curing of the adhesive layers 2, 3 are likely to be insufficient, and the crosslinking density is also reduced, particularly when the content of alkenyl groups bonded to silicon atoms of the silicone gum (G) is small. As a result, the adhesive layers 2 and 3 have a low storage modulus at 200 ℃ in the He atmosphere, and therefore the amount of outgas generated increases, and the adhesion decreases in interaction with the case where the amount of the silicone resin (R) is large. In this case, there is a concern that the appearance of the functional film formed well is deteriorated, and there is a concern that the film substrate may be left with adhesive residue when the adhesive tapes 10, 20 are peeled off after the film formation. Further, even if the content of the alkenyl group bonded to the silicon atom of the silicone resin (G) is within the preferred range of the present invention, the amount of the silicone resin (R) is still increased, and thus the adhesion becomes excessively large, and there is a concern that the film substrate may be broken or the film substrate may be left adhesive when the adhesive tapes 10, 20 are peeled off after film formation.
In contrast, in the case where the mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin included in the adhesive layers 2 and 3 of the present embodiment is set to the above range, the content of the alkenyl group bonded to the silicon atom of the addition reaction type silicone resin is set to the above 1.0×10 -5 ～1.0×10 -3 In the case of the range of mol/g, the storage modulus of the adhesive layer at 200℃measured under the atmosphere of He can be designed to be 1.0X10 5 ～1.0×10 7 In the Pa range, the adhesive tapes 10, 20 were subjected to a vacuum degree of 1.0X10 -4 The total amount of outgas generated when the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under the atmosphere of Torr and then maintained at 200 ℃ for 30 minutes is controlled to be 180mg/m 2 The following becomes easy. As a result, the following effects can be achieved. That is, as a first effect, a temporary fixing force for protecting a thin film substrate such as glass from falling off during the film formation of a functional thin film can be ensured, and an increase in adhesion force can be suppressed even under high vacuum and high temperature. As a second effect, the influence of outgas can be suppressed, and the appearance and characteristics of the functional film formed, for example, an antireflection film can be improved. As a third effect, the film substrate after film formation can be peeled off from the carrier glass substrate or the like without breakage or residual adhesive.
Further, as the addition reaction type silicone resin of the present invention, a commercially available addition reaction type silicone resin or a commercially available silicone gum (G) in which a silicone gum (G) and a silicone resin (R) are substantially mixed may be used. As a commercially available addition reaction type silicone resin, examples thereof include KR-3700, KR-3701, KR-3704, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3270, X-40-3306, KSN-320-A, KSN-3002, KS-776-841, KS-3601, KS-830E, X-62-2825, X-62-2829, X-92-128 (all trade names), TSR1512, TSR1516, XR37-B9204, TSE-201, XE-25-511, SL6210, SL6510, SL6562, SL6962, SL6062, SL6162 (all trade names), SD4580, SD4584, SD4585, SD4586, 4587 4592 4560, SD4570, SD4600, SD 92, SD A, SD, SD 35-312, and BY 35C 35-35, and the like manufactured BY Migaku-new materials. The present invention is not limited to the above-described one, as long as the mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin and the content of the alkenyl group bonded to the silicon atom are the same In the range of (2), 1 or more may be used singly or in combination. In addition, the addition reaction type silicone resin to which the later-described crosslinking agent is not added is added to a type such as SD4600FC manufactured by Topo Corp., as long as the storage modulus at 200℃measured in accordance with the adhesive layer under the He atmosphere is 1.0X10 5 ～1.0×10 7 The range of Pa may be used by adding a crosslinking agent after that.
[ Cross-linking agent ]
The crosslinking agent in the present embodiment is used to crosslink the alkenyl groups bonded to the silicon atoms of the silicone gum (G) included in the addition reaction type silicone resin. As the crosslinking agent, an organopolysiloxane (organohydrogen polysiloxane) having at least 2, preferably 3 or more hydrogen atoms (SiH) bonded to silicon atoms in 1 molecule is used. In the following description, an organopolysiloxane having a hydrogen atom (SiH) bonded to a silicon atom is sometimes simply referred to as an organohydrogen polysiloxane.
Examples of the molecular structure of the organopolysiloxane used as the crosslinking agent include linear, partially branched linear, branched, and network. The viscosity of the organopolysiloxane at 25℃is preferably in the range of 1 to 5,000 mPas. The viscosity may be measured using a BM-type rotational viscometer.
The organopolysiloxane used as the crosslinking agent may be any conventionally known organopolysiloxane. For example, the organohydrogen polysiloxane represented by the following general formula (3) or general formula (4) can be used as the organohydrogen polysiloxane, but the present invention is not limited thereto.
[ chemical 3]
H b R 3 (3-b) SiO-(HR 3 SiO) P -(R 3 2 SiO) q -SiR 3 (3-b) H b General formula (3)
[ chemical 4]
Here, in the general formulae (3) and (4), R 3 The organic hydrogen-containing polysiloxane has a viscosity of 1 to 5,000 mPas at 25 ℃ and is a 1-valent hydrocarbon group having 1 to 10 carbon atoms, b is 0 or 1, and p and q are integers. r is an integer of 2 or more, s is an integer of 0 or more, and r+s is not less than 3, preferably not less than 8 and not less than 3. The organopolysiloxane may be a mixture of 2 or more kinds.
R3 is a 1-valent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Examples thereof include alkyl groups such as methyl, ethyl, propyl and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl, and alkenyl groups such as vinyl and allyl. Methyl or phenyl is particularly preferred.
The content of the organopolysiloxane used as the crosslinking agent is changed in a suitable range so that the content of the silicon atom-bonded alkenyl groups in the organopolysiloxane (G) and the content of the silicon atom-bonded hydrogen atoms in the organopolysiloxane are balanced, and thus, for example, it is not generally preferable to set the molar ratio (SiH groups/alkenyl groups) of the total amount of the silicon atom-bonded hydrogen atoms (SiH) in the organopolysiloxane to the total amount of alkenyl groups in the organopolysiloxane (G) formed from an organopolysiloxane such as polydimethylsiloxane containing alkenyl groups bonded to silicon atoms to an amount in the range of 0.15 to 15.0, more preferably an amount in the range of 0.5 to 10.0, and most preferably an amount in the range of 1.5 to 5.0.
When the content of the organopolysiloxane is less than the lower limit, crosslinking and curing of the adhesive layers 2 and 3 become insufficient, and the storage modulus at 200 ℃ in the He atmosphere decreases, so that the amount of outgas generated increases and the cohesive force also decreases. In this case, there is a concern that the appearance of the functional film to be formed is deteriorated, and there is a concern that the film substrate may be left with adhesive residue when the adhesive tapes 10 and 20 are peeled off after the film formation. On the other hand, when the content of the organopolysiloxane exceeds the upper limit, the remaining hydrogen atoms (SiH) bonded to silicon atoms undergo silanol (si—oh), and moisture generated during the dehydration condensation reaction during film formation becomes outgas, and there is a concern that the appearance of the functional film to be formed may be deteriorated. Further, the adhesion force with the film substrate increases, and when the adhesive tapes 10 and 20 are peeled off after film formation, there is a concern that the film substrate is broken and there is a concern that the film substrate may be left with adhesive residue.
The content of the crosslinking agent in the adhesive layers 2 and 3 of the present embodiment may be adjusted so that the total amount of hydrogen atoms (SiH) bonded to silicon atoms in the organopolysiloxane is in the range of 0.15 to 15.0mol equivalent relative to the total amount of alkenyl groups in the silicone gel (G) formed from the organopolysiloxane such as polydimethylsiloxane having alkenyl groups bonded to silicon atoms, as described above. If the preferable content of the crosslinking agent satisfying the above range is expressed as the added mass part, the amount of the hydrogen atoms (SiH) bonded to silicon atoms in the crosslinking agent is changed within an appropriate range so as to be balanced, and therefore, the crosslinking agent cannot be generally added in such a manner that the amount of the crosslinking agent is in the range of 0.1 to 15.0 mass parts in terms of solid content, for example, based on 100 mass parts of the solid content of the addition reaction type silicone resin.
By setting the content of the crosslinking agent to the above-described range of 0.15 to 15.0mol equivalent relative to the addition reaction type silicone resin, hydrosilylation reaction, that is, crosslinking and curing of the adhesive layers 2 and 3, is sufficiently performed between the alkenyl group of the silicone gum (G) and the SiH group of the crosslinking agent, and the cohesive force and the storage modulus at 200 ℃ under He atmosphere can be set to appropriate values. The remaining amount of SiH groups can be set to a level that does not adversely affect the adhesive layers 2 and 3 as described above.
In a preferred embodiment, the adhesive layer is adjusted so that the number of hydrogen atoms bonded to silicon atoms included in the adhesive layer is larger than the number of alkenyl groups bonded to silicon atoms. In such a case, the content of alkenyl groups bonded to silicon atoms corresponds to the amount of crosslinking, and therefore, it is easy to appropriately adjust the storage modulus.
Therefore, when the adhesive tapes 10 and 20 having the adhesive layers 2 and 3 formed of the addition reaction type silicone resin crosslinked and cured in this way are used as a tape for temporarily fixing a film substrate when a functional film is formed on the film substrate by a vacuum film forming process such as sputtering or vapor deposition, the amount of outgas generated from the adhesive tapes 10 and 20 can be reduced, and thus the appearance of the formed functional film can be improved. In addition, when the adhesive tapes 10 and 20 are peeled off after film formation, breakage of the film substrate and occurrence of residual adhesive on the film substrate can be greatly suppressed.
The crosslinking agent is not particularly limited as long as it is an organopolysiloxane (organohydrogen polysiloxane) having at least 2 hydrogen atoms (SiH) bonded to silicon atoms in 1 molecule, which is a crosslinking agent used as a crosslinking agent for addition reaction type silicone resins. Specifically, for example, X-92-122 (trade name) manufactured BY Xinyue chemical Co., ltd., BY24-741 (trade name) manufactured BY Topo Corning Co., ltd.) and the like are mentioned.
[ catalyst ]
In order to carry out the hydrosilylation reaction between the alkenyl groups of the silicone gum (G) in the addition reaction type silicone resin and the SiH groups of the crosslinking agent, a platinum group metal-based catalyst is required. Examples of the central metal of the catalyst include platinum, palladium, iridium, rhodium, osmium, ruthenium, and the like, and among them, platinum is suitably used. The platinum-based catalyst is not particularly limited, and examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and a vinyl-containing siloxane. As the platinum-based catalyst, a commercially available catalyst can be used. As the commercial catalyst, for example, CAT-PL-50T manufactured by Xinyue chemical industry Co., ltd., SRX-212Cat manufactured by Toli Corning Co., ltd., NC-25 and the like can be mentioned. The content of the platinum group metal catalyst is not particularly limited, but is preferably in the range of 1 to 500ppm by mass of metal relative to the mass of the silicone gum (G). When the metal mass is less than 1ppm, the reaction is slow, the crosslinking and curing of the adhesive layers 2 and 3 become insufficient, and the storage modulus at 200 ℃ in He atmosphere is reduced, so that the generation amount of outgas is increased and the cohesive force is also reduced. In this case, there is a concern that the appearance of the functional film to be formed is deteriorated, and there is a concern that the film substrate may be left with adhesive residue when the adhesive tape 10 is peeled off after the film formation. On the other hand, if the metal mass exceeds 500ppm, there is a concern that the solution of the resin composition containing the addition reaction type silicone resin may be thickened or gelled. In addition, the cost becomes high and uneconomical.
[ reaction retarder ]
The reaction retarder may be optionally added to the resin composition containing the addition-reaction-type silicone resin of the present embodiment. The reaction retarder is a component which is added arbitrarily to prepare a solution of the resin composition or to coat the solution of the resin composition on a substrate without thickening or gelling the solution before heating and curing, and is used to coordinate with a platinum group metal as an addition reaction catalyst in the solution of the resin composition to inhibit the addition reaction, and is used to release the coordination and exhibit catalytic activity when heated to cure the coated adhesive layer, thereby allowing the hydrosilylation reaction to proceed. As the reaction retarder, a reaction retarder such as 1-ethynyl cyclohexanol which has been conventionally used as an addition reaction type silicone adhesive can be used. As the retarder, a commercially available reaction retarder may be used. As a commercially available reaction retarder, for example, CAT PLR-2 manufactured BY Xinyue chemical industry Co., ltd., BY24-808 manufactured BY Toli Corning Co., ltd. The content of the reaction retarder is not particularly limited, but is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the silicone gum (G). If the amount of the reaction retarder to be added is less than 0.01 parts by mass, the reaction may not be suppressed, and the solution of the resin composition containing the addition reaction type silicone resin may be thickened or gelled. On the other hand, if the amount of the reaction retarder added exceeds 5 parts by mass, the reaction may be slow, and crosslinking and curing may be insufficient.
[ thickness ]
The thickness of the adhesive layers 2, 3 is not particularly limited, and if the thickness of the adhesive layers 2, 3 becomes thicker, the outgas generation amount at high vacuum and high temperature tends to naturally increase. Therefore, it is necessary to perform the vacuum degree of 1.0X10 -4 Heating the adhesive tapes 10 and 20 from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or lessThe total amount of outgas generated when further maintained at 200℃for 30 minutes was then 180mg/m 2 The setting is performed in the following manner. The thickness of the adhesive layers 2, 3 varies in an appropriate range depending on the storage modulus of the adhesive layers 2, 3 at 200 ℃ under He atmosphere, etc., and thus cannot be generally said, for example, the lower limit of the thickness is preferably 3 μm or more, more preferably 10 μm or more, from the viewpoint of securing temporary fixing force. On the other hand, the upper limit of the thickness is preferably 200 μm or less, more preferably 100 μm or less, from the viewpoints of suppression of the total amount of outgas, uniform coating property of the adhesive layer, suppression of the amount of residual solvent, and easy peelability of the adhesive tapes 10, 20.
(adhesive tape)
The adhesive tape of the present embodiment is either one of a single-sided adhesive tape 10 having an adhesive layer 2 on one side of a substrate 1 and a double-sided adhesive tape 20 having an adhesive layer 2 and an adhesive layer 3 on both sides of a substrate 1, and has a vacuum degree of 1.0x10 - 4 The total amount of outgas generated when the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes is 180mg/m 2 Hereinafter, more preferably 100mg/m 2 The following is given. If the total amount of the above-mentioned outgas exceeds 180mg/m 2 In the process of transporting atoms ejected from a target of a film forming material to a film substrate for film formation and in the process of depositing, the presence of the outgas may hinder the original activity of the atoms and affect the growth of the functional thin film, so that there is a concern that the appearance and characteristics of the functional thin film formed on the film substrate by a vacuum process may be deteriorated.
(method for producing adhesive tape)
Next, an example of a method for producing the single-sided adhesive tape 10 described in fig. 1 will be described. The single-sided adhesive tape 10 can be produced in a roll-like manner as in the conventional method for producing a silicone-based adhesive tape, for example, the silicone-based adhesive tape for molding plastic lenses described in japanese unexamined patent publication No. 2012-107125, and is produced by laminating the adhesive layer 2 on one side of the base material 1 and winding the laminated adhesive layer into a roll-like raw tape.
< formation of adhesive layer >
On one surface of the substrate 1, an anchor coating agent for improving adhesion to the adhesive layer 2 is first applied and dried to form an anchor coating layer, and a resin composition (adhesive composition) solution for the adhesive layer 2 containing an addition reaction type silicone resin as a main component is continuously applied on the anchor coating layer and dried to form the adhesive layer 2. Next, the release agent for improving the releasability of the adhesive layer 2 was applied to the other surface of the base material 1, and dried to form a release treated layer, and the release treated layer was wound into a roll of the adhesive tape raw tape. The release film may be bonded to the adhesive layer 2 without forming the release treatment layer, and the adhesive tape raw tape may be wound in a roll. In the formation of the adhesive layer 2, if more specifically described, a resin composition solution for the adhesive layer 2 is first prepared by adding a crosslinking agent, a catalyst, or the like to a solution in which an adhesive containing an alkenyl group-containing silicone resin (G) and an alkenyl group-free silicone resin (R) as main components bonded to silicon atoms is dissolved in an organic solvent such as toluene or xylene. Next, the resin composition solution is applied to the anchor coat layer of the base material 1 by a corner-roll coater (registered trademark), a lip coater or the like so that the thickness after drying becomes uniform. Then, the coated adhesive composition is heated and dried at a predetermined temperature, thereby forming an adhesive layer 2 on the substrate 1 via the anchor coating layer. Through the above steps, the single-sided adhesive tape 10 shown in fig. 1 is obtained. In fig. 1, the anchor coat layer and the release treatment layer are not shown.
As the conditions for heating and drying the adhesive composition, for example, the conditions disclosed in japanese patent application laid-open No. 2012-107125 and the like can be used as references. Specifically, for example, the resin composition solution for the adhesive layer 2 may be applied to the base material 1 through the anchor coat layer, the initial drying may be performed by stepwise increasing the temperature at 40 to 90 ℃ in the first half region of the drying furnace, and then the heating drying may be performed for 1 to 5 minutes in the second half region of the drying furnace at 130 to 200 ℃ to wind the raw tape in a roll form. In particular byThe heat-drying treatment in the latter half region of the drying furnace causes the low-molecular-weight dimethylpolysiloxane contained in the material of the addition-reaction-type silicone resin from the beginning to volatilize from the adhesive layer 2 and reduce the same according to the drying treatment conditions, and promotes the hydrosilylation reaction of the silicone material (G) in the addition-reaction-type silicone resin, so that the adhesive layer 2 is crosslinked and cured. Here, since the adhesive layer 2 of the single-sided adhesive tape 10 of the present embodiment is formed by optimizing the alkenyl groups of the silicone gum (G) and the content of the silicone gum (G) in the addition reaction type silicone resin as described above for the purpose of vacuum process, the adhesive layer 2 can be crosslinked and structured to a higher degree than the conventional general silicone adhesive tape by the above-described heat drying, and the storage modulus of the adhesive layer 2 under high vacuum and high temperature can be increased, in other words, the storage modulus at 200 ℃ measured under He atmosphere can be increased to 1.0×10 5 ～1.0×10 7 Pa. That is, as described above, the movement of the molecular chains of the silicone gum (G) and the silicone resin (R) is restricted by the highly crosslinked structure, and the interaction between the main chain backbones and the interaction within the same backbone can be suppressed, so that the phenomenon of the regeneration of the low molecular weight component which causes outgas in the vacuum film forming process can be greatly suppressed. As a result, even if the high-temperature and long-time annealing process of the single sheet of the adhesive sheet is not performed as in the conventional technique, the single-sided adhesive tape 10 can be easily designed to have a vacuum degree of 1.0×10 by the roll-to-roll method -4 The total amount of outgas generated when the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is maintained at 200 ℃ for 30 minutes is 180mg/m 2 In the following, when the adhesive tape 10 is used as an adhesive tape for temporary fixation in forming a functional thin film on a heat-resistant substrate by a vacuum film forming process such as sputtering or vapor deposition, the generation of outgas from the adhesive tape 10 generated in the vacuum film forming process can be suppressed, and the appearance of the obtained functional thin film can be improved. In addition, after securing a temporary fixing force that prevents the film substrate from falling off during vacuum film formation, breakage of the film substrate can be greatly suppressed when the adhesive tape 10 is peeled off after film formation And the generation of residual glue on the film substrate.
Next, an example of a method of manufacturing the double-sided adhesive tape 20 will be described with reference to fig. 2. An anchor coating agent for improving adhesion to the adhesive layer 3 is applied to one surface (1 surface side) of the substrate 1, and dried to form an anchor coating layer, and a resin composition solution for the adhesive layer 3 containing an addition reaction type silicone resin as a main component is continuously applied to the anchor coating layer, and dried to form the adhesive layer 3. Next, a first release film is attached to the surface of the adhesive layer 3, and the tape is wound into a roll. Further, in the same manner as the above method, an anchor coat layer and an adhesive layer 2 are formed on the other surface (surface side 2) of the base material 1 on which the adhesive layer 3 is formed, and a second release film is attached to the surface of the adhesive layer 2, and the base tape is wound in a roll form. Through the above steps, the double-sided adhesive tape 20 shown in fig. 2 is obtained. The conditions for coating and drying may be set in the same manner as the conditions described above. In fig. 2, the first and second release films are not shown.
(temporary fixing method of film substrate to Carrier substrate by adhesive tape)
As described above, the adhesive tapes 10 and 20 according to the present embodiment are used for forming functional thin films such as antireflection films on thin film substrates represented by cover glass of smart phones by a batch process through a vacuum film forming process using a carousel sputtering apparatus or the like, and as shown in fig. 3 and 4, a plurality of thin film substrates 12 such as cover glass are temporarily fixed to a carrier substrate 11 made of glass, SUS or the like. In the case of forming functional thin films, the carrier substrate 11 to which the plurality of thin film substrates 12 are temporarily fixed is attached to a rotating fixture of a carousel sputtering apparatus, and the functional thin films such as an antireflection film are formed on the surfaces of the thin film substrates 12 at once. Next, an example of a temporary fixing method of the film substrate 11 using the single-sided adhesive tape 10 of the present embodiment will be described.
< temporary fixing method Using Single-sided adhesive tape 10 >)
Fig. 5 is a diagram schematically showing an example of a temporary fixing method 50 of the carrier substrate 11 using the single-sided adhesive tape 10 according to an embodiment of the present invention. First, the single-sided adhesive tape 10 is placed on the carrier substrate 11 such that the release film of the single-sided adhesive tape 10 is peeled off and the adhesive layer 2 is on the upper surface side, and the single-sided adhesive tape 10' (which may be the same as or different from the single-sided adhesive tape 10) in the form of a long single-sided adhesive tape 10 of the present embodiment is used, and both ends of the single-sided adhesive tape 10 are adhered to the carrier substrate 11, so that the carrier substrate 11 and the single-sided adhesive tape 10 are fixed. Next, a plurality of film substrates 12 are placed and stuck (temporarily fixed) at equal intervals on the surface of the adhesive layer 2 of the single-sided adhesive tape 10, and film formation by a vacuum process is performed.
Fig. 6 is a diagram schematically showing another example of a temporary fixing method of a film substrate using the single-sided adhesive tape 10 according to the embodiment. First, the second release film on the adhesive layer 3 side is peeled off from the carrier substrate 11, and 2 long double-sided adhesive tapes 20 according to the present embodiment are attached side by side. Next, the first release film on the adhesive layer 2 side of the double-sided adhesive tape 20 is peeled off, and the single-sided adhesive tape 10 is attached to the surface of the adhesive layer 2 of the double-sided adhesive tape 20 such that the adhesive layer 2 of the single-sided adhesive tape 10 (with the release film) is on the upper side. Next, the release film on the adhesive layer 2 side of the single-sided adhesive tape 10 is peeled off, and a plurality of film substrates 12 are placed and stuck (temporarily fixed) at equal intervals on the surface of the adhesive layer 2 of the single-sided adhesive tape 10, and film formation by a vacuum process is performed.
< temporary fixing method Using double-sided adhesive tape 20 >)
Fig. 7 is a diagram schematically showing an example of a temporary fixing method 70 of the film substrate 11 using the double-sided adhesive tape 20 as another embodiment of the present invention. First, the first release film on the adhesive layer 3 side is peeled off from the carrier substrate 11, and the double-sided adhesive tape 20 is attached. Next, the second release film on the adhesive layer 2 side of the double-sided adhesive tape 20 is peeled off, and a plurality of film substrates 12 are placed and stuck (temporarily fixed) at equal intervals on the surface of the adhesive layer 2 of the double-sided tape 20, and film formation by a vacuum process is performed.
Fig. 8 is a diagram schematically showing another example of a temporary fixing method of the film substrate 11 using the double-sided adhesive tape 20 as another embodiment of the present invention. First, the double-sided adhesive tape 20 is punched to have the same size as the film substrate 11. Next, the second release film on the adhesive layer 3 side is peeled off from the carrier substrate 11, and the punched double-sided adhesive tape 20 is stuck at equal intervals. Next, the first release film on the adhesive layer 2 side of the double-sided adhesive tape 20 is peeled off, and a plurality of film substrates 12 (temporary fixing) are respectively stuck on the surface of the adhesive layer 2 of the double-sided adhesive tape 20, and film formation by a vacuum process is performed.
(film formation of functional thin film by vacuum Process)
The method for forming a functional thin film such as an antireflection film by a vacuum process is not particularly limited, and examples thereof include a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plating method, a sputtering method, and the like. Among them, sputtering is suitably used from the viewpoints of hardness and adhesion of the functional film obtained. In a sputtering method using a carousel-type sputtering apparatus or the like, a carrier substrate 11 temporarily holding a plurality of thin film substrates 12 as illustrated in fig. 5 to 8 is mounted on a substrate holder placed on a drum of the carousel-type sputtering apparatus in vertical positions 30 and 40 as illustrated in fig. 3 and 4, and then the carrier substrate 11 (thin film substrate 12) is heated to a temperature of 150 to 200 ℃ for example, while the chamber is set to 10 -5 ～10 -6 A pressure of the degree of Torr. Next, the functional thin film material (atoms constituting the target material) is scattered by sputtering from the target material disposed outside the circular orbit toward the thin film substrate 12 held in the vertical placement posture in which the chamber is rotated along the circular orbit, and the material is deposited as the functional thin film on the surface and the side surface of the thin film substrate 12 facing the outside of the circular orbit, thereby forming the desired functional thin film. Examples of the functional film include, in addition to an antireflection film, films that can be formed by a vacuum process, such as an antiglare film, an antifouling film, a colored film, an abrasion resistance imparting film, a corrosion resistance imparting film, a conductivity imparting film, a reinforcing film, and an infrared reflection film.
(method for peeling adhesive tape after film formation)
Next, a method of peeling the adhesive tape after film formation will be described. After the chamber is cooled and the pressure is restored to the atmospheric pressure, the carrier substrate 11 to which the film-formed thin film substrate 12 is temporarily fixed is removed from the substrate holder. As shown in fig. 5, when the film substrate 12 is temporarily fixed by the single-sided adhesive tape 10, first, the single-sided adhesive tape 10' at both ends of the single-sided adhesive tape 10 is peeled off, and the single-sided adhesive tape 10 is removed from the carrier substrate 11 in a state where the film-formed film substrate 12 is temporarily fixed. Finally, the single-sided adhesive tape 10 was peeled off from the film-formed film substrate 12 while taking care of not damaging the film substrate 12. At this time, the film formation processing surface of the film substrate 12 may be vacuum-sucked to a clean stage, and the single-sided adhesive tape 10 may be peeled from the film substrate 12 subjected to the film formation processing. By the above operation, the thin film substrate 12 on which the functional thin film is formed is obtained.
As shown in fig. 6, when the film substrate 12 is temporarily fixed by the single-sided adhesive tape 10, first, the single-sided adhesive tape 10 is gradually peeled from the double-sided adhesive tape 20 in a state where the film-formed film substrate 12 is temporarily fixed. Finally, the single-sided adhesive tape 10 is peeled off from the film-formed film substrate 12 while taking care of not damaging the film substrate 12. At this time, the film formation processing surface of the film substrate 12 may be vacuum-sucked to a clean stage, and the single-sided adhesive tape 10 may be peeled from the film substrate 12 subjected to the film formation processing. By the above operation, the thin film substrate 12 on which the functional thin film is formed is obtained.
As shown in fig. 7 and 8, when the film substrate 12 is temporarily fixed by the double-sided adhesive tape 20, a sharp stainless steel cutter is gradually inserted between the adhesive layer 2 of the double-sided adhesive tape 20 and the corner portion of the film substrate 12 subjected to the film formation treatment in a state where the carrier substrate 11 is vacuum-sucked to the clean stage, and peeling is triggered between the film substrate 12 and the adhesive layer 2. Next, the film substrate 12 subjected to the film formation treatment was peeled from the adhesive layer 2 by gradually lifting up from the corner portion of the film substrate 12 using a vacuum suction pad. In the case where peeling can be performed even by using only the vacuum suction pad without triggering peeling, the present invention is not limited thereto. By the above operation, the thin film substrate 12 on which the functional thin film is formed is obtained.
Examples
The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited to the following examples. Hereinafter, each example and each comparative example will be described in detail.
In order to prepare various adhesives used in the present examples and comparative examples, the following silicone resins (a) to (D) were used as main components of the adhesives, and the following organopolysiloxanes (organopolysiloxanes) having hydrogen atoms (SiH) bonded to silicon atoms were used as crosslinking agents. The silicone resins (a) and (B) are a mixture of silicone gum (G) and silicone resin (R)/(R) mass ratio=40/60]The silicone resin (G) uses a dimethylsiloxane-methylvinylsiloxane copolymer terminated by dimethylvinylsiloxy groups at both ends of the molecular chain and having a polymerization average molecular weight (Mw) of about 50 ten thousand, and the silicone resin (R) uses a silicone resin having a polymerization average molecular weight (Mw) of about 5000 and having R 2 3 SiO 0.5 Unit (M unit) and SiO 2 Organopolysiloxane of unit (Q unit) (MQ resin). The silicone resins (C) and (D) were resins of the silicone resin (C) alone, the silicone resin (G) of the silicone resin (C) was a dimethylsiloxy-terminated dimethylsiloxane-methylhexenyl siloxane copolymer having an average molecular weight (Mw) of about 20 ten thousand at both ends of the molecular chain, and the silicone resin (D) was a dimethylsiloxy-terminated dimethylsiloxane-methylhexenyl siloxane copolymer having an average molecular weight (Mw) of about 60 ten thousand at both ends of the molecular chain. In addition, the silicone resin (E) is a resin of a silicone resin (R) alone, and the silicone resin (R) has a polymerization average molecular weight (Mw) of about 5000 and has R 2 3 SiO 0.5 Unit (M unit) and SiO 2 Organopolysiloxane of unit (Q unit) (MQ resin).
·Organosilicon systemResin (A)
Silicone gum (G)/silicone resin (R) =40 mass%/60 mass% mixture
Alkenyl (vinyl) content: 2.0X10 -5 mol/g
·Organosilicon resin (B)
Silicone gum (G)/silicone resin (R) =40 mass%/60 mass% mixture
Alkenyl (vinyl) content: 2.0X10 -6 mol/g
·Organosilicon resin (C)
Organosilicon gum material (G)
Alkenyl (hexenyl) content: 2.0X10 -4 mol/g
·Organosilicon resin (D)
Organosilicon gum material (G)
Alkenyl (hexenyl) content: 1.0X10 -2 mol/g
·Organosilicon resin (E)
Silicone resin (R)
·Crosslinking agent (A)
Organopolysiloxane containing hydrogen
SiH group content: 1.0X10 -2 mol/g
·Crosslinking agent (B)
Organopolysiloxane containing hydrogen
SiH group content: 4.0X10 -2 mol/g
1. Production of adhesive tape and film formation of functional thin film (antireflection film) on thin film substrate 12
Example 1
An addition reaction type silicone resin (S1) obtained by mixing the silicone resin (a) and the silicone resin (C) so that the mass ratio (a)/(C) became 83/17 was diluted with toluene and stirred to prepare an addition reaction type silicone resin solution (solid content concentration: 30 mass%). The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S1) was 50/50, and the alkenyl group content was 5.0X10 -5 mol/g. Incidentally, the organic silica gel materialG) The alkenyl content in the mixture was 1.0X10 -4 mol/g。
Next, 1.01 parts by mass (SiH group/alkenyl group molar ratio=2.02) of the crosslinking agent (a) was blended with 333 parts by mass (100 parts by mass in terms of solid content conversion) of the addition reaction type silicone resin solution by a disperser, and uniformly stirred and mixed. Next, 1.0 parts by mass of a platinum-based catalyst "NC-25" (trade name) manufactured by Topo Co., ltd was blended by a disperser, and the mixture was uniformly stirred and mixed to prepare an adhesive solution for coating.
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 20 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃ and dried for 2 minutes, and the release film was bonded to obtain a single-sided adhesive tape 10 having a total thickness of 95 μm. The single-sided adhesive tape 10 'was also produced in the same manner as the single-sided adhesive tape 10' in which the thickness of the base material 1 was changed to 58 μm in total.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 2.2X10 at 200℃measured under an atmosphere of He 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 72.5mg/m 2 。
Next, using the single-sided adhesive tape 10 (size 310mm×340 mm) and the single-sided adhesive tape 10 '(size 20mm×360 mm), as shown in fig. 4, first, the single-sided adhesive tape 10 from which the release film was peeled was fixed to the carrier substrate 11 (SUS, size 370mm×380mm, thickness 2 mm) with the single-sided adhesive tape 10' so that the adhesive layer 2 was on the upper surface side. Next, 6 film substrates 12 (cover glass, size 140mm×70mm, thickness 0.4 mm) were placed on the adhesive layer 2 of the single-sided adhesive tape 10 at equal intervals, and temporarily fixed. The carrier substrate 11 having 6 film substrates 12 temporarily fixed thereto by the single-sided adhesive tape 10 was prepared into a total of 8 groups (total of 48 film substrates 12: 48 sheets/1 lot) for film formation of functional films (antireflection films).
Next, the above-mentioned carrier substrates were each mounted in a vertically placed posture on a substrate holder arranged on a drum of a carousel-type radical assisted sputtering apparatus, and the inside of the apparatus was set to 10 by exhausting air by a vacuum pump while heating the carrier substrate (thin film substrate) to 200 ℃ -6 Pressure of Torr. Then, the drum was rotated with silicon (Si) as a target, and a high refractive index layer (silicon nitride: siNx) and a low refractive index layer (silicon oxide: siO) were formed by post-reaction sputtering under the following conditions 2 ) The total 6 antireflection layers formed by alternately stacking are formed on the surface of the thin film substrate 12 (cover glass).
·Sputtering conditions
High refractive index layer (silicon nitride: siNx)
N 2 Air: 10sccm
Ar gas: 10sccm
Sputtering power: 2.0KW
Low refractive index layer (silicon oxide: siO) 2 )
O 2 Air: 10sccm
Ar gas: 10sccm
Sputtering power: 1.5KW
·Antireflection film (//film substrate)
SiO 2 (110nm)/SiNx(60nm)/SiO 2 (43nm)/SiNx(33nm)/SiO 2 (50 nm)/SiNx (140 nm) (//thin film substrate)
Example 2
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S2) obtained by mixing the silicone resin (a) and the silicone resin (C) in such a manner that the mass ratio (a)/(C) was 50/50 was used instead of the addition reaction type silicone resin (S1), and the amount of the crosslinking agent (a) was changed to 2.20 parts by mass (SiH group/alkenyl group molar ratio=2.00). The addition reaction type organic silicon resin (S2) contains organic silicon sizing material (G) and organic siliconThe mass ratio (G)/(R) of the resin (R) was 70/30 and the alkenyl content was 1.1X10 -4 mol/g. Incidentally, the alkenyl group content in the above-mentioned silicone gum (G) was 1.5X10 -4 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 50 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 160 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 125 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 5.9X10 at 200℃measured under an atmosphere of He 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 65.1mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 3
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S3) obtained by mixing the silicone resin (a), the silicone resin (B) and the silicone resin (E) so that the mass ratio (a)/(B)/(E) became 50/42/8 was used instead of the addition reaction type silicone resin (S1), the amount of the crosslinking agent (a) was changed to 0.22 parts by mass (SiH group/alkenyl group molar ratio=2.17), and the amount of the platinum catalyst "NC-25" was changed to 0.5 parts by mass. The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S2) was 35/65, and the alkenyl group content was 1.0X10 -5 mol/g. Incidentally, the alkenyl group content in the above-mentioned silicone gum (G) was 2.9X10 -5 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 30 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 105 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 1.0X10 at 200℃measured under He atmosphere 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 159.8mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 4
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S4) obtained by mixing the silicone resin (C) and the silicone resin (D) in such a manner that the mass ratio (C)/(D) was 92/8 was used instead of the addition reaction type silicone resin (S1), 1.01 parts by mass of the crosslinking agent (a) was changed to 4.90 parts by mass of the crosslinking agent (B) (molar ratio of SiH group/alkenyl group=1.97), and the amount of the platinum catalyst "NC-25" was changed to 3.0 parts by mass. The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S2) was 100/0, and the alkenyl group content was 1.0X10 -3 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 75 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 200 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 150 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 7.2X10 at 200℃measured under an atmosphere of He 6 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature was raised from 23℃to 200℃at a heating rate of 10℃per minute under an atmosphere of Torr or less and then the mixture was further maintained at 200℃for 30 minutes, the total amount of outgas generated was 31.2mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 5
A single-sided adhesive tape 10 having a total thickness of 125 μm was obtained in the same manner as in example 2, except that the amount of the crosslinking agent (a) was changed to 0.55 parts by mass (SiH group/alkenyl group molar ratio=0.50).
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 1.5X10 at 200℃measured under an atmosphere of He 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature was raised from 23℃to 200℃at a heating rate of 10℃per minute under an atmosphere of Torr or less and then the mixture was further maintained at 200℃for 30 minutes, the total amount of outgas generated was 122.3mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 6
A single-sided adhesive tape 10 having a total thickness of 125 μm was obtained in the same manner as in example 2, except that the amount of the crosslinking agent (a) was changed to 1.65 parts by mass (SiH group/alkenyl group molar ratio=1.50).
Adhesive layer of the single-sided adhesive tape 102 has a storage modulus of 4.7X10 at 200℃measured under He atmosphere 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 70.3mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 7
A single-sided adhesive tape 10 having a total thickness of 125 μm was obtained in the same manner as in example 2, except that the amount of the crosslinking agent (a) was changed to 5.55 parts by mass (SiH group/alkenyl group molar ratio=5.00).
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 6.0X10 at 200℃measured under He atmosphere 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature was raised from 23℃to 200℃at a heating rate of 10℃per minute under an atmosphere of Torr or less and then the mixture was further maintained at 200℃for 30 minutes, the total amount of outgas generated was 84.2mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 8
A single-sided adhesive tape 10 having a total thickness of 125 μm was obtained in the same manner as in example 2, except that 5.55 parts by mass of the crosslinking agent (a) was changed to 2.80 parts by mass of the crosslinking agent (B) (molar ratio of SiH group/alkenyl group=10.00).
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 6.7X10 at 200℃measured under an atmosphere of He 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 105.7mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Example 9
First, as an adhesive solution for coating for the adhesive layer 3, an adhesive solution for coating formed of the same composition as in example 1 (using an addition reaction type silicone resin (S1)) was prepared. Next, the adhesive solution for coating was applied to the 1-side of the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 3 became 30 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 3 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the first release film was bonded to the adhesive layer 3, whereby an intermediate laminate having a total thickness of 105 μm was obtained.
Next, as the adhesive solution for coating for the adhesive layer 2, an adhesive solution for coating formed of the same composition as in example 2 (using an addition reaction type silicone resin (S2)) was prepared. Next, the adhesive solution for coating was applied to the surface (2-side of the substrate) of the intermediate laminate opposite to the surface on which the adhesive layer 3 was formed so that the dry thickness of the adhesive layer 2 became 30 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 160 ℃, and the second release film was bonded to the adhesive layer 2, whereby the double-sided adhesive tape 20 having a total thickness of 135 μm was obtained.
The adhesive layer 2 and the adhesive layer 3 of the double-sided adhesive tape 20 had storage moduli of 5.9X10 at 200℃as measured under He atmosphere, respectively 5 Pa、2.5×10 5 Pa. Further, the double-sided adhesive tape 10 was used in a vacuum degree of 1.0X10 -4 Heating from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under the atmosphere of Torr or less, and further maintaining at 200 ℃ for 30 min to obtainThe total amount of generated outgas was 128.3mg/m 2 。
Next, using the double-sided adhesive tape 20 (size 310mm×340 mm), as shown in fig. 6, first, the first release film on the adhesive layer 3 side of the double-sided adhesive tape 20 was peeled off, the adhesive layer 3 side was stuck to the carrier substrate 11 (SUS, size 370mm×380mm, thickness 2 mm), and the double-sided adhesive tape 20 was fixed. Next, the second release film on the adhesive layer 2 side of the double-sided adhesive tape 20 was peeled off, and 6 film substrates 12 (cover glass, size 140mm×70mm, thickness 0.4 mm) were placed on the adhesive layer 2 of the double-sided adhesive tape 20 at equal intervals, and temporarily fixed. The carrier substrate 11 having 6 film substrates 12 temporarily fixed thereto by the double-sided adhesive tape 20 was prepared into a total of 8 groups (total of 48 film substrates 12: 48 sheets/1 lot) for film formation of functional films (antireflection films).
Then, in the same manner as in example 1, an antireflection film was formed on the surface of the thin film substrate 12 (cover glass).
Comparative example 1
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S5) obtained by mixing the silicone resin (a) and the silicone resin (B) so that the mass ratio (a)/(B) became 40/60 was used instead of the addition reaction type silicone resin (S1), and the amount of the crosslinking agent (a) was changed to 0.18 parts by mass (SiH group/alkenyl group molar ratio=2.00). The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S5) was 40/60, and the alkenyl group content was 9.2X10 -6 mol/g. Incidentally, the alkenyl group content in the above-mentioned silicone gum (G) was 2.3X10 -5 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 20 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 95 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 7.4X10 at 200℃measured under He atmosphere 4 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 193.3mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Comparative example 2
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S6) obtained by mixing the silicone resin (C) and the silicone resin (D) so that the mass ratio (C)/(D) became 70/30 was used instead of the addition reaction type silicone resin (S1), and that 1.01 parts by mass of the crosslinking agent (a) was changed to 15.7 parts by mass of the crosslinking agent (B) (molar ratio of SiH group/alkenyl group=2.09). The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S6) was 100/0, and the alkenyl group content was 3.0X10 -3 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 40 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 115 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 1.9X10 at 200℃measured under an atmosphere of He 7 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 Heating from 23 ℃ to at a heating rate of 10 ℃/min under an atmosphere of Torr or lessWhen further maintained at 200℃for 30 minutes after 200℃the total amount of outgas generated was 33.6mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Comparative example 3
An adhesive solution for coating was prepared in the same manner as in example 1, except that the addition reaction type silicone resin (S7) obtained by mixing the silicone resin (a), the silicone resin (C) and the silicone resin (E) so that the mass ratio (a)/(C)/(E) became 63/5/32 was used instead of the addition reaction type silicone resin (S1), and the amount of the crosslinking agent (a) was changed to 0.45 parts by mass (SiH group/alkenyl group molar ratio=1.97). The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S6) was 30/70, and the alkenyl group content was 2.3X10 - 5 mol/g. Incidentally, the alkenyl group content in the above-mentioned silicone gum (G) was 7.3X10 -5 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 15 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the release film was bonded to the adhesive layer 2, whereby the single-sided adhesive tape 10 having a total thickness of 90 μm was obtained.
The adhesive layer 2 of the single-sided adhesive tape 10 has a storage modulus of 1.5X10 at 200℃measured under an atmosphere of He 5 Pa. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 135.7mg/m 2 。
Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in example 1, an antireflection film was formed on the surface of the film substrate 12 (protective glass) in the same manner as in example 1.
Comparative example 4
A coating adhesive solution was produced in the same manner as in example 2, except that the crosslinking agent (a) was not added. The mass ratio (G)/(R) of the silicone gum (G) to the silicone resin (R) in the addition reaction type silicone resin (S2) was 70/30, and the alkenyl group content was 1.1X10 -4 mol/g。
Next, the adhesive solution for coating was applied to the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 2 became 50 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the single-sided adhesive tape 10 having a total thickness of 125 μm was obtained by drying the adhesive layer 2 by heating it for 2 minutes in the region where the highest temperature of the heat treatment provided in the latter half of the drying furnace became 200 ℃, but the adhesive layer 2 had a high tackiness, and the problem of sticking to a conveyor roller or the like occurred, and therefore, the single-sided adhesive tape 10 was not produced satisfactorily.
In the same manner as in the above-described drying conditions, the storage modulus of the adhesive layer 2 at 200 ℃ under He atmosphere was evaluated for the single-sided adhesive tape 10 produced in a monolithic manner, and as a result, it was observed that the storage modulus was rapidly decreased with the increase in temperature, and it was not possible to confirm the storage modulus around 200 ℃. In addition, the single-sided adhesive tape 10 has a vacuum degree of 1.0X10 -4 The amount of outgas generated when the temperature was raised from 23℃to 200℃at a heating rate of 10℃per minute under an atmosphere of Torr or less and then the temperature was further maintained at 200℃for 30 minutes was 251.1mg/m 2 。
Comparative example 5
First, as an adhesive solution for coating for the adhesive layer 3, an adhesive solution for coating formed of the same composition as in example 3 (using an addition reaction type silicone resin (S3)) was prepared. Next, the adhesive solution for coating was applied to the 1-side of the polyester film base material 1 (thickness 75 μm) manufactured by ori corporation so that the dry thickness of the adhesive layer 3 became 30 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 3 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the first release film was bonded to the adhesive layer 3, whereby an intermediate laminate having a total thickness of 105 μm was obtained.
Next, as the adhesive solution for coating for the adhesive layer 2, an adhesive solution for coating formed of the same composition as in example 1 (using the addition reaction type silicone resin (S1)) was prepared. Next, the adhesive solution for coating was applied to the surface (2-side of the substrate) of the intermediate laminate opposite to the surface on which the adhesive layer 3 was formed so that the dry thickness of the adhesive layer 2 became 20 μm, and initial drying was performed stepwise at a temperature of 40 to 90 ℃ in the first half of the drying furnace. Then, the adhesive layer 2 was heated and cured in a region where the highest temperature of the heat treatment provided in the second half of the drying furnace was 180 ℃, and the second release film was bonded to the adhesive layer 2, whereby a double-sided adhesive tape 20 having a total thickness of 125 μm was obtained.
The adhesive layer 2 and the adhesive layer 3 of the double-sided adhesive tape 20 had storage moduli of 2.2X10 at 200℃as measured under He atmosphere, respectively 5 Pa、1.3×10 5 Pa. Further, the double-sided adhesive tape 20 was used in a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 201.2mg/m 2 。
Next, using the double-sided adhesive tape 20 (size 310 mm. Times.340 mm), the same procedure as in example 9 was followed, an antireflection film is formed by forming a film on the surface of the film substrate 12 (cover glass) temporarily fixed to the adhesive layer 2.
2. Evaluation method
(1) Quantification of alkenyl group content of silicone-based resin and SiH group content of crosslinking agent
The silicone gum (G) formed of the organopolysiloxane containing an alkenyl group bonded to a silicon atom and the silicone resin (R) formed of the organopolysiloxane containing no alkenyl group bonded to a silicon atom of the present invention are prepared by the following methodsIn addition reaction type organic silicon resin mixed in such a way that the ratio of (G)/(R) =35/65-100/0 is in the range, the alkenyl content is measured by 500MHz 1 H-NMR spectrum. Specifically, the nonvolatile components of the addition reaction type silicone resin were sufficiently dissolved in deuterated chloroform containing dimethyl sulfoxide as an internal standard sample, and the resulting mixture was measured using an NMR apparatus "JNM ECA500" (product name) manufactured by japan electronics corporation 1 H-NMR spectrum. Next, the resonance signal area (integral value) of dimethyl sulfoxide and the resonance signal area (integral value) of alkenyl group of the internal standard sample in the measurement spectrum were obtained, and the alkenyl group content per 1g of the addition reaction type silicone resin was calculated from the ratio thereof. In addition, the same procedure was also conducted for the crosslinking agent formed of the organopolysiloxane containing hydrogen, and the measurement was performed 1 The H-NMR spectrum was obtained, and the ratio of the area of the resonance signal (integral value) of dimethyl sulfoxide to the area of the resonance signal (integral value) of SiH groups in the internal standard sample in the measurement spectrum was used to calculate the SiH group content per 1g of the crosslinking agent. In the case where the crosslinking agent is added to the addition reaction type silicone resin from the beginning, the crosslinking agent is added only by the addition reaction type silicone resin 1 The H-NMR spectrum may be used to calculate the contents of alkenyl groups and SiH groups simultaneously.
(2) Storage modulus of adhesive layer
The storage modulus of the adhesive layers 2 and 3 was measured for the adhesive tapes 10 and 20 of examples 1 to 9 and comparative examples 1 to 5 by the following method. First, the adhesive solutions for coating prepared in each of examples and comparative examples were applied to the first release film, and the first release film was dried and cured under the same conditions as in each of examples and comparative examples, and the second release film was bonded to obtain an adhesive tape (without a base material). Next, each of the obtained adhesive tapes was cut into small pieces, and the release film was peeled off to obtain a thickness of about 500 μm, thereby preparing a sample having only the adhesive layer superimposed thereon. For these samples, dynamic viscoelasticity was measured using a viscoelasticity measuring device "DMA6100" (product name) manufactured by hitachi high technology corporation, ltd, to determine the storage modulus of the adhesive layer. The measurement conditions were that the dynamic viscoelasticity spectrum was measured by changing the temperature from 30℃to 280℃at a heating rate of 2℃per minute while applying a shear strain having a frequency of 1Hz under an atmosphere of He. The storage modulus at 200℃of the obtained spectrum was set as the storage modulus at 200℃of the adhesive layer measured under an He atmosphere.
(3) Total amount of outgas generated by adhesive tape
For the adhesive tapes 10, 20 of examples 1 to 9 and comparative examples 1 to 5, the total amount of outgas generated from the adhesive tapes 10, 20 was measured using heat generated gas mass spectrometry (TPD-MS). First, samples (except for release films) were prepared in which the adhesive tapes 10 and 20 were cut into a size of 4mm×20 mm. Next, each adhesive tape sample was placed in a quartz sample tube with a differential level differential balance "MB6" (product name) of an infrared heating furnace, manufactured by Kagaku Co., ltd, and the inside of the sample tube was adjusted to 1.0X10 by exhausting by a vacuum pump -5 ～1.0×10 -6 Pressure of Torr. Then, the sample tube was heated from room temperature to 200℃at a heating rate of 10℃per minute, and further kept at 200℃for 30 minutes, and a mass spectrum analysis was performed on a gas component generated from the sample using a mass spectrum analyzer "Q-MS5973A" (product name) manufactured by Hewlett Packard Co., ltd.) to obtain an MS total ion flow (TIC) chromatogram. In addition, as a standard sample, CO generated when calcium oxalate was heated was used 2 (carbon dioxide) A standard curve was prepared from the prepared concentration and peak area, and the adhesive tape was subjected to a vacuum degree of 1.0X10 based on the standard curve and the total peak area of TIC of the gas component generated from the adhesive tape sample -4 The gas is heated from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under the atmosphere of Torr or less, and then further maintained at 200 ℃ for 30 min, and then passed through CO 2 The total amount of outgas generated by the adhesive tape was calculated by conversion.
(4) Evaluation in vacuum film Forming Process
The adhesive tapes 10 and 20 of examples 1 to 9 and comparative examples 1 to 5 were evaluated on the basis of 3 grades a to C for the following 4 items when film formation was performed on the surface of the film substrate 12 (cover glass) temporarily fixed to the adhesive layer 2 of each adhesive tape 10 and 20 by the post-reaction sputtering method using a carousel-type radical assisted sputtering apparatus.
< temporary fixing force with respect to film substrate >
The presence or absence of detachment was confirmed for 48 thin film substrates in a standing posture after the completion of the film formation of the antireflection film.
A: the number of the detached film substrates was 0.
B: the number of the detached film substrates was 1.
C: the number of the detached film substrates is more than 2.
< re-peelability of film substrate >
After the film formation of the antireflection film was completed, when the adhesive tape was peeled off from the film substrate or when the film substrate was peeled off from the adhesive tape by the above method, it was evaluated whether the film substrate could be peeled off again without breakage.
A: the number of the film substrates broken at the time of peeling was 0, and the film substrates were peeled again.
B: the number of film substrates broken at the time of peeling was 1, and the other film substrates were peeled again.
C: the number of the film substrates damaged during peeling was 2 or more.
< production of residual glue >
After the film formation of the antireflection film was completed, the average state of the residual adhesive on the film substrate was visually confirmed when the adhesive tape was peeled off from the film substrate or when the film substrate was peeled off from the adhesive tape by the above method.
A: no clear gum residue was observed.
B: the level of gum residue was slightly observed, but could be easily removed by washing.
C: a clear gum residue was observed.
Appearance of antireflection film
The average state of the appearance of the antireflection film formed on the thin film substrate was visually observed.
A: no clear film formation unevenness was observed.
B: depending on the viewing angle, a slight but insignificant level of film formation unevenness was observed.
C: a clear uneven film formation was observed.
In all the items, the evaluation of a or B was judged to be a level having no problem in practical use.
3. Test results
The structures and evaluation results of the adhesive tapes 10 and 20 of examples 1 to 9 and comparative examples 1 to 5 are shown in tables 1 to 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As shown in tables 1 to 3, the adhesive layer of each of the single-sided adhesive tapes 10 of examples 1 to 8 and the double-sided adhesive tape 20 of example 9, which were manufactured in a roll-to-roll manner, had a storage modulus of 1.0X10 at 200℃measured under He atmosphere 5 ～1.0×10 7 Pa, in a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 180mg/m 2 The following follows, therefore, can be seen: when these adhesive tapes are used as adhesive tapes for temporary fixation in forming an antireflection film on a film substrate by a vacuum film forming process using a carousel sputtering apparatus, the temporary fixation force of the film substrate is sufficient even in a vertical posture, and outgas from the adhesive tapes occurring in the film forming process can be suppressed, without adversely affecting the appearance of the obtained antireflection filmIn addition, the film substrate and the adhesive tape after film formation have excellent removability (no residual adhesive on the film substrate, and the film substrate is not broken during peeling). The visible light reflectance required for the properties of the antireflection film is 1.0% or less, and there is no particular problem in practical use.
For the appearance of the antireflection film on the film substrate, there is a tendency that the smaller the total amount of outgas generated by the adhesive tape, the better the result is, wherein the total amount of outgas is 100mg/m when used 2 The single-sided adhesive tapes 10 of examples 1 to 2, 4 and 6 to 7 are particularly preferable.
In the comparison of example 2 and examples 5 to 8 in which the adhesive layer was used in which the molar ratio of SiH group of the crosslinking agent to alkenyl group of the addition reaction type silicone resin was the same, in the case of the single-sided adhesive tape 10 of example 2 and examples 6 to 7 in which the molar ratio of SiH group/alkenyl group was in the range of 1.5 to 5.0, good results were obtained in all the evaluations of the temporary fixing force of the film substrate, the re-peelability of the film substrate, the adhesive residue on the film substrate, and the appearance of the antireflection film on the film substrate. In the case of the single-sided adhesive tape 10 of example 5 in which the molar ratio of SiH groups to alkenyl groups was 0.5, the crosslinking and curing of the adhesive layer were slightly insufficient, and the storage modulus was slightly decreased, so that the total amount of outgas was slightly increased, and the appearance of the antireflection film on the film substrate was slightly deteriorated. In addition, the adhesive force of the adhesive layer slightly increases, and the re-peeling property of the film substrate also slightly deteriorates. However, the single-sided adhesive tape 10 of example 8, in which the molar ratio of SiH groups to alkenyl groups was 10.0, was used at a practically unproblematic level, and the amount of residual SiH groups was slightly increased, and the SiH was silanol-converted to SiOH, and the water generated during the dehydration condensation reaction during heating and film formation was released as a gas, so that the total amount of released gas was slightly increased, and the appearance of the antireflection film on the film substrate was slightly deteriorated. In addition, the adhesive force of the adhesive layer slightly increases, and the re-peeling property of the film substrate also slightly deteriorates. However, they are all levels which are practically free from problems.
Further, in the case of the single-sided adhesive tape 10 of example 3 in which the mass ratio (G)/(R) of the silicone resin (R) to the silicone resin (G) is 35/65 of the lower limit of the present invention, the storage modulus of the adhesive layer also becomes the lower limit of the present invention, and the total amount of outgas is slightly increased, so that the appearance of the antireflection film on the film substrate is slightly deteriorated. In addition, the ratio of the silicone resin (R) is as high as 65 mass%, and the adhesive force of the adhesive layer is slightly increased, so that the re-peelability of the film substrate and the residual adhesive on the film substrate are also slightly deteriorated. However, they are all levels which are practically free from problems.
In the case of the single-sided adhesive tape 10 of example 4 in which the mass ratio (G)/(R) of the silicone resin (R) to the silicone resin (G) is 100/0 of the upper limit of the present invention, the storage modulus of the adhesive layer also becomes the upper limit of the present invention, and the adhesive layer becomes slightly hard and the adhesive force becomes slightly small, so that only the temporary fixing force of the film substrate becomes slightly poor. However, the method is a level which is practically free from problems.
In the case of using the double-sided adhesive tape 20 of example 9 in which the adhesive layer of example 1 was provided on the 1-side of the substrate and the adhesive layer of example 2 was provided on the 2-side of the substrate, the total amount of outgas from the double-sided adhesive tape 20 slightly increased as the total thickness of the adhesive layer increased, and therefore the appearance of the antireflection film on the film substrate was slightly deteriorated, but other evaluations were good, and were all levels of practically no problem.
From this, it can be confirmed that: as the adhesive layer, "the silicone resin containing alkenyl groups (G) and the silicone resin containing no alkenyl groups (R) are blended so that the mass ratio is in the range of (G)/(R) =35/65 to 100/0 and the alkenyl group content is 1.0X10 ×" is used -5 ～1.0×10 -3 An addition reaction type silicone resin having a mol/g range, which is obtained by heating and curing a resin composition comprising an organopolysiloxane having SiH groups and a platinum group metal catalyst, to form an adhesive layer having a storage modulus of 1.0X10 at 200 ℃ as measured under He atmosphere 5 ～1.0×10 7 Pa, and at a vacuum level of 1.0X10 -4 In an atmosphere of Torr or less, the temperature is raised from 23 ℃ at a heating rate of 10 ℃/minThe total amount of outgas generated by the adhesive tape was 180mg/m when further maintained at 200℃for 30 minutes after the temperature was reached 200 ℃ 2 The single-sided adhesive tapes 10 of examples 1 to 8 and the double-sided adhesive tape 20 of example 9, which are designed in the following manner, are suitable as adhesive tapes for vacuum processes.
On the other hand, as shown in tables 3 to 4, when the single-sided adhesive tapes of comparative examples 1 to 4 and the double-sided adhesive tape 20 of comparative example 5 were used, the results of evaluation of at least any one of the temporary fixing force of the film substrate, the re-peelability of the film substrate, the residual adhesive on the film substrate and the appearance of the antireflection film on the film substrate were inferior to those of examples 1 to 9, because the constitution of the present invention was not satisfied.
Specifically, in the single-sided adhesive tape 10 of comparative example 1, the content of alkenyl groups in the addition-reaction type silicone resin is small, and the storage modulus of the adhesive layer after crosslinking and curing is small, so that the total amount of outgas increases, and the appearance of the antireflection film on the film substrate is inferior to that of the example. Further, since the adhesive layer also has a large adhesive force, the film substrate also has a poor re-peelability as compared with the examples.
In the single-sided adhesive tape 10 of comparative example 2, the content of alkenyl groups in the addition-reaction type silicone resin is large, and the storage modulus of the adhesive layer after crosslinking and curing is excessively large, so that the adhesive force of the adhesive layer becomes excessively small, and the film substrate cannot be sufficiently temporarily fixed, and the film substrate falls off during the film forming process, and the antireflection film cannot be formed by film formation.
Further, in the single-sided adhesive tape 10 of comparative example 3, the mass ratio (G)/(R) of the silicone resin (R) to the silicone gel (G)/(R) was 30/70, and the ratio of the silicone resin (R) was large, and the adhesive force of the adhesive layer became excessively large, so that the re-peelability of the film substrate and the residual adhesive on the film substrate were inferior to those of the examples.
In the single-sided adhesive tape 10 of comparative example 4, the crosslinking agent is not blended, and the crosslinking and curing of the adhesive layer are not performed, so that the cohesive force is small, and a good adhesive tape cannot be produced by the roll-to-roll method. In addition, the amount of outgas from the adhesive tape produced in a monolithic manner is still large.
The double-sided adhesive tape 20 of comparative example 5 was a double-sided adhesive tape in which the adhesive layer of example 3 was provided on the 1-side of the substrate and the adhesive layer of example 1 was provided on the 2-side of the substrate, but the amount of outgas from the adhesive layer on the 1-side of the substrate was slightly large, so that the total amount of outgas from the double-sided adhesive tape 20 was increased after the combination of the amounts of outgas from the adhesive layer on the 2-side of the substrate, and the appearance of the antireflection film on the film substrate was inferior to that of the example.
Claims (3)
1. A pressure-sensitive adhesive tape for vacuum processing comprising a base material and an adhesive layer on at least one surface of the base material,
the adhesive layer is formed from a resin composition containing an addition reaction type silicone-based resin as a main component, an organopolysiloxane having at least 2 or more hydrogen atoms (SiH) bonded to silicon atoms in 1 molecule as a crosslinking agent, and a platinum group metal-based catalyst as a catalyst,
the addition reaction type organic silicon resin is formed by compounding an organic silicon material (G) formed by organic polysiloxane containing alkenyl groups bonded with silicon atoms and an organic silicon resin (R) formed by organic polysiloxane not containing alkenyl groups bonded with silicon atoms according to the mass ratio (G)/(R) being in the range of (G)/(R) =35/65-100/0, and the content of alkenyl groups bonded with silicon atoms is 1.0x10 -5 ～1.0×10 -3 The range of the mol/g is that,
the adhesive layer has a storage modulus of 1.0X10 at 200℃measured under an atmosphere of He 5 ～1.0×10 7 In the range of Pa,
the adhesive tape has a vacuum degree of 1.0X10 -4 When the temperature is raised from 23 ℃ to 200 ℃ at a heating rate of 10 ℃/min under an atmosphere of Torr or less and then the temperature is further maintained at 200 ℃ for 30 minutes, the total amount of outgas generated is 180mg/m 2 The following is given.
2. The adhesive tape for vacuum process according to claim 1, wherein the substrate is a polyethylene terephthalate film.
3. The adhesive tape for vacuum process according to claim 1 or 2, which is suitable for forming a functional film selected from the group consisting of an antireflection film, an antiglare film, an antifouling film, and a colored film on a heat-resistant substrate.
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| JP2017214528A (en) * | 2016-06-02 | 2017-12-07 | 日東電工株式会社 | Pressure-sensitive adhesive tape for vacuum process |
| JP2019031623A (en) * | 2017-08-08 | 2019-02-28 | 王子ホールディングス株式会社 | Adhesive tape with base material |
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| JP4678847B2 (en) | 2004-10-28 | 2011-04-27 | 信越化学工業株式会社 | Adhesive film having an adhesive layer obtained from a silicone composition |
| JP4487264B2 (en) | 2006-06-26 | 2010-06-23 | 旭硝子株式会社 | Sputtering apparatus and sputter deposition method |
| JP5775826B2 (en) | 2010-01-13 | 2015-09-09 | 東レ・ダウコーニング株式会社 | Silicone-based releasable pressure-sensitive adhesive composition, sheet-like substrate having a re-peelable pressure-sensitive adhesive layer formed by curing the composition, use as a protective film or a fixed sheet |
| JP6030280B2 (en) | 2010-11-17 | 2016-11-24 | 日立マクセル株式会社 | Adhesive tape for plastic lens molding and plastic lens molding method |
| JP2016210930A (en) | 2015-05-12 | 2016-12-15 | Dic株式会社 | Adhesive sheet, surface protective member and electronic device |
| JP6743377B2 (en) | 2015-12-01 | 2020-08-19 | 三菱ケミカル株式会社 | Method for producing pressure-sensitive adhesive article with release film, and method for producing laminate for optical device configuration |
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