TW202304715A - Release film for molding resin sheets - Google Patents
Release film for molding resin sheets Download PDFInfo
- Publication number
- TW202304715A TW202304715A TW111123149A TW111123149A TW202304715A TW 202304715 A TW202304715 A TW 202304715A TW 111123149 A TW111123149 A TW 111123149A TW 111123149 A TW111123149 A TW 111123149A TW 202304715 A TW202304715 A TW 202304715A
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- release
- film
- release film
- release layer
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 155
- 229920005989 resin Polymers 0.000 title claims abstract description 155
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 103
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 67
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 344
- 239000002245 particle Substances 0.000 claims description 95
- 239000000919 ceramic Substances 0.000 claims description 66
- 239000002344 surface layer Substances 0.000 claims description 54
- 229920006267 polyester film Polymers 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 18
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 238000004804 winding Methods 0.000 claims description 12
- 150000002484 inorganic compounds Chemical class 0.000 claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims description 10
- 230000007547 defect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 218
- 239000000047 product Substances 0.000 description 29
- 239000011254 layer-forming composition Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 25
- 239000010954 inorganic particle Substances 0.000 description 25
- 229920000139 polyethylene terephthalate Polymers 0.000 description 23
- 239000005020 polyethylene terephthalate Substances 0.000 description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 20
- 238000012545 processing Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 125000002723 alicyclic group Chemical group 0.000 description 13
- 238000001723 curing Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000003746 surface roughness Effects 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 210000002257 embryonic structure Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 101100029848 Arabidopsis thaliana PIP1-2 gene Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- MWOZJZDNRDLJMG-UHFFFAOYSA-N [Si].O=C=O Chemical compound [Si].O=C=O MWOZJZDNRDLJMG-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000004814 ceramic processing Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
Description
本發明係關於一種樹脂片成型用離型膜，更詳細而言，本發明係關於一種於成型超薄層之樹脂片時所用之離型膜。The present invention relates to a release film for forming a resin sheet. More specifically, the present invention relates to a release film used for forming an ultra-thin layer of resin sheet.
先前，將聚酯膜作為基材，並且於該基材上積層有離型層之離型膜被用作為步驟膜，該步驟膜係用於將黏著片、覆膜、高分子膜、光學透鏡等樹脂片進行成型。Previously, a polyester film was used as a base material, and a release film with a release layer laminated on the base material was used as a step film, which is used for adhesive sheets, coatings, polymer films, optical lenses Wait for the resin sheet to be molded.
前述離型膜亦被用作為積層陶瓷電容器、陶瓷基板等要求高平滑性之陶瓷生胚成型用步驟膜。近年來，伴隨積層陶瓷電容器之小型化、大容量化，陶瓷生胚之厚度亦有薄膜化之傾向。陶瓷生胚係藉由將含有鈦酸鋇等陶瓷成分及黏合劑樹脂之漿料塗敷於離型膜上並加以乾燥而成型。於所成型之陶瓷生胚印刷電極並自離型膜剝離後，將陶瓷生胚加以積層、壓製，煅燒並塗布外部電極，藉此製造積層陶瓷電容器。The above-mentioned release film is also used as a step film for ceramic green body molding that requires high smoothness, such as multilayer ceramic capacitors and ceramic substrates. In recent years, with the miniaturization and increase in capacity of laminated ceramic capacitors, the thickness of ceramic green bodies also tends to be thinner. The ceramic green body is formed by coating a slurry containing ceramic components such as barium titanate and a binder resin on a release film and drying it. After the formed ceramic green body prints electrodes and peels off the release film, the ceramic green body is laminated, pressed, calcined and coated with external electrodes, thereby manufacturing a laminated ceramic capacitor.
於聚酯膜基材之離型層表面成型出陶瓷生胚之情況，自離型膜將陶瓷生胚加以剝離時之剝離性逐漸變得重要。若剝離力大、不均勻則於剝離步驟中會對於陶瓷生胚造成損傷，發生片缺陷、厚度不均等，有發生針孔、片破裂等不佳情形之問題。因此，也需要以更低且均勻的力來剝離陶瓷生胚。When ceramic green bodies are molded on the surface of the release layer of the polyester film substrate, the detachability of the ceramic green bodies from the release film becomes increasingly important. If the peeling force is large and uneven, the ceramic green body will be damaged during the peeling step, and chip defects, uneven thickness, etc., pinholes, chip cracks, and other unfavorable situations may occur. Therefore, it is also necessary to peel off the ceramic green body with a lower and uniform force.
近年來，陶瓷生胚之薄膜化邁進，逐漸要求厚度為1.0μm以下、更詳而言之為0.2μm至1.0μm之陶瓷生胚。因而關於離型膜所需剝離性之要求更為提高。In recent years, the thinning of ceramic green bodies has progressed, and ceramic green bodies with a thickness of 1.0 μm or less, more specifically, 0.2 μm to 1.0 μm, are gradually required. Therefore, the requirements for the peelability required for the release film are even higher.
作為剝離性優異之離型膜可舉出以下所記載之專利文獻中的離型膜。例如專利文獻1中提議了一種離型膜，具有使用自由基硬化型樹脂作為主成分之離型層。As a release film excellent in peelability, the release film in the patent document described below is mentioned. For example, Patent Document 1 proposes a release film having a release layer mainly composed of a radical-curable resin.
但是專利文獻1之離型膜由於使用了自由基硬化型樹脂，故於大氣中加工離型層之情況，將遭受氧阻礙的影響，有離型層表面成為硬化不良之問題。一旦發生離型層表面之硬化不良，離型層會因為陶瓷生胚加工或內部電極印刷時之有機溶劑而受到侵蝕，出現剝離力之增大或是剝離均勻性受損，故剝離時恐對於陶瓷生胚造成損傷。However, since the release film of Patent Document 1 uses a radical-curable resin, when the release layer is processed in the air, it will be affected by oxygen hindrance, and there is a problem that the surface of the release layer becomes poorly cured. Once the hardening of the surface of the release layer is poor, the release layer will be eroded by the organic solvent during the green ceramic processing or internal electrode printing, and the peeling force will increase or the peeling uniformity will be damaged. Ceramic green embryos cause damage.
為了解決上述課題，專利文獻2提議了將陽離子硬化型樹脂用作主成分之離型層。陽離子硬化型樹脂由於不會發生氧阻礙，即便在大氣中加工離型層也不會發生硬化不良，可得到剝離性優異之離型膜。 [先前技術文獻] [專利文獻] In order to solve the above-mentioned problems, Patent Document 2 proposes a release layer using a cation-curable resin as a main component. Cationic hardening resins do not cause oxygen barriers, so even if the release layer is processed in the air, there will be no poor curing, and a release film with excellent peelability can be obtained. [Prior Art Literature] [Patent Document]
[專利文獻1]國際公開第2013/145864。 [專利文獻2]國際公開第2018/079337。 [Patent Document 1] International Publication No. 2013/145864. [Patent Document 2] International Publication No. 2018/079337.
[發明所欲解決之課題][Problem to be Solved by the Invention]
但是，專利文獻2之離型膜所使用之陽離子硬化型樹脂相較於自由基硬化型樹脂在反應速度上較慢，故僅是照射活性能量線的話反應不會完成結束，而有隨時間經過進行聚合反應之傾向。 因此，使用陽離子硬化型樹脂製造離型膜之情況，於基材膜之一面塗布離型層形成組成物，乾燥後照射活性能量線使得離型層形成組成物硬化之後，在捲取成輥狀來保管之狀態下完成結束陽離子聚合反應，可形成獲得優異剝離性之離型層。 再者，有時捲取成輥狀進行保管不久，聚合反應尚未完成結束，有可能對於離型層之表面形狀造成影響。因此，希望能進而減低離型層之表面形狀之缺點。 However, the cation-curable resin used in the release film of Patent Document 2 has a slower reaction rate than the radical-curable resin, so the reaction will not be completed when only irradiated with active energy rays. Tendency to undergo polymerization. Therefore, in the case of using a cation-curable resin to produce a release film, a release layer-forming composition is applied to one side of the base film, dried, irradiated with active energy rays to harden the release layer-forming composition, and wound into a roll. In the state of storage, the cationic polymerization reaction is completed and the release layer with excellent peeling properties can be formed. In addition, it may affect the surface shape of the release layer even after it has been wound up into a roll and stored for a short time before the polymerization reaction is completed. Therefore, it is desired to further reduce the defects of the surface shape of the release layer.
此外，陽離子硬化型樹脂受到水的影響有產生硬化不良之傾向。於加工離型膜時，為了將離型膜捲取成輥狀來保管，係以離型層與基材膜之反離型面呈接觸之狀態來保管。因此，受到被認為是在基材膜之反離型面側微量存在著的水分的影響，陽離子硬化型樹脂之經時反應受到阻礙，有離型層之硬化變得不充分之問題。In addition, cation-curable resins tend to be poorly cured under the influence of water. When processing the release film, the release film is stored in a state where the release layer is in contact with the opposite release surface of the base film in order to roll the release film and store it. Therefore, the reaction of the cation-curable resin over time is hindered by the influence of moisture that is believed to exist in a small amount on the side opposite to the release surface of the base film, and there is a problem that the release layer becomes insufficiently hardened.
此種因離型膜之反離型面側之影響所致離型層之硬化不良的影響隨著陶瓷生胚邁向薄膜化而變得愈為顯著，而尋求具有更優異剝離性之離型膜。The influence of poor hardening of the release layer due to the influence of the anti-release surface side of the release film becomes more and more significant as the ceramic green body becomes thinner, and a release with better peelability is sought. membrane.
本發明係基於此種先前技術之課題為背景所獲致者。亦即，目的在於提供一種離型膜，可抑制以陽離子硬化型樹脂作為主成分之離型層發生硬化不良，具有優異之剝離性。The present invention is based on the background of such prior art problems. That is, the object is to provide a release film which can suppress the occurrence of poor curing of a release layer mainly composed of a cation-curable resin, and which has excellent peelability.
本發明人等為了解決上述課題經過努力研究之結果，發現具有下述構成之離型膜可達成前述目的，從而完成了本發明。 [用以解決課題之手段] As a result of earnest research by the present inventors to solve the above-mentioned problems, they found that a release film having the following constitution can achieve the above-mentioned object, and completed the present invention. [Means to solve the problem]
亦即，本發明具有以下構成。 ［1］一種樹脂片成型用離型膜，具有基材膜以及設置於基材膜之一面的離型層；離型膜在前述基材膜之與前述離型層為相反側之面具有疏水化層；前述離型層係由具有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物所形成之層；前述疏水化層之水接觸角為90°以上至130°以下；將前述樹脂片成型用離型膜暫時捲取成輥狀後再捲出所得之離型膜中所測定之離型層之常態剝離力(I)與加熱後剝離力(II)為(II)/(I)＝1.00以上至1.50以下。 ［2］於一態樣中，前述捲出所得之離型膜中之離型層之常態剝離力(I)為1500mN/50mm以下。 ［3］於一態樣中，將前述離型膜捲取為輥狀所得離型膜輥以100m/分鐘抽出時之帶電量為未達±1kV。 ［4］於一態樣中，前述疏水化層係由具有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物所構成之層。 ［5］於一態樣中，前述疏水化層之厚度為0.001μm以上至0.5μm以下。 ［6］於一態樣中，前述離型層以及前述疏水化層實質上不含粒徑1.0μm以上之粒子。 ［7］於一態樣中，前述基材膜為具有實質上不含粒徑1.0μm以上之無機粒子之表面層A以及含有粒子之表面層B之聚酯膜，離型層係積層於前述表面層A上，疏水化層係積層於前述表面層B上。 ［8］於一態樣中，為含有無機化合物之樹脂片成型用離型膜。 ［9］於一態樣中，含有無機化合物之樹脂片為陶瓷生胚。 ［10］於一態樣中，為厚度為0.2μm以上至1.0μm以下之樹脂片成型用離型膜。 ［11］於一態樣中，提供一種陶瓷生胚之製造方法，係使用上述陶瓷生胚製造用離型膜來成型出陶瓷生胚，經成型之陶瓷生胚具有0.2μm至1.0μm之厚度。 [發明功效] That is, the present invention has the following constitutions. [1] A release film for molding a resin sheet, comprising a base film and a release layer disposed on one side of the base film; Chemicalized layer; the aforementioned release layer is a layer formed of a cured product having a composition of cation-curable polydimethylsiloxane (a); the water contact angle of the aforementioned hydrophobized layer is not less than 90° and not more than 130° ; The normal peeling force (I) and the peeling force (II) of the released layer measured in the release film obtained after temporarily winding the aforementioned release film into a roll shape are (II) )/(I)=1.00 or more and 1.50 or less. [2] In one aspect, the normal peeling force (I) of the release layer in the release film obtained by rolling out is 1500 mN/50 mm or less. [3] In one aspect, the charge amount when the release film roll obtained by winding up the release film into a roll shape is drawn out at 100 m/min is less than ±1 kV. [4] In one aspect, the hydrophobized layer is a layer composed of a cured product having a composition of cation-curable polydimethylsiloxane (a). [5] In one aspect, the thickness of the aforementioned hydrophobized layer is not less than 0.001 μm and not more than 0.5 μm. [6] In one aspect, the release layer and the hydrophobic layer substantially do not contain particles having a particle diameter of 1.0 μm or more. [7] In one aspect, the aforementioned substrate film is a polyester film having a surface layer A substantially free of inorganic particles having a particle diameter of 1.0 μm or larger and a surface layer B containing particles, and the release layer is laminated on the aforementioned On the surface layer A, the hydrophobic layer is laminated on the above-mentioned surface layer B. [8] In one aspect, a release film for molding a resin sheet containing an inorganic compound. [9] In one aspect, the resin sheet containing the inorganic compound is a ceramic green body. [10] In one aspect, a release film for molding a resin sheet having a thickness of not less than 0.2 μm and not more than 1.0 μm. [11] In one aspect, a method for manufacturing ceramic green bodies is provided, which uses the release film for manufacturing ceramic green bodies to form ceramic green bodies, and the formed ceramic green bodies have a thickness of 0.2 μm to 1.0 μm . [Efficacy of the invention]
本發明之樹脂片成型用離型膜於基材膜之一面具有離型層、於基材膜之與前述離型層為相反側之面(反離型面)設置有疏水化層，藉此，可抑制產生離型層之硬化阻礙，可提供薄膜之樹脂片、尤其可提供可缺陷地剝離陶瓷生胚之離型膜。The release film for resin sheet molding of the present invention has a release layer on one side of the base film, and a hydrophobizing layer is provided on the side (reverse release surface) of the base film opposite to the release layer, whereby , can suppress the hardening barrier of the release layer, can provide a thin film resin sheet, especially a release film that can peel off the ceramic green body defectively.
以下，針對本發明詳細說明。Hereinafter, the present invention will be described in detail.
本發明係一種樹脂片成型用離型膜，具有：基材膜、設置於基材膜之一面的離型層，且於基材膜之與前述離型層為相反側之面(反離型面)具有疏水化層。藉由於基材膜之反離型面設置疏水化層，由於以輥狀保管時，離型層與疏水化層會接觸，故無發生離型層之硬化不良之虞，可獲得具有優異剝離性之離型膜。 再者，由於可抑制發生離型層之硬化不良，故例如以輥狀保管之際，可減低離型面之平滑性受到與離型面接觸之反離型面之凹凸的影響而惡化。因此，可更為減低從離型膜之製造到使用為止所可能發生之離型層之表面形狀的缺點。 The present invention relates to a release film for resin sheet molding, which has: a base film, a release layer arranged on one side of the base film, and on the side opposite to the release layer of the base film (reverse release layer) Surface) has a hydrophobic layer. By providing a hydrophobized layer on the anti-release surface of the base film, since the release layer and the hydrophobized layer will be in contact when stored in a roll shape, there is no risk of poor hardening of the release layer, and excellent peelability can be obtained. The release film. Furthermore, since the hardening failure of the release layer can be suppressed, for example, when storing in a roll shape, the deterioration of the smoothness of the release surface due to the unevenness of the opposite release surface in contact with the release surface can be reduced. Therefore, the defect of the surface shape of the release layer that may occur from the manufacture of the release film to the use can be further reduced.
離型層較佳為不用擔心因氧阻礙而發生硬化不良之具有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物。藉由使用陽離子硬化型聚二甲基矽氧烷(a)，於大氣中製造離型膜之時，可無硬化阻礙而穩定地進行硬化，可獲得具有優異剝離性之離型膜。The release layer is preferably a cured product of a composition having cation-curable polydimethylsiloxane (a) that does not cause poor curing due to oxygen barrier. By using the cation-curable polydimethylsiloxane (a), when the release film is produced in the air, it can be cured stably without hindrance to hardening, and a release film with excellent peelability can be obtained.
疏水化層較佳為具有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物。於一態樣中，陽離子硬化型聚二甲基矽氧烷(a)可為和離型層所含陽離子硬化型聚二甲基矽氧烷(a)為相同組成，也可為不同組成。較佳為和離型層所含陽離子硬化型聚二甲基矽氧烷(a)為相同組成。此外，本說明書中，當含有相同組成之硬化型聚二甲基矽氧烷(a)之情況，在用於疏水化層時，也可適當進行分子量、調配量等之調整。 藉由使用陽離子硬化型聚二甲基矽氧烷(a)，由於以輥狀態保管時和所接觸之離型層之摩電電序接近而可抑制帶電，故可在無剝離帶電的情況下以輕力來無缺陷地剝離陶瓷生胚。此外，由於反離型面受到疏水化，故以輥狀態保管時，也可抑制反離型面之水分影響，可防止離型層之硬化不良。 硬化型聚二甲基矽氧烷(a)之詳細將於後述。 The hydrophobized layer is preferably a cured product having a composition of cation-curable polydimethylsiloxane (a). In one aspect, the cation-curable polydimethylsiloxane (a) may have the same composition as the cation-curable polydimethylsiloxane (a) contained in the release layer, or may have a different composition. Preferably, it has the same composition as that of the cation-curable polydimethylsiloxane (a) contained in the release layer. In addition, in this specification, when containing the hardening type polydimethylsiloxane (a) of the same composition, when using for a hydrophobization layer, molecular weight, compounding quantity, etc. can also be adjusted suitably. By using cation-curing polydimethylsiloxane (a), since the triboelectric sequence of the release layer in contact with the roll state is close to that of the release layer when stored in a roll state, charging can be suppressed, so it can be used without peeling charging. Light force to peel off the ceramic green body without defects. In addition, since the anti-release surface is hydrophobized, it can also suppress the influence of moisture on the anti-release surface when it is stored in a roll state, and prevent poor hardening of the release layer. Details of the curable polydimethylsiloxane (a) will be described later.
(聚酯膜) 構成本發明中作為基材膜(以下有時記載為基材)來使用之聚酯膜的聚酯並無特別限定，可使用將作為離型膜用基材通常一般所使用的聚酯加以膜成形而得者。較佳為由芳香族二元酸成分與二醇成分所構成之結晶性線狀飽和聚酯，例如聚對苯二甲酸乙二酯、聚萘二甲酸-2,6-乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸丙二酯或是以此等樹脂之構成成分作為主成分之共聚物為更適宜。尤其是聚對苯二甲酸乙二酯所形成之聚酯膜為特別適宜。聚對苯二甲酸乙二酯中，對苯二甲酸乙二酯之重複單元較佳為90莫耳%以上，更佳為95莫耳%以上，亦可少量共聚其他二羧酸成分、二醇成分。例如以成本考量，較佳為僅由對苯二甲酸與乙二醇所製造者。此外，在不妨礙本發明之離型膜功效的範圍內，亦可添加公知的添加劑，例如抗氧化劑、光穩定劑、紫外線吸收劑、結晶化劑等。基於聚酯膜在兩方向之彈性模數的高低等理由，較佳為雙軸配向聚酯膜。 (polyester film) The polyester constituting the polyester film used as the base film (hereinafter sometimes referred to as the base material) in the present invention is not particularly limited, and a polyester film generally used as a base material for a release film can be used. Those who get formed. It is preferably a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, such as polyethylene terephthalate, polyethylene naphthalate-2,6-ethylene glycol, polyethylene terephthalate Butyl phthalate, polytrimethylene terephthalate, or a copolymer using these resin constituents as the main component is more suitable. In particular, a polyester film formed of polyethylene terephthalate is particularly suitable. In polyethylene terephthalate, the repeating unit of ethylene terephthalate is preferably more than 90 mole%, more preferably more than 95 mole%. A small amount of other dicarboxylic acid components and diols can also be copolymerized Element. For example, in consideration of cost, it is preferable to manufacture only terephthalic acid and ethylene glycol. In addition, known additives such as antioxidants, photostabilizers, ultraviolet absorbers, crystallizers, and the like may be added within the range of not hindering the effect of the release film of the present invention. For reasons such as the elastic modulus of the polyester film in two directions, etc., a biaxially oriented polyester film is preferred.
上述聚酯膜之固有黏度較佳為0.50dl/g至0.70dl/g，更佳為0.52dl/g至0.62dl/g。於固有黏度為0.50dl/g以上之情形時，不會於延伸步驟中大量發生斷裂而較佳。反之，於為0.70dl/g以下之情形時，裁斷為預定之製品寬度時之裁斷性良好，不產生尺寸不良，故較佳。另外，原料顆粒較佳為充分進行真空乾燥。 再者，本說明書中，於簡單記載為「聚酯膜」之情形時，意指具有表面層A及表面層B之(經積層之)聚酯膜。 The intrinsic viscosity of the polyester film is preferably from 0.50dl/g to 0.70dl/g, more preferably from 0.52dl/g to 0.62dl/g. When the intrinsic viscosity is 0.50 dl/g or more, it is preferable that a large amount of fractures do not occur in the stretching step. Conversely, when it is 0.70 dl/g or less, the cutting performance when cutting to a predetermined product width is good, and dimensional defects do not occur, which is preferable. In addition, the raw material particles are preferably sufficiently vacuum-dried. In addition, in this specification, when simply describing it as a "polyester film", it means the (laminated) polyester film which has surface layer A and surface layer B.
本發明中之聚酯膜之製造方法並無特別限定，可使用先前一般使用之方法。例如，可藉由下述方式獲得：利用擠出機將前述聚酯熔融並擠出成膜狀，利用旋轉冷卻滾筒加以冷卻，藉此獲得未延伸膜，將該未延伸膜加以雙軸延伸。雙軸延伸膜係可藉由將縱向或橫向之單軸延伸膜於橫向或縱向逐步雙軸延伸之方法、或者將未延伸膜於縱向與橫向同步雙軸延伸之方法獲得。The manufacturing method of the polyester film in this invention is not specifically limited, The method generally used previously can be used. For example, it can be obtained by melting and extruding the aforementioned polyester into a film with an extruder, cooling with a rotating cooling drum to obtain an unstretched film, and biaxially stretching the unstretched film. The biaxially stretched film can be obtained by biaxially stretching a longitudinally or transversely uniaxially stretched film stepwise in the transverse or longitudinal direction, or by synchronously biaxially stretching an unstretched film in the longitudinal and transverse directions.
於本發明中，聚酯膜延伸時之延伸溫度較佳為設為聚酯之二次轉移點(Tg)以上。較佳為於縱向、橫向之各方向進行1倍至8倍之延伸，尤佳為進行2倍至6倍之延伸。In the present invention, the stretching temperature at the time of stretching the polyester film is preferably at least the secondary transition point (Tg) of the polyester. It is preferably stretched 1 to 8 times in each of the longitudinal and transverse directions, and particularly preferably stretched 2 to 6 times.
上述聚酯膜之厚度以12μm至50μm為佳，更佳為15μm至38μm，又更佳為19μm至33μm。膜之厚度只要為12μm以上，則於膜生產時之加工步驟、成型時，無受熱變形之虞故較佳。另一方面，膜之厚度只要為50μm以下，則使用後廢棄之膜量不會極度變多，以減少環境負荷而言為佳。The thickness of the polyester film is preferably from 12 μm to 50 μm, more preferably from 15 μm to 38 μm, and still more preferably from 19 μm to 33 μm. As long as the thickness of the film is 12 μm or more, it is preferable because there is no risk of thermal deformation during the processing steps and molding during film production. On the other hand, as long as the thickness of the film is 50 μm or less, the amount of film discarded after use will not increase extremely, which is preferable in terms of reducing environmental load.
上述聚酯膜基材可為單層亦可為2層以上之多層。例如，基材膜也可為由具有實質上不含粒徑1.0μm以上之粒子的表面層A以及含有粒子之表面層B而成的聚酯膜。較佳為表面層A為實質上不含粒徑1.0μm以上之無機粒子。 此態樣中，表面層A中也可存在粒徑1nm以上至未達1.0μm之粒子。表面層A藉由實質上不含粒徑1.0μm以上之粒子(例如無機粒子)，可減低基材中之粒子形狀轉印至樹脂片而發生不良情形。 於一態樣中，表面層A藉由也不含粒徑未達1.0μm之粒子而可更有效地抑制基材中之粒子形狀轉印至樹脂片而發生不良情形。 於一態樣中，上述聚酯膜基材較佳為於至少單面具有實質上不含無機粒子之表面層A而成的積層膜。藉此，可更有效地抑制基材中之粒子形狀轉印至樹脂片而發生不良情形。 例如，實質上不含粒徑未達1.0μm之粒子的表面層A之較佳態樣為也實質上不含粒徑1.0μm以上之粒子。 The above polyester film substrate may be a single layer or a multilayer of two or more layers. For example, the base film may be a polyester film having a surface layer A substantially free of particles having a particle size of 1.0 μm or more and a surface layer B containing particles. Preferably, the surface layer A does not substantially contain inorganic particles having a particle diameter of 1.0 μm or more. In this aspect, particles having a particle diameter of 1 nm or more and less than 1.0 μm may exist in the surface layer A. Since the surface layer A does not substantially contain particles (such as inorganic particles) with a particle size of 1.0 μm or more, it can reduce the occurrence of problems caused by the transfer of the shape of the particles in the substrate to the resin sheet. In one aspect, since the surface layer A also does not contain particles with a particle size of less than 1.0 μm, it is possible to more effectively suppress the occurrence of defects caused by transfer of the shape of particles in the substrate to the resin sheet. In one aspect, the above-mentioned polyester film substrate is preferably a laminated film having a surface layer A substantially free of inorganic particles on at least one side. Thereby, it is possible to more effectively suppress the occurrence of defects caused by the transfer of the particle shape in the base material to the resin sheet. For example, a preferable aspect of the surface layer A that does not substantially contain particles having a particle diameter of less than 1.0 μm is also to substantially not contain particles having a particle diameter of 1.0 μm or more.
此處，本發明中，所謂「實質上不含粒子」，例如為未達1.0μm之無機粒子之情況，意指以螢光X射線分析來定量無機元素的情況為50ppm以下、較佳為10ppm以下、最佳為成為檢測極限以下的含量。這是由於即便未積極地於膜中添加粒子，仍有源自外部異物之污染成分、於原料樹脂或是膜之製造步驟中附著至生產線或裝置的污染物會混入膜中之情況之故。此外，所謂「實質上不含粒徑1.0μm以上之粒子」意指積極地不含粒徑1.0μm以上之粒子。 由2層以上之多層構成所構成之積層聚酯膜之情況，於實質上不含無機粒子之表面層A之相反面具有可含有無機粒子等之表面層B為佳。 以積層構成而言，若將塗布離型層之側的層設為A層、將相反面之層設為B層、將這些層以外的芯層設為C層，則厚度方向之層構成可舉出離型層/A/B或是離型層/A/C/B等之積層結構。當然C層也可為複數之層構成。此外，表面層B也可不含無機粒子。此情況下，為了賦予將膜捲取成為輥狀之滑動性，較佳為在表面層B上設置至少含有無機粒子與黏結劑之塗覆層。 Here, in the present invention, the term "substantially free of particles" means, for example, inorganic particles of less than 1.0 μm, which means that the inorganic elements are quantified by fluorescent X-ray analysis to be 50 ppm or less, preferably 10 ppm Below, preferably, it is a content below the detection limit. This is because even if particles are not actively added to the film, contamination components derived from external foreign matter, contaminants attached to the production line or equipment in the raw material resin or film manufacturing steps may still be mixed into the film. In addition, "substantially not including particles having a particle diameter of 1.0 μm or more" means actively not containing particles having a particle diameter of 1.0 μm or more. In the case of a laminated polyester film composed of two or more layers, it is preferable to have a surface layer B that may contain inorganic particles on the opposite side of the surface layer A that does not substantially contain inorganic particles. In terms of laminated structure, if the layer on the side where the release layer is applied is defined as layer A, the layer on the opposite side is defined as layer B, and the core layer other than these layers is defined as layer C, the layer configuration in the thickness direction can be List the laminated structure of release layer/A/B or release layer/A/C/B. Of course, layer C may also be composed of plural layers. In addition, the surface layer B may not contain inorganic particles. In this case, it is preferable to provide a coating layer containing at least inorganic particles and a binder on the surface layer B in order to impart slipperiness for winding the film into a roll shape.
本發明中之聚酯膜基材，用以形成塗布離型層之面的相反面之表面層B基於膜之滑動性、空氣排除容易度之觀點以含有無機粒子為佳，尤其以使用二氧化矽粒子以及/或是碳酸鈣粒子為佳。所含無機粒子之含量在表面層B中以無機粒子之合計而言以含有5000pp至15000ppm為佳。 此時，表面層B之膜之區域表面平均粗糙度(Sa)以1nm至40nm之範圍為佳。更佳為5nm至35nm之範圍。當二氧化矽粒子以及/或是碳酸鈣粒子之合計為5000ppm以上、Sa為1nm以上之情況，將膜捲成輥狀時，可使得空氣均勻地逸散，捲繞狀態良好而平面性良好，因此適合於超薄層陶瓷生胚之製造。此外，當二氧化矽粒子以及/或是碳酸鈣粒子之合計為15000ppm以下、Sa為40nm以下之情況，不易產生滑劑之凝聚，不會形成粗大突起，故於超薄層之陶瓷生胚製造時品質穩定故較佳。 The polyester film substrate in the present invention is used to form the surface layer B on the opposite side of the surface coated with the release layer. Based on the film's sliding properties and the ease of air removal, it is better to contain inorganic particles, especially when using carbon dioxide Silicon particles and/or calcium carbonate particles are preferred. The content of the inorganic particles contained in the surface layer B is preferably 5000ppm to 15000ppm based on the total of the inorganic particles. In this case, the area average surface roughness (Sa) of the film of the surface layer B is preferably in the range of 1 nm to 40 nm. More preferably, it is in the range of 5nm to 35nm. When the total amount of silica particles and/or calcium carbonate particles is more than 5000ppm, and Sa is more than 1nm, when the film is rolled into a roll, the air can escape evenly, and the winding state is good and the planarity is good. Therefore, it is suitable for the manufacture of ultra-thin layer ceramic green bodies. In addition, when the total amount of silicon dioxide particles and/or calcium carbonate particles is less than 15000ppm, and Sa is less than 40nm, it is difficult to produce agglomeration of the lubricant and no coarse protrusions are formed, so it is suitable for the manufacture of ultra-thin ceramic green bodies. It is better when the quality is stable.
上述B層所含粒子除了可使用二氧化矽以及/或是碳酸鈣以外，也可使用非活性無機粒子以及/或是耐熱性有機粒子等，但基於透明性、成本之觀點以使用二氧化矽粒子以及/或是碳酸鈣粒子為更佳。此外，其他可使用之無機粒子可舉出氧化鋁-二氧化矽複合氧化物粒子、羥基磷灰石粒子等。此外，作為耐熱性有機粒子可舉出交聯聚丙烯酸系粒子、交聯聚苯乙烯粒子、苯并胍胺系粒子等。當使用有二氧化矽粒子之情況，以多孔質之膠體二氧化矽為佳，當使用有碳酸鈣粒子之情況，從防止滑劑脫落之觀點來看，以聚丙烯酸系高分子化合物施以表面處理過之輕質碳酸鈣為佳。In addition to silicon dioxide and/or calcium carbonate, inactive inorganic particles and/or heat-resistant organic particles can also be used for the particles contained in the above-mentioned B layer, but silicon dioxide is preferred for transparency and cost. Particles and/or calcium carbonate particles are more preferred. In addition, other usable inorganic particles include alumina-silica composite oxide particles, hydroxyapatite particles, and the like. Furthermore, examples of the heat-resistant organic particles include cross-linked polyacrylic particles, cross-linked polystyrene particles, benzoguanamine-based particles, and the like. When using silicon dioxide particles, porous colloidal silicon dioxide is preferable. When using calcium carbonate particles, from the viewpoint of preventing the slipping agent from falling off, the surface is coated with polyacrylic polymer compound. Treated light calcium carbonate is preferred.
對於上述表面層B所添加之無機粒子之平均粒徑以0.1μm以上至2.0μm以下為佳，以0.5μm以上至1.0μm以下為特佳。只要無機粒子之平均粒徑為0.1μm以上，則離型膜之滑動性良好故較佳。此外，只要平均粒徑為2.0μm以下，由於不用擔心對於離型層表面之平滑性造成不良影響，故無庸擔心於陶瓷生胚發生針孔故較佳。The average particle size of the inorganic particles added to the surface layer B is preferably from 0.1 μm to 2.0 μm, and particularly preferably from 0.5 μm to 1.0 μm. As long as the average particle diameter of the inorganic particles is 0.1 μm or more, the sliding properties of the release film are good, so it is preferable. In addition, as long as the average particle diameter is 2.0 μm or less, since there is no fear of adversely affecting the smoothness of the release layer surface, there is no fear of pinholes in the ceramic green body, so it is preferable.
設置上述離型層之側之層亦即表面層A基於減低針孔之觀點較佳為使用再生原料等以防止滑劑等無機粒子之混入。The surface layer A, which is the layer on the side where the above-mentioned release layer is provided, is preferably made of recycled raw materials to prevent the incorporation of inorganic particles such as lubricants, from the viewpoint of reducing pinholes.
屬於設置前述離型層之側的層亦即表面層A之厚度比率以基材膜之總層厚度之20%以上至50%以下為佳。只要為20%以上，不易承受到來自膜內部之表面層B等所含粒子之影響，可使得區域表面平均粗糙度Sa容易滿足上述範圍故較佳。若為基材膜之總層厚度之50%以下，可增加表面層B中之再生原料之使用比率，環境負荷變小故較佳。The thickness ratio of the surface layer A, which is the layer on the side where the release layer is provided, is preferably 20% or more and 50% or less of the total layer thickness of the base film. As long as it is more than 20%, it is not easy to be affected by the particles contained in the surface layer B inside the film, and the average surface roughness Sa of the area can easily satisfy the above range, so it is preferable. If it is 50% or less of the total layer thickness of the base film, the use ratio of the recycled raw material in the surface layer B can be increased, and the environmental load is reduced, so it is preferable.
此外，基於經濟性之觀點，上述表面層A以外之層(表面層B或是前述中間層C)中可使用50質量%至90質量%之膜屑或寶特瓶之再生原料。即便是此種情況，B層所含滑劑之種類與量、粒徑以及區域表面平均粗糙度(Sa)也以滿足上述範圍為佳。In addition, from an economic point of view, 50% to 90% by mass of film scraps or recycled plastic bottles can be used in layers other than the above-mentioned surface layer A (surface layer B or the aforementioned intermediate layer C). Even in this case, it is preferable that the type and amount of the lubricant contained in the B layer, the particle size, and the average surface roughness (Sa) of the area satisfy the above-mentioned range.
此外，為了提高後續塗布之離型層等之密接性、或是防止帶電等，也可於表面層A以及/或是表面層B之表面對於製膜步驟內之延伸前或是單軸延伸後之膜設置塗覆層或施以電暈處理等。In addition, in order to improve the adhesion of the release layer and the like to be applied later, or to prevent electrification, the surface of the surface layer A and/or the surface layer B may be stretched before or after uniaxial stretching in the film forming step. The film is provided with a coating layer or corona treatment, etc.
(離型層) 本發明中，離型層係形成於基材膜之一面。當使用具有實質上不含無機粒子之表面層A的基材膜之情況，以於表面層A上形成離型層為佳。藉由於實質上不含無機粒子之表面層A上設置離型層，可實現平滑性優異之離型層表面，可抑制在離型層上所設置之樹脂片的變形、缺陷故較佳。 (release layer) In the present invention, the release layer is formed on one surface of the base film. When using the base film which has the surface layer A which does not contain an inorganic particle substantially, it is preferable to form a release layer on the surface layer A. By providing the release layer on the surface layer A substantially free of inorganic particles, a release layer surface with excellent smoothness can be realized, and deformation and defects of the resin sheet provided on the release layer can be suppressed, so it is preferable.
離型層為含有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物的離型層。離型層藉由具有此種特徴，可抑制氧阻礙所致硬化不良，可展現離型層之高交聯。發揮此種功效之本發明例如可提高離型層表面之耐溶劑性。藉由提高離型層表面之耐溶劑性，可抑制因著陶瓷生胚之成型時，內部電極之印刷時所使用之有機溶媒造成離型層受到侵蝕，可具有高剝離性。 此外，陽離子硬化型聚二甲基矽氧烷由於利用活性能量線來進行硬化，故無須於硬化反應中使用130℃以上之高熱。因此，可抑制加工時之熱造成離型膜之平面性受損。其結果，可抑制異物混入樹脂片成型用離型膜，抑制發生離型層之傷痕，對於陶瓷生胚等被離型體可抑制異物、傷痕之轉印所致片損傷的發生。 The release layer is a release layer containing a cured product of the composition of cation-curable polydimethylsiloxane (a). By having such characteristics, the release layer can suppress poor hardening caused by oxygen hindrance, and can exhibit high cross-linking of the release layer. The present invention that exerts such effects can improve the solvent resistance of the surface of the release layer, for example. By improving the solvent resistance of the surface of the release layer, it is possible to suppress the erosion of the release layer due to the organic solvent used in the printing of the internal electrodes during the molding of the ceramic green body, and it can have high peelability. In addition, cationic hardening polydimethylsiloxane uses active energy rays to harden, so it is not necessary to use high heat above 130°C in the hardening reaction. Therefore, damage to the planarity of the release film due to heat during processing can be suppressed. As a result, foreign matter can be suppressed from being mixed into the release film for resin sheet molding, and scratches on the release layer can be suppressed, and sheet damage caused by transfer of foreign matter and scratches can be suppressed for ceramic green bodies and other to-be-released objects.
本發明之離型膜中之離型層之常態剝離力(I)與加熱後剝離力(II)為(II)/(I)＝1.00以上至1.50以下。 藉由使得本發明相關之離型層之常態剝離力(I)與加熱後剝離力(II)之比具有預定條件，例如可評價離型層之硬化度。 離型膜有時在將以陶瓷生胚為代表之樹脂片成型於離型膜上之時或是剝離時會受熱。 本發明中藉由使得常態剝離力(I)與加熱後剝離力(II)在預定範圍內，可於加熱前後穩定地保持陶瓷生胚並展現剝離性。 例如，雖不應限定於特定的理論來解釋，但只要常態剝離力(I)與加熱後剝離力(II)沒有差異或是落於本發明之範圍內，則可展現穩定的剝離性。常態剝離力(I)與加熱後剝離力(II)之比亦即(II)/(I)為1.00以上至1.50以下，以1.00以上至1.45以下為更佳。例如亦可為1.00以上至1.40以下。例如亦可為1.05以上，亦可為1.10以上。 只要常態剝離力(I)與加熱後剝離力(II)之比(II)/(I)為1.50以下，表示離型層之硬化可充分進行，少有未反應物，對於陶瓷生胚等樹脂片具有優異剝離性故而為佳。一般而言加熱後剝離力高於常態剝離力，故以1.00以上為佳。詳細之評價方法將於後述。 本發明中，可將樹脂片成型用離型膜暫時捲取成為輥狀之後，再對於捲出所得之離型膜測定離型層之常態剝離力(I)與加熱後剝離力(II)，藉此來就經時性進行之離型層之聚合反應的進行度做間接性的評價。此外可對於也考慮到因輥狀態保管所產生之離型層之平面性之影響的剝離力進行評價。 於設置疏水化層之後，能以輥狀保管以更為加速離型層之反應，可獲得剝離力穩定、保持優異表面形狀之狀態的離型層，可得到加熱後剝離力也優異之離型膜。 The normal peeling force (I) and the peeling force (II) after heating of the release layer of the release film of the present invention are (II)/(I)=1.00 to 1.50. By making the ratio of the normal peel force (I) to the heated peel force (II) of the release layer related to the present invention have predetermined conditions, for example, the degree of hardening of the release layer can be evaluated. The release film may be heated when a resin sheet represented by a ceramic green body is formed on the release film or when it is peeled off. In the present invention, by making the normal peeling force (I) and the peeling force after heating (II) within a predetermined range, the ceramic green body can be stably maintained before and after heating and exhibit peelability. For example, although the interpretation should not be limited to a specific theory, as long as there is no difference between the normal peeling force (I) and the peeling force after heating (II) or falls within the scope of the present invention, stable peeling properties can be exhibited. The ratio (II)/(I) of the normal peel force (I) to the heated peel force (II) is 1.00 to 1.50, more preferably 1.00 to 1.45. For example, it may be 1.00 or more and 1.40 or less. For example, it may be 1.05 or more, and may be 1.10 or more. As long as the ratio (II)/(I) of the normal peeling force (I) to the peeling force (II) after heating is 1.50 or less, it means that the hardening of the release layer can be fully carried out, and there are few unreacted substances. For resins such as ceramic green embryos It is preferable that the sheet has excellent peelability. Generally speaking, the peeling force after heating is higher than the normal peeling force, so it is better to be above 1.00. The detailed evaluation method will be described later. In the present invention, the release film for resin sheet molding can be temporarily wound into a roll shape, and then the normal peeling force (I) and the peeling force after heating (II) of the release layer are measured for the released film obtained by rolling out, This is used to indirectly evaluate the progress of the polymerization reaction of the release layer over time. In addition, it is also possible to evaluate the peeling force that also takes into account the influence of the planarity of the release layer due to roll state storage. After the hydrophobized layer is installed, it can be stored in a roll shape to accelerate the reaction of the release layer, and a release layer with stable peeling force and excellent surface shape can be obtained, and a release film with excellent peeling force after heating can be obtained .
此外，藉由使得常態剝離力(I)與加熱後剝離力(II)之比(II)/(I)為1.00以上至1.50以下，於捲取成輥狀保管之情況下，相較於以往的離型膜可更良好地減少對於離型層之表面形狀的影響，可保持高平滑性。此外，由於表示離型層之硬化係充分地進行，故於輥狀態下不易發生黏連，也可抑制捲出帶電量。In addition, by setting the ratio (II)/(I) of the normal peel force (I) to the heated peel force (II) from 1.00 to 1.50, when wound up into a roll and stored, compared with the conventional The release film can better reduce the influence on the surface shape of the release layer and maintain high smoothness. In addition, since the hardening of the release layer is sufficiently advanced, it is difficult to cause sticking in the roll state, and the amount of unwinding charge can also be suppressed.
例如，離型層實質上不含粒徑1.0μm以上之粒子。此態樣中，離型層中也可存在粒徑1nm以上至未達1.0μm之粒子。若離型層實質上不含粒徑1.0μm以上之無機粒子，則可抑制對於要求高平滑性之超薄膜樹脂片(例如陶瓷生胚)發生針孔，可形成均勻膜厚之樹脂片。 於一態樣中，離型層以具有高平滑性為佳，故較佳為於具有表面層A(實質上不含無機粒子，具體而言實質上不含粒徑未達1.0μm之粒子，較佳為實質上不含粒子)之基材膜上設置本發明相關之離型層。 例如，實質上不含粒徑未達1.0μm之粒子的離型層之較佳態樣為連粒徑1.0μm以上之粒子也實質不含。 於實質上不含無機粒子之表面層A設置離型層之情況，離型層之區域表面粗糙度Sa為7nm以下，且最大突起高度為50nm以下。 離型層若具有此種特徴，可形成要求高平滑性之超薄膜樹脂片，例如可形成可抑制對陶瓷生胚發生針孔之均勻膜厚的樹脂片。 For example, the release layer does not substantially contain particles having a particle diameter of 1.0 μm or more. In this aspect, particles having a particle diameter of 1 nm or more and less than 1.0 μm may exist in the release layer. If the release layer does not substantially contain inorganic particles with a particle size of 1.0 μm or more, pinholes can be suppressed for ultra-thin film resin sheets (such as green ceramics) that require high smoothness, and resin sheets with uniform film thickness can be formed. In one aspect, it is preferable that the release layer has high smoothness, so it is preferable to have a surface layer A (substantially free of inorganic particles, specifically, substantially free of particles with a particle diameter of less than 1.0 μm, Preferably, the release layer related to the present invention is provided on a base film substantially free of particles. For example, a preferable aspect of the release layer substantially not containing particles having a particle diameter of less than 1.0 μm is to substantially contain particles having a particle diameter of 1.0 μm or more. When a release layer is provided on the surface layer A substantially free of inorganic particles, the surface roughness Sa of the release layer region is 7 nm or less, and the maximum protrusion height is 50 nm or less. If the release layer has such characteristics, it can form an ultra-thin film resin sheet that requires high smoothness, for example, it can form a resin sheet with uniform film thickness that can suppress the occurrence of pinholes on ceramic green embryos.
離型層之區域表面平均粗糙度(Sa)為7nm以下，且最大突起高度(Sp)為50nm以下為佳。形成有離型層之膜表面為了不使於膜表面上塗布、成型之陶瓷生胚片產生缺陷，而具有上述區域表面平均粗糙度及最大突起高度。若區域表面粗糙度為7nm以下，並且最大突起高度為50nm以下，則於陶瓷生胚片形成時不產生針孔等缺陷，良率良好而較佳。 進而，本發明之離型膜藉由具有本發明之離型層及疏水化層，而具有對樹脂片之優異剝離性，而且，於捲取樹脂片並保存時，能夠抑制針孔、皺褶及偏離之產生。此外，本發明能夠抑制捲出帶電變高。如此，本發明之離型膜不僅藉由高平滑性及優異之剝離性而能夠良好地製造樹脂片，而且能夠提高膜之捲取時及搬運時之操作性，可藉由抑制捲出帶電而減少異物混入。 The average surface roughness (Sa) of the release layer is preferably 7nm or less, and the maximum protrusion height (Sp) is preferably 50nm or less. The surface of the film on which the release layer is formed has the above average surface roughness and maximum protrusion height in order not to cause defects in the ceramic green sheet coated and molded on the film surface. If the area surface roughness is less than 7nm and the maximum protrusion height is less than 50nm, defects such as pinholes will not occur when the ceramic green sheet is formed, and the yield rate is good, which is preferable. Furthermore, the release film of the present invention has excellent peelability to the resin sheet by having the release layer and the hydrophobizing layer of the present invention, and can suppress pinholes and wrinkles when the resin sheet is wound up and stored. and the occurrence of deviations. In addition, the present invention can suppress an increase in unwinding electrification. In this way, the release film of the present invention can not only produce a resin sheet well due to its high smoothness and excellent peelability, but also can improve the operability of the film when it is taken up and transported, and can be improved by suppressing unwinding electrification. Reduce foreign matter mixing.
於一態樣中，離型層之區域表面平均粗糙度(Sa)為5nm以下，且最大突起高度(Sp)為30nm以下。最大突起高度愈低愈佳。區域表面平均粗糙度(Sa)愈小愈佳，亦可為0.1nm以上，亦可為0.3nm以上。另外，區域表面平均粗糙度(Sa)亦可為3nm以下，例如亦可為未達2nm。 最大突起高度(Sp)亦愈小愈佳，亦可為1nm以上，亦可為3nm以上。另外，最大突起高度(Sp)亦可為25nm以下，亦可為20nm以下。 In one aspect, the average surface roughness (Sa) of the release layer is less than 5nm, and the maximum protrusion height (Sp) is less than 30nm. The lower the maximum protrusion height, the better. The smaller the average surface roughness (Sa) of the region, the better, and it may be more than 0.1 nm, or more than 0.3 nm. In addition, the area surface average roughness (Sa) may be 3 nm or less, for example, may be less than 2 nm. The smaller the maximum protrusion height (Sp), the better, and it may be 1 nm or more, or 3 nm or more. In addition, the maximum protrusion height (Sp) may be 25 nm or less, or may be 20 nm or less.
離型層以至少含有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物為佳。本案發明中所謂陽離子硬化型聚二甲基矽氧烷(a)意指具有陽離子硬化性官能基之聚二甲基矽氧烷。所謂陽離子硬化性官能基可舉出顯示陽離子硬化性之反應性官能基，具體上可舉出乙烯醚基、氧雜環丁基、環氧基、脂環式環氧基為例。基於反應性之觀點，當中又以具有選自氧雜環丁基、環氧基、脂環式環氧基中至少1種之官能基為佳，以脂環式環氧基為最佳。藉由具有此種官能基，可藉由陽離子硬化反應來形成交聯結構，成為耐溶劑性優異、具有優異剝離性之離型層故較佳。The release layer is preferably a cured product of a composition containing at least cation-curable polydimethylsiloxane (a). The cation-curable polydimethylsiloxane (a) in the present invention refers to a polydimethylsiloxane having a cationic-curable functional group. The cation-curable functional group includes reactive functional groups exhibiting cation-curable properties, and specifically, vinyl ether groups, oxetanyl groups, epoxy groups, and alicyclic epoxy groups are examples. From the viewpoint of reactivity, among them, it is preferable to have at least one functional group selected from the group consisting of oxetanyl, epoxy, and alicyclic epoxy, and alicyclic epoxy is most preferred. By having such a functional group, a cross-linked structure can be formed by a cationic hardening reaction, and it becomes a release layer having excellent solvent resistance and excellent peelability, so it is preferable.
陽離子硬化型聚二甲基矽氧烷(a)之黏度以100mPa・s以上至10000mPa・s以下為佳，以100mPa・s以上至5000mPa・s以下為更佳，以100mPa・s以上至1000mPa・s以下為甚佳。若為100mPa・s以上則以輥狀態保管後之未反應成分量變少，可獲得充分硬化之離型層故較佳。若為10000mPa・s以下，則於離型層形成組成物中所含有機溶媒展現溶解性，可進行均勻塗布故較佳。此外，本發明中之黏度為25℃氛圍下所測定之值。The viscosity of cationic hardening polydimethylsiloxane (a) is preferably from 100mPa·s to 10000mPa·s, more preferably from 100mPa·s to 5000mPa·s, and from 100mPa·s to 1000mPa·s s below is better. If it is 100mPa·s or more, the amount of unreacted components after storage in the roll state will be reduced, and a sufficiently hardened release layer can be obtained, so it is preferable. If it is 10000 mPa·s or less, the organic solvent contained in the release layer forming composition exhibits solubility and uniform coating is possible, so it is preferable. In addition, the viscosity in this invention is the value measured in 25 degreeC atmosphere.
陽離子硬化型聚二甲基矽氧烷(a)所具有之陽離子硬化性官能基之數量只要為1個以上即可。例如，藉由具有2個以上的陽離子硬化性官能基，陽離子硬化反應變得更容易進行，成為交聯密度高的離型層故較佳。陽離子硬化性官能基之導入位置並無特別限定，一般可位於聚二甲基矽氧烷之側鏈或末端。聚二甲基矽氧烷之結構可為直鏈結構也可為分支結構，即便具有陽離子硬化性官能基以外之官能基也可無問題地使用。The number of the cation-curable functional groups which the cation-curable polydimethylsiloxane (a) has should just be 1 or more. For example, by having two or more cation-curable functional groups, the cation-curing reaction proceeds more easily, and it is preferable to form a release layer with a high crosslink density. The introduction position of the cation-curable functional group is not particularly limited, and generally can be located at the side chain or terminal of polydimethylsiloxane. The structure of polydimethylsiloxane may be a linear structure or a branched structure, and it can be used without any problem even if it has a functional group other than a cation-curable functional group.
陽離子硬化型聚二甲基矽氧烷(a)可適宜地使用市售者。舉例包括荒川化學工業公司製之矽利康利斯(註冊商標)UV POLY200、UV POLY201、UV POLY215、UV RCA200、UV RCA251、信越化學工業公司公司製之X-62-7622、X-62-7629、X-62-7660、KF-101、KF-105、X-22-343、X-22-169AS、X-22-169B、X-22-163、X-22-173BX、X-22-173DX、X-22-9002、Momentive Performance Materials公司製之UV9440E、UV9430等。As the cation-curing polydimethylsiloxane (a), a commercially available one can be used suitably. Examples include UV POLY200, UV POLY201, UV POLY215, UV RCA200, UV RCA251 manufactured by Arakawa Chemical Co., Ltd., X-62-7622, X-62-7629 manufactured by Shin-Etsu Chemical Co., Ltd. X-62-7660, KF-101, KF-105, X-22-343, X-22-169AS, X-22-169B, X-22-163, X-22-173BX, X-22-173DX, X-22-9002, UV9440E, UV9430 manufactured by Momentive Performance Materials, etc.
本發明之離型層形成組成物中除了含有陽離子硬化型聚二甲基矽氧烷(a)也可含有其他樹脂。當在實質上不含無機粒子之基材膜之表面層A上設置離型層之情況，較佳為以陽離子硬化型聚二甲基矽氧烷(a)作為主成分來硬化之離型層。此情況，即使離型層之膜厚薄，也可製作具有極高平滑性之離型層故較佳。此外，由於離型層之膜厚薄，故硬化反應容易進行，可更高速地進行加工，可經濟性地獲得離型層。The release layer-forming composition of the present invention may contain other resins in addition to the cation-curable polydimethylsiloxane (a). When the release layer is provided on the surface layer A of the substrate film substantially free of inorganic particles, it is preferably a release layer hardened with cation-curable polydimethylsiloxane (a) as the main component . In this case, even if the film thickness of the release layer is thin, a release layer having extremely high smoothness can be produced, so it is preferable. In addition, since the film thickness of the release layer is thin, the hardening reaction is easy to proceed, processing can be performed at a higher speed, and the release layer can be obtained economically.
以陽離子硬化型聚二甲基矽氧烷(a)為主成分之組成物經硬化之離型層之情況，離型層之膜厚以0.001μm以上至未達0.050μm為佳。若為0.001μm以上由於離型性優異故較佳。若為未達0.050μm可防止離型層形成組成物之凝聚，成為平滑之離型層故較佳。 此外，本發明中，以陽離子硬化型聚二甲基矽氧烷(a)為主成分之情況，相對於離型層之樹脂固形物100質量份，組成物至少含有陽離子硬化型聚二甲基矽氧烷(a)50質量份，例如超過50質量份，較佳為70質量份以上，例如含有80質量份以上，於一態樣中含有90質量份以上。此外，亦可為實質上於離型層之樹脂固形物整體含有陽離子硬化型聚二甲基矽氧烷(a)之態樣。 In the case of a hardened release layer composed of a cation-curable polydimethylsiloxane (a) as the main component, the film thickness of the release layer is preferably 0.001 μm or more and less than 0.050 μm. If it is 0.001 μm or more, it is preferable because the release property is excellent. If it is less than 0.050 μm, it is preferable to prevent the aggregation of the release layer-forming composition and form a smooth release layer. In addition, in the present invention, when the main component is cation-curable polydimethylsiloxane (a), the composition contains at least cation-curable polydimethylsiloxane (a) relative to 100 parts by mass of resin solids in the release layer. Siloxane (a) 50 parts by mass, for example more than 50 parts by mass, preferably more than 70 parts by mass, for example more than 80 parts by mass, 90 parts by mass or more in one form. In addition, it may be an aspect in which the cation-hardening type polydimethylsiloxane (a) is contained substantially in the solid resin content of the release layer as a whole.
本發明之離型層形成組成物中除了含有陽離子硬化型聚二甲基矽氧烷(a)亦可含有不具聚矽氧骨架之陽離子硬化型樹脂(b)。此時(b)為有別於(a)之樹脂，樹脂(b)為不具聚二甲基矽氧烷結構之樹脂。The release layer-forming composition of the present invention may contain a cation-curable resin (b) not having a polysiloxane skeleton in addition to the cation-curable polydimethylsiloxane (a). At this time, (b) is a resin different from (a), and resin (b) is a resin without polydimethylsiloxane structure.
於一態樣中，離型層形成組成物除了含有陽離子硬化型聚二甲基矽氧烷(a)，進而含有不具聚矽氧骨架之陽離子硬化型樹脂(b)。作為不具聚矽氧骨架之陽離子硬化型樹脂(b)之例可舉出分子內具有2個以上陽離子硬化性官能基且不具聚矽氧骨架之聚合物、單體。當中又以具有2個以上之環氧基或是脂環式環氧基之樹脂為佳，具有2個以上之脂環式環氧基之樹脂為更佳。例如，脂環式環氧基之數量可為6個以下。 藉由具有2個以上脂環式環氧基，可藉由陽離子硬化反應而進行交聯反應，成為耐溶劑性優異之離型層。此外，同時也和離型層所含聚二甲基矽氧烷(a)進行交聯反應，故剝離性優異，且聚二甲基矽氧烷(a)朝陶瓷生胚之移動受到抑制故較佳。 In one aspect, the release layer forming composition contains not only cation-curable polydimethylsiloxane (a), but also cation-curable resin (b) not having a polysiloxane skeleton. Examples of the cation-curable resin (b) that does not have a silicone skeleton include polymers and monomers that have two or more cation-curable functional groups in the molecule and do not have a silicone skeleton. Among them, a resin having two or more epoxy groups or alicyclic epoxy groups is preferable, and a resin having two or more alicyclic epoxy groups is more preferable. For example, the number of alicyclic epoxy groups may be 6 or less. By having 2 or more alicyclic epoxy groups, a crosslinking reaction can progress by cationic hardening reaction, and it can become the release layer excellent in solvent resistance. In addition, it also undergoes a cross-linking reaction with polydimethylsiloxane (a) contained in the release layer, so the release property is excellent, and the migration of polydimethylsiloxane (a) to the ceramic green body is suppressed. better.
於一態樣中，離型層形成組成物同時含有不具聚矽氧骨架之陽離子硬化性樹脂(b)與聚二甲基矽氧烷(a)，故可實現具有高平滑性之離型層。藉由製成含有樹脂(b)之離型層，可將存在於基材膜之微細凹凸或極微小異物、源自寡聚物之突起等加以填埋，成為超平滑的離型層。此外，由於藉由活性能量線來進行硬化反應，而成為具有高平滑性之離型層。雖不應限定於特定理論來解釋，但可推測於離型層加工時之離型層形成組成物中的乾燥步驟中，均勻地使得不具聚矽氧骨架之陽離子硬化性樹脂(b)與聚二甲基矽氧烷(a)均平，於提升了平面性之後再進行硬化，而可獲得具有高平滑性之離型層。此外，同時所含之聚二甲基矽氧烷(a)在本發明中由於在乾燥步驟中偏析於離型層表面，而可獲得剝離性也優異之離型層。In one aspect, the composition for forming the release layer contains both the cation-curable resin (b) and polydimethylsiloxane (a) without a polysiloxane skeleton, so that a release layer with high smoothness can be realized . By making the release layer containing the resin (b), it is possible to fill the fine asperities, extremely small foreign matters, protrusions derived from oligomers, etc. existing in the base film, and to form an ultra-smooth release layer. In addition, due to the hardening reaction by active energy rays, it becomes a release layer with high smoothness. Although the explanation should not be limited to a specific theory, it can be speculated that in the drying step of the release layer forming composition during the release layer processing, the cation-curable resin (b) without the polysiloxane skeleton is uniformly mixed with the polysiloxane. The dimethylsiloxane (a) is even and hardened after improving the planarity, so that a release layer with high smoothness can be obtained. In addition, since the polydimethylsiloxane (a) contained at the same time is segregated on the surface of the release layer in the drying step in the present invention, a release layer having excellent releasability can be obtained.
不具聚矽氧骨架之陽離子硬化型樹脂(b)以低分子量之單體為佳。具體而言，數量平均分子量以200以上至未達5000為佳，以200以上至未達2500為更佳，以200以上至未達1000為更佳。若數量平均分子量為200以上，沸點不會變低，於離型層加工時之離型層形成組成物的乾燥步驟中，陽離子硬化型樹脂(b)無揮發之虞故較佳。若未達5000，離型層之交聯密度高，耐溶劑性優異故較佳。此外，由於在乾燥步驟中能以具流動性之液狀狀態來存在，故均平性優異，成為超平滑的離型層故較佳。The cation-curable resin (b) not having a polysiloxane skeleton is preferably a low-molecular-weight monomer. Specifically, the number average molecular weight is preferably from 200 to less than 5,000, more preferably from 200 to less than 2,500, and more preferably from 200 to less than 1,000. If the number average molecular weight is 200 or more, the boiling point will not be lowered, and the cation-curable resin (b) is preferable because there is no risk of volatilization in the drying step of the release layer forming composition during release layer processing. If it is less than 5000, the crosslinking density of the release layer is high and the solvent resistance is excellent, so it is better. In addition, since it can exist in a liquid state with fluidity in the drying step, it is excellent in leveling property and is preferable as an ultra-smooth release layer.
不具聚矽氧骨架之陽離子硬化型樹脂(b)可適宜使用市售者。作為具脂環式環氧基之化合物之例可舉出Daicel公司製之Celloxide 2021P、Celloxide 2081、Epolead GT401、EHPE3150、四國化成公司製之HiREM-1、ENEOS公司製之THI-DE、DE-102、DE-103等。作為具有環氧基之樹脂之例可舉出DIC公司之EPICLON(註冊商標)830、 840、850、1051-75M、N-665、N-670、N-690、N-673-80M、N-690-75M、Nagasechemtex公司製之Denacol(註冊商標)EX-611、EX-313、EX-321等。As the cation-curable resin (b) not having a silicone skeleton, commercially available ones can be used suitably. Examples of compounds having an alicyclic epoxy group include Celloxide 2021P, Celloxide 2081, Epolead GT401, EHPE3150 manufactured by Daicel, HiREM-1 manufactured by Shikoku Kasei Co., Ltd., THI-DE, DE- 102, DE-103, etc. Examples of resins having epoxy groups include EPICLON (registered trademark) 830, 840, 850, 1051-75M, N-665, N-670, N-690, N-673-80M, N- 690-75M, Denacol (registered trademark) EX-611, EX-313, EX-321 etc. manufactured by Nagasechemtex Co., Ltd.
在離型層包含不具聚矽氧骨架之陽離子硬化型樹脂(b)之態樣中，相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型樹脂(b)之合計100質量份，不具聚矽氧骨架之陽離子硬化型樹脂(b)之含量可超過50質量%，以80質量%以上為佳，以85質量%以上為更佳，以90質量%以上為甚佳。 若將陽離子硬化型樹脂(b)之含量設為超過50質量%、例如設為80質量%以上而成為離型層中之主成分，則成為交聯密度高且剝離性優異之離型層故較佳。此外，可減少離型層中所含陽離子硬化型聚二甲基矽氧烷(a)之含量，可抑制於乾燥步驟中源自聚二甲基矽氧烷(a)之組成凝聚於離型層表面，無平面性惡化之虞故較佳。雖陽離子硬化型樹脂(b)之含量愈多則愈能成為平滑性優異之離型層，但為了含有陽離子硬化型聚二甲基矽氧烷(a)來確保剝離性，陽離子硬化型樹脂(b)以99.9質量%以下為佳。 本發明中，離型層形成組成物經硬化之離型層中，存在有源自不具聚矽氧骨架之陽離子硬化型樹脂(b)的化合物(硬化物)。本說明書中，有時候針對離型層中所存在之源自不具聚矽氧骨架之陽離子硬化型樹脂(b)之化合物也簡記為不具聚矽氧骨架之陽離子硬化型樹脂(b)。 In the aspect where the release layer contains a cation-curable resin (b) without a polysiloxane skeleton, the cation-curable polydimethylsiloxane (a) and the cation-curable resin (b) in the release layer ) in a total of 100 parts by mass, the content of cation-curable resin (b) without polysiloxane skeleton can exceed 50 mass%, preferably 80 mass% or more, more preferably 85 mass% or more, and 90 mass% or more Why is it good. If the content of the cation-curable resin (b) is more than 50% by mass, for example, 80% by mass or more, and becomes the main component of the release layer, it will become a release layer with high crosslink density and excellent releasability. better. In addition, the content of cation-hardening polydimethylsiloxane (a) contained in the release layer can be reduced, and the composition derived from polydimethylsiloxane (a) can be inhibited from agglomerating on the release layer during the drying step. The surface of the layer is preferable because there is no risk of deterioration of planarity. The more the content of the cation-curable resin (b), the more smooth the release layer can be. However, in order to ensure the peelability by containing the cation-curable polydimethylsiloxane (a), the cation-curable resin ( b) Preferably at most 99.9% by mass. In the present invention, the compound (cured product) derived from the cation-curable resin (b) that does not have a polysiloxane skeleton exists in the release layer in which the release layer forming composition is cured. In this specification, the compound derived from the cation-curable resin (b) which does not have a silicone skeleton which exists in a release layer may also be abbreviated as the cation-curable resin (b) which does not have a silicone skeleton.
當離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型樹脂(b)之情況，由於離型層之交聯密度高，耐溶劑性優異，成為具有優異之剝離力的離型層故較佳。此外，若含有陽離子硬化型樹脂(b)，由於可一邊將陽離子硬化型聚二甲基矽氧烷(a)之含量控制在預定範圍、一邊增厚離型層之膜厚故較佳。藉由增厚離型層之膜厚，可將存在於基材膜之傷痕、極微小凹凸加以填埋，如前述般可獲得平滑的離型層故較佳。When the release layer forming composition contains cation-curable polydimethylsiloxane (a) and cation-curable resin (b), since the release layer has a high crosslink density and excellent solvent resistance, it becomes an excellent The release layer with higher peeling force is better. In addition, if the cation-curable resin (b) is contained, it is preferable because the film thickness of the release layer can be increased while controlling the content of the cation-curable polydimethylsiloxane (a) within a predetermined range. By increasing the film thickness of the release layer, it is preferable to fill the scratches and tiny unevenness existing in the substrate film, and to obtain a smooth release layer as described above.
當離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型樹脂(b)之情況，離型層之膜厚以0.01μm以上至1.0μm以下為佳，以0.05μm以上至0.5μm以下為更佳。若為0.01μm以上，會成為平滑的離型層故較佳。若為1.0μm以下，不會發生翹曲而可獲得平面性優異之離型膜故較佳。When the release layer forming composition contains cation-curable polydimethylsiloxane (a) and cation-curable resin (b), the film thickness of the release layer is preferably 0.01 μm or more and 1.0 μm or less. More preferably, it is 0.05 μm or more and 0.5 μm or less. If it is 0.01 micrometer or more, it will become a smooth release layer, so it is preferable. If it is 1.0 μm or less, it is preferable to obtain a release film having excellent planarity without warping.
本發明中，為了形成離型層必須進行陽離子硬化反應。因此，離型層形成組成物以含有酸產生劑(c)為佳。此外，離型層可存在源自酸產生劑(c)之化合物。此處，針對離型層中所存在之源自酸產生劑(c)之化合物有時也簡稱為酸產生劑(c)。 酸產生劑並無特別限定可使用一般的酸產生劑，但藉由使用在紫外線照射下會產生酸的光酸產生劑，可抑制加工時之熱量，成為平面性優異之離型層故較佳。 In the present invention, it is necessary to carry out a cation hardening reaction in order to form a release layer. Therefore, it is preferable that the composition for forming a release layer contains an acid generator (c). In addition, a compound derived from an acid generator (c) may exist in the release layer. Here, the compound derived from the acid generator (c) present in the release layer may also be simply referred to as the acid generator (c). The acid generator is not particularly limited. General acid generators can be used, but by using a photoacid generator that generates acid under ultraviolet radiation, heat during processing can be suppressed, and it is preferable to form a release layer with excellent planarity. .
基於反應性之觀點，光酸產生劑以使用由鎓離子與非親核性陰離子所成之鹽為適宜。此外，也可使用以鐵芳烴錯合物為代表之有機金屬錯合物、以鋽為代表之碳陽離子鹽，也可使用以蔥衍生物或吸電子基所取代之酚類，例如五氟苯酚。From the viewpoint of reactivity, it is preferable to use a salt of an onium ion and a non-nucleophilic anion as a photoacid generator. In addition, organometallic complexes represented by iron arene complexes, carbocation salts represented by arborium, and phenols substituted with onion derivatives or electron-withdrawing groups, such as pentafluorophenol, can also be used. .
當使用由前述鎓離子與非親核性陰離子所成之鹽作為光酸產生劑之情況，鎓離子可使用例如錪鎓、鋶、銨。作為鎓離子之有機基可使用三芳基、二芳基(單烷基)、單芳基(二烷基)、三烷基，也可導入二苯甲酮、9-芴，可使用其他的有機基。非親核性陰離子以使用六氟磷酸鹽、六氟銻酸鹽、六氟硼酸鹽、四(五氟苯基)硼酸鹽為適宜。此外，也可使用四(五氟苯基)鎵離子、將數個氟陰離子取代於全氟烷基或有機基之陰離子，也可使用其他的陰離子成分。When using a salt formed of the aforementioned onium ion and a non-nucleophilic anion as the photoacid generator, the onium ion can be, for example, iodonium, perium, or ammonium. As the organic group of the onium ion, triaryl, diaryl (monoalkyl), monoaryl (dialkyl), and trialkyl can be used, and benzophenone and 9-fluorene can also be introduced, and other organic groups can be used. base. As the non-nucleophilic anion, hexafluorophosphate, hexafluoroantimonate, hexafluoroborate, and tetrakis(pentafluorophenyl)borate are preferably used. In addition, tetrakis(pentafluorophenyl)gallium ions, anions obtained by substituting several fluorine anions for perfluoroalkyl groups or organic groups, or other anion components may also be used.
光酸產生劑之添加量相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型樹脂(b)之合計100質量份為0.1質量%至10質量%，更佳為0.5質量%至8質量%，更佳為1質量%至5質量%。若為0.1質量%以上，無須擔心所產生之酸量變得不充分而成為硬化不足故較佳。此外，若為10質量%以下，所產生之酸量成為適量，可抑制酸往所成型之陶瓷生胚的移動量故較佳。The amount of the photoacid generator added is 0.1% by mass to 10% by mass relative to the total of 100 parts by mass of the cation-curable polydimethylsiloxane (a) and the cation-curable resin (b) in the release layer. Preferably, it is 0.5 mass % to 8 mass %, More preferably, it is 1 mass % to 5 mass %. If it is 0.1% by mass or more, there is no need to worry about insufficient hardening due to an insufficient amount of generated acid. In addition, if it is 10% by mass or less, the amount of generated acid becomes appropriate, and the amount of acid migration to the molded ceramic green body can be suppressed, so it is preferable.
本說明書中，所謂離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型樹脂(b)之合計100質量份，意指陽離子硬化型聚二甲基矽氧烷(a)之固形物、陽離子硬化型樹脂(b)之固形物之合計值。此外，在離型層不含陽離子硬化型樹脂(b)之態樣中，陽離子硬化型聚二甲基矽氧烷(a)之重量相當於離型層中之樹脂固形物100質量份。In this specification, the total of 100 parts by mass of cation-curable polydimethylsiloxane (a) and cation-curable resin (b) in the release layer means cation-curable polydimethylsiloxane ( The total value of the solid content of a) and the solid content of the cation-curable resin (b). In addition, in the form where the release layer does not contain the cation-curable resin (b), the weight of the cation-curable polydimethylsiloxane (a) corresponds to 100 parts by mass of the resin solids in the release layer.
本發明中，只要在不阻礙本發明之功效的範圍內，亦可於離型層添加密接提升劑、抗靜電劑等添加劑等，但以不含粒子為佳。若離型層不含粒子、可抑制離型層表面之平滑性之惡化、以及因粒子脫落造成粒子混入樹脂片。為了提高相對於基材之密接性，也可在設置離型塗布層之前於聚酯膜表面施以錨固塗布、電暈處理、電漿處理、大氣壓電漿處理等之前處理。In the present invention, additives such as adhesion improving agent and antistatic agent can also be added to the release layer as long as the effect of the present invention is not hindered, but it is preferable not to contain particles. If the release layer does not contain particles, the deterioration of the surface smoothness of the release layer and the mixing of particles into the resin sheet due to falling off of particles can be suppressed. In order to improve the adhesiveness with respect to the base material, it is also possible to apply anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. pre-treatment on the surface of the polyester film before the release coating layer is provided.
(疏水化層) 疏水化層是形成於基材膜中設有離型層之面的相反側之面。當於實質上不含無機粒子或是可含有極為少量之粒子之表面層A上設置有離型層之情況，係於基材膜之另一面之表面層B上形成疏水化層。 例如，疏水化層實質上不含粒徑1.0μm以上之粒子。此態樣中，疏水化層也可存在粒徑1nm以上至未達1.0μm之粒子。離型層若實質上不含粒徑1.0μm以上之無機粒子，當將離型膜捲取成輥狀時，不用擔心受到反離型面(疏水化層)所存在之粒子之影響而對於樹脂片造成變形(缺陷)故較佳。 疏水化層以實質上不含粒徑未達1.0μm之粒子為佳，以不含粒子為佳。若實質上不含粒徑未達1.0μm之粒子，則於離型膜上成型出樹脂片之後以輥狀保管之際，不用擔心疏水化層中之粒子形狀轉印造成樹脂片變形故較佳。此外，也不用擔心疏水化層中之粒子脫落而混入樹脂片中故較佳。尤其，若實質上不含粒子，可更良好地發揮上述功效。 例如，較佳態樣為實質上不含粒徑未達1.0μm之粒子的表面層A也實質上不含粒徑1.0μm以上之粒子。此外，此種態樣係和實質上不具有粒子之態樣相同。 (hydrophobic layer) The hydrophobized layer is formed on the surface opposite to the surface provided with the release layer in the base film. When a release layer is provided on the surface layer A that does not contain inorganic particles substantially or may contain a very small amount of particles, a hydrophobizing layer is formed on the surface layer B on the other side of the substrate film. For example, the hydrophobized layer does not substantially contain particles having a particle diameter of 1.0 μm or more. In this aspect, particles having a particle diameter of 1 nm or more and less than 1.0 μm may exist in the hydrophobized layer. If the release layer does not substantially contain inorganic particles with a particle size of 1.0 μm or more, when the release film is rolled into a roll, there is no need to worry about being affected by the particles existing on the anti-release surface (hydrophobic layer) and affecting the resin. It is preferable that the sheet causes deformation (defect). The hydrophobized layer preferably does not substantially contain particles with a particle diameter of less than 1.0 μm, and preferably does not contain particles. If there are substantially no particles with a particle size of less than 1.0 μm, it is better to mold the resin sheet on the release film and store it in a roll shape, because there is no need to worry about the deformation of the resin sheet due to the shape transfer of the particles in the hydrophobic layer. . In addition, there is no fear that the particles in the hydrophobized layer will come off and be mixed into the resin sheet, so it is preferable. In particular, when the particles are not substantially contained, the above-mentioned effects can be exhibited more favorably. For example, in a preferred aspect, the surface layer A that does not substantially contain particles with a particle diameter of less than 1.0 μm also does not substantially contain particles with a particle diameter of 1.0 μm or more. Furthermore, such an aspect is the same as an aspect that does not have particles substantially.
疏水化層以含有陽離子硬化型聚二甲基矽氧烷(a)之組成物之硬化物為佳。若疏水化層具有此種特徴，則將離型膜捲取成為輥狀來保管之際，會成為離型層與疏水化層相接觸之狀態，故離型層不會遭受水分所致硬化阻礙之影響而可進行反應故較佳。此外，由於離型層也含有陽離子硬化型聚二甲基矽氧烷(a)，故以輥狀態保管時疏水化層接近於所接觸之離型層的摩電電序，可抑制帶電故較佳。若可抑制帶電，則能以無剝離帶電之低的施力來缺陷地剝離陶瓷生胚等樹脂片。進而，可抑制步驟中之極微小環境異物、分切時所產生之膜屑等因静電而附著。其結果，可防止異物混入樹脂片而污染。例如，本發明之離型膜即便在樹脂片之成型前所施行之輥捲出步驟中也可抑制帶電，可防止離型層之污染。進而，即便是在離型層形成有樹脂片之狀態下，也可抑制捲出帶電，可發揮本說明書所記載之各種功效。The hydrophobized layer is preferably a cured product of a composition containing cation-curable polydimethylsiloxane (a). If the hydrophobized layer has such characteristics, when the release film is rolled into a roll and stored, the release layer will be in a state of contact with the hydrophobized layer, so the release layer will not be hindered by hardening due to moisture It is better to react because of the influence. In addition, since the release layer also contains cation-hardening polydimethylsiloxane (a), it is preferable that the hydrophobized layer is close to the triboelectric series of the release layer in contact with it when stored in a roll state, which can suppress charging. . If the electrification can be suppressed, resin sheets such as ceramic green sheets can be defectively peeled with a low applied force without peeling electrification. Furthermore, it can suppress the adhesion of very small environmental foreign matter in the process, film scraps generated during slitting, etc. due to static electricity. As a result, foreign matter can be prevented from being mixed into the resin sheet to cause contamination. For example, the release film of the present invention can suppress electrification even in the roll-out step performed before molding the resin sheet, and can prevent contamination of the release layer. Furthermore, even in the state in which the release layer was formed with the resin sheet, unwinding electrification can be suppressed, and various functions described in this specification can be exhibited.
本發明之疏水化層之水接觸角為90°以上至130°以下。若水接觸角設定於此範圍，可減少被認為是吸附在基材膜之反離型面處的水分，不用擔心引發以輥狀態接觸之離型層之硬化阻礙故較佳。 於一態樣中，疏水化層之水接觸角為95°以上至130°以下，例如亦可為98°以上至130°以下。 本發明中，尤其若疏水化層之水接觸角在上述範圍內，且疏水化層含有離型層所含陽離子硬化型聚二甲基矽氧烷(a)，則可減少被認為是吸附於基材膜之反離型面處的水分，可更顯著地解決引發在輥狀態下接觸之離型層之硬化阻礙此種課題。此外，捲出輥狀膜之際，可抑制異物附著於離型層，可保持離型層之高平滑性。再者，以輥狀態保管時或運送時變得不易吸附水分，也可防止吸濕皺褶或捲取偏差等輥外觀品級惡化故較佳。 The water contact angle of the hydrophobized layer of the present invention is not less than 90° and not more than 130°. If the water contact angle is set within this range, the moisture that is considered to be adsorbed on the release surface of the substrate film can be reduced, and there is no need to worry about causing hardening resistance of the release layer that is in contact with the roll state. Therefore, it is better. In one aspect, the water contact angle of the hydrophobized layer is not less than 95° and not more than 130°, for example, it may be not less than 98° and not more than 130°. In the present invention, especially if the water contact angle of the hydrophobized layer is within the above-mentioned range, and the hydrophobized layer contains cation-hardening polydimethylsiloxane (a) contained in the release layer, it is possible to reduce the amount of water that is considered to be adsorbed on Moisture on the anti-release surface of the substrate film can more significantly solve the problem of hardening and hindering the release layer that is in contact with the roll state. In addition, when the roll-shaped film is unwound, foreign matter can be suppressed from adhering to the release layer, and the high smoothness of the release layer can be maintained. In addition, it becomes difficult to absorb moisture when stored in a roll state or during transportation, and it is also preferable to prevent deterioration of the roll appearance quality such as moisture absorption wrinkles and uneven winding.
本發明中之疏水化層也可為除了含有陽離子硬化型聚二甲基矽氧烷(a)尚含有不具聚矽氧骨架之陽離子硬化型樹脂(b)之組成物之硬化物。藉由使用陽離子硬化型樹脂(b)可提高疏水化層之彈性模數。藉由製作成高彈性模數之疏水化層，不僅可提高離型膜之操作性，也可抑制捲出帶電故較佳。若提高疏水化層之彈性模數，則輥保管時相接觸之離型層與疏水化層之滑動性提高(變得容易滑動)。雖不應限定於特定的理論來解釋，一旦疏水化層變得容易滑動，由於相對於離型膜面在垂直方向上施加之應力變得容易釋放到水平方向，可降低以輥狀保管之際之離型層與樹脂片或是離型層與疏水化層之密接力，可抑制帶電故較佳。The hydrophobized layer in the present invention may be a cured product of a composition containing a cation-curable resin (b) not having a polysiloxane skeleton in addition to the cation-curable polydimethylsiloxane (a). The modulus of elasticity of the hydrophobized layer can be increased by using the cation-curable resin (b). By making the hydrophobized layer with high modulus of elasticity, it can not only improve the operability of the release film, but also suppress the unwinding electrification, so it is preferable. If the modulus of elasticity of the hydrophobized layer is increased, the sliding properties of the release layer and the hydrophobized layer which are in contact with each other during storage of the roll will be improved (it will become easier to slide). Although it should not be limited to a specific theory to explain, once the hydrophobized layer becomes easy to slide, since the stress applied in the vertical direction relative to the release film surface becomes easy to release to the horizontal direction, it can reduce the time of storage in a roll shape. The adhesive force between the release layer and the resin sheet or between the release layer and the hydrophobic layer can suppress electrification, so it is preferable.
做為形成疏水化層之陽離子硬化型聚二甲基矽氧烷(a)以及陽離子硬化型樹脂(b)之例，可使用和前述離型層所能使用之例為相同者。離型層與疏水化層之構成無須完全相同，只要於離型層、疏水化層之兩方含有陽離子硬化型聚二甲基矽氧烷(a)即可獲得具有本發明功效之離型膜。As examples of the cation-curable polydimethylsiloxane (a) and the cation-curable resin (b) that form the hydrophobized layer, the same ones as those that can be used for the aforementioned release layer can be used. The composition of the release layer and the hydrophobic layer does not have to be exactly the same, as long as the release layer and the hydrophobic layer contain cationic hardening polydimethylsiloxane (a), the release film with the effect of the present invention can be obtained .
當為使得以陽離子硬化型聚二甲基矽氧烷(a)為主成分之組成物進行硬化而成之疏水化層之情況，疏水化層之膜厚以0.001μm以上至0.050μm以下為佳。若為0.001μm以上，則與疏水化層相接觸之離型層之硬化阻礙抑制功效成為充分故較佳。若為0.050μm以下，可防止疏水化層之彈性模數降低，防止捲出帶電之增加、於輥狀態下發生黏連故較佳。In the case of a hydrophobized layer formed by curing a composition mainly composed of cation-curable polydimethylsiloxane (a), the film thickness of the hydrophobized layer is preferably 0.001 μm or more and 0.050 μm or less . If it is 0.001 μm or more, the effect of inhibiting hardening of the release layer in contact with the hydrophobized layer becomes sufficient, so it is preferable. If it is 0.050 μm or less, it is preferable to prevent the elastic modulus of the hydrophobized layer from decreasing, to prevent the increase of unwinding electrification, and to prevent the occurrence of sticking in the roll state.
若疏水化層係由含有陽離子硬化型聚二甲基矽氧烷(a)與不具聚矽氧骨架之陽離子硬化型樹脂(b)之組成物之硬化物而成之情況，相對於合計100質量份，不具聚矽氧骨架之陽離子硬化型樹脂(b)之含量以80質量%以上為佳，以85質量%以上為更佳，以90質量%以上為特佳。若陽離子硬化型樹脂(b)之含量設為80質量%以上而成為離型層中之主成分，則成為交聯密度高且彈性模數高之疏水化層故較佳。此時之疏水化層之膜厚以0.001μm至0.5μm為佳，以0.001μm至0.3μm為更佳。若疏水化層之膜厚為0.001μm，則離型層之硬化阻礙抑制功效、帶電抑制功效成為充分故較佳。若為0.5μm以下，不會將反離型面側之凹凸完全填埋，搬送性優異，捲取時不會發生黏連故較佳。If the hydrophobized layer is made of a cured product containing a cation-curing polydimethylsiloxane (a) and a cation-curing resin (b) without a polysiloxane skeleton, the total mass of 100 The content of the cation-curable resin (b) without a polysiloxane skeleton is preferably at least 80% by mass, more preferably at least 85% by mass, and most preferably at least 90% by mass. When the content of the cation-curable resin (b) is 80% by mass or more and becomes the main component of the release layer, it is preferable because it becomes a hydrophobized layer with a high crosslink density and a high modulus of elasticity. At this time, the film thickness of the hydrophobized layer is preferably 0.001 μm to 0.5 μm, more preferably 0.001 μm to 0.3 μm. When the film thickness of the hydrophobized layer is 0.001 μm, the hardening of the release layer prevents the suppressing effect and the electrification suppressing effect from being sufficient, so it is preferable. If it is 0.5 μm or less, the unevenness on the side of the anti-release surface will not be completely filled, and the conveyability is excellent, and it is preferable that sticking does not occur during coiling.
疏水化層之表面以較離型層之表面來得粗為佳。若疏水化層表面較離型層來得粗，則輥之搬送性、捲取性變佳，可防止傷痕、異物混入、捲出帶電之增加故較佳。The surface of the hydrophobized layer is preferably thicker than the surface of the release layer. If the surface of the hydrophobized layer is thicker than that of the release layer, the transferability and take-up performance of the roll will be improved, and it will prevent scratches, foreign matter from entering, and increase in unwinding electrification.
疏水化層之表面粗糙度Sa只要大於離型層之表面粗糙度即可獲得所期望之功效，較佳為Sa在1nm至40nm之範圍，更佳為2nm至30nm之範圍，甚佳為3nm至20nm之範圍。若Sa為1nm以上，可防止輥之搬送性、捲取性之惡化故較佳。若為40nm以下，不用擔心疏水化層之表面形狀轉印至樹脂片而發生不良情況故較佳。The desired effect can be obtained as long as the surface roughness Sa of the hydrophobized layer is greater than the surface roughness of the release layer, preferably Sa is in the range of 1nm to 40nm, more preferably in the range of 2nm to 30nm, even more preferably in the range of 3nm to 20nm range. When Sa is 1 nm or more, it is preferable to prevent deterioration of roll conveyance and winding properties. If it is 40 nm or less, it is preferable because there is no fear of problems caused by transfer of the surface shape of the hydrophobized layer to the resin sheet.
本發明中，為了形成疏水化層必須進行陽離子硬化反應。因此，疏水化層形成組成物以含有酸產生劑(c)為佳。關於所使用之酸產生劑之量、種類和前述離型層同樣。 此處，疏水化層中在水接觸角不致超出本發明之範圍的範圍內可含有酸產生劑(c)。 此外，即便是形成離型層之組成物與形成疏水化層之組成物為包含同種樹脂之態樣，各組成物中所含溶劑量有可能不同。因此，鑑定所得高分子之結構或是基於鑑定結果來界定申請專利範圍並非易事，存在有不符實際的事情。 In the present invention, it is necessary to carry out a cation hardening reaction in order to form a hydrophobized layer. Therefore, the composition for forming a hydrophobized layer preferably contains an acid generator (c). The amount and kind of the acid generator to be used are the same as the aforementioned release layer. Here, the acid generator (c) may be contained in the hydrophobized layer within the range where the water contact angle does not exceed the range of the present invention. In addition, even if the composition forming the release layer and the composition forming the hydrophobized layer contain the same resin, the amount of solvent contained in each composition may be different. Therefore, it is not easy to identify the structure of the obtained polymer or to define the scope of the patent application based on the identification results, and there are some unrealistic things.
(離型膜之製造方法) 於本發明中，形成離型層之離型層形成組成物之塗布較佳為於聚酯膜之製造過程中實施的在線方式、或者於聚酯膜之製造後實施的離線方式。 於以在線方式塗布之情形時，較佳為下述方法：於沿膜行進方向(縱向)延伸而經單軸配向之膜，塗布溶解或分散有離型性樹脂之塗液，然後於橫向(與膜行進方向正交之方向)延伸，進行雙軸配向之同步形成離型層。 於以離線方式塗布之情形時，可使用下述方法：於雙軸配向聚酯膜的一個面塗布溶解或經分散有離型性樹脂之塗液，藉由乾燥將溶媒等加以去除後，進行加熱乾燥、熱硬化或紫外線硬化。 (Manufacturing method of release film) In the present invention, the coating of the release layer-forming composition that forms the release layer is preferably an in-line method performed during the production of the polyester film, or an off-line system performed after the production of the polyester film. In the case of in-line coating, the following method is preferred: on a film that is uniaxially aligned along the traveling direction (longitudinal direction) of the film, apply a coating solution that dissolves or disperses a release resin, and then in the transverse direction ( The direction perpendicular to the film traveling direction) extends to form a release layer synchronously with biaxial alignment. In the case of off-line coating, the following method can be used: apply a coating solution in which a release resin is dissolved or dispersed on one side of a biaxially oriented polyester film, remove the solvent, etc. by drying, and then perform Heat drying, heat curing or UV curing.
以在線方式塗布時之塗液較佳為使用水性塗液。水性塗液之種類並無特別限定，較佳為添加水溶性之有機溶媒、例如醇類等。 以離線方式塗布時之塗液並無特別限定，較佳為使用有機溶劑，較佳為添加沸點為90℃以上之溶劑。藉由添加沸點為90℃以上之溶劑，而能夠防止乾燥時之突沸，將塗膜調平，能夠提高乾燥後之塗膜表面之平滑性。 It is preferable to use a water-based coating liquid as the coating liquid in the case of in-line coating. The type of water-based coating solution is not particularly limited, and it is preferable to add water-soluble organic solvents, such as alcohols. The coating solution for off-line coating is not particularly limited, but an organic solvent is preferably used, and a solvent having a boiling point of 90° C. or higher is preferably added. By adding a solvent with a boiling point of 90°C or higher, bumping during drying can be prevented, the coating film can be leveled, and the smoothness of the coating film surface after drying can be improved.
關於疏水化層之形成方法並無特別限定，可採行和離型層同時進行雙面加工之方法、或是單面加工後再加工相反面之方法來進行加工。後者之情況，較佳為於加工離型層之後再加工疏水化層。由於樹脂片係被直接積層，故離型層必須較疏水化層來得平滑。因此，先加工疏水化層的作法可使得背面之滑動性良好，於離型層加工時不易產生皺摺等，可更均勻地進行塗敷故較佳。There is no particular limitation on the method of forming the hydrophobized layer, and the method of processing the release layer on both sides at the same time, or the method of processing the opposite side after processing on one side can be adopted. In the latter case, it is preferable to process the hydrophobic layer after processing the release layer. Since the resin sheets are directly laminated, the release layer must be smoother than the hydrophobic layer. Therefore, the method of processing the hydrophobized layer first can make the slipperiness of the back surface good, and it is not easy to produce wrinkles when the release layer is processed, and it can be coated more uniformly, so it is better.
疏水化層之加工並非是聚酯膜製膜時進行塗敷之線上方式而是於聚酯膜製膜後進行加工之離線方式來加工為佳。以離線方式來進行，可高度地控制塗敷時之張力、捲取時之張力等，故加工時之操作優異。The processing of the hydrophobizing layer is preferably not an online method of coating when the polyester film is formed, but an offline method of processing the polyester film after the film is formed. It is carried out offline, and the tension during coating and winding can be highly controlled, so the operation during processing is excellent.
作為前述離型層形成組成物以及疏水化層形成組成物之塗布法可適用周知之任意塗布法，例如可利用凹版塗布法以及逆向塗布法等輥塗布法、線棒等之棒式塗布法、模具塗布法、噴塗法、氣刀塗布法等以往已知之方法。As the coating method of the release layer forming composition and the hydrophobizing layer forming composition, any known coating method can be applied, for example, a roll coating method such as a gravure coating method and a reverse coating method, a bar coating method such as a wire bar, etc., Conventionally known methods such as die coating method, spray coating method, and air knife coating method.
本發明之離型膜在離型層之加工以及疏水化層之加工時係以輥對輥方式來搬送基材膜。因此，離型層以及疏水化層之加工後，離型膜係被捲取成輥狀而受到保管。此外，樹脂片之成型、樹脂片之剝離也是以輥對輥方式進行。The release film of the present invention transports the substrate film in a roll-to-roll manner during the processing of the release layer and the processing of the hydrophobized layer. Therefore, after the processing of the release layer and the hydrophobization layer, the release film is wound up into a roll and stored. In addition, the molding of the resin sheet and the peeling of the resin sheet are also carried out in a roll-to-roll manner.
將離型膜捲取成為輥狀時之張力以10N/m至300N/m為佳。若捲取張力為10N/m以上，不會出現捲取偏差故較佳。此外，以輥狀保管時不會發生倒捲，不用擔心傷痕混入離型層或是捲出帶電量增加故較佳。若捲取張力為300N/m以下，不用擔心捲緊所致離型膜之變形或是發生黏連故較佳。The tension when winding the release film into a roll is preferably 10N/m to 300N/m. If the coiling tension is 10 N/m or more, it is preferable because coiling deviation does not occur. In addition, when it is stored in a roll shape, it will not be rewound, so there is no need to worry about scratches being mixed into the release layer or an increase in the amount of charge when it is rolled out. If the take-up tension is below 300N/m, there is no need to worry about the deformation or adhesion of the release film due to tight winding, so it is better.
將離型膜捲取成為輥狀時，以使用接觸輥來進行捲取為佳。接觸輥之接觸壓以100N/m至3000N/m為佳。若為100N/m以上，可減少捲取時所混入之伴隨空氣，可抑制捲取偏移之發生故較佳。若為3000N/m以下，可抑制接觸輥壓所致離型膜之變形，可獲得平面性優異之離型膜故較佳。When winding up a release film into a roll shape, it is preferable to wind up using a touch roll. The contact pressure of the contact roller is preferably 100N/m to 3000N/m. If it is 100 N/m or more, it is preferable to reduce the accompanying air mixed in during coiling and suppress the occurrence of coiling deviation. If it is 3000 N/m or less, it is preferable to suppress the deformation of the release film caused by contact roll pressure and obtain a release film with excellent planarity.
(其他特性) 本發明中，將以輥狀態保管之離型膜捲出時之捲出帶電量可被壓低。將捲取成為輥狀之離型膜以100m/min捲出時之帶電量以未達±1.0kV為佳。若未達±1.0kV，不用擔心步驟中之極微小異物附著於離型膜故較佳。此外，剝離樹脂片時之剝離帶電也可被壓低，能以更低、均勻的力量來進行剝離故較佳。 (other features) In the present invention, the unwinding charge amount at the time of unwinding the release film stored in the roll state can be suppressed. When the roll-shaped release film is unwound at 100m/min, it is preferable that the charge amount is less than ±1.0kV. If it is less than ±1.0kV, there is no need to worry about the extremely small foreign matter adhering to the release film during the process, so it is better. In addition, the peeling charge at the time of peeling off the resin sheet can also be suppressed, and the peeling can be performed with lower and uniform force, which is preferable.
針對輥狀態之保管環境，只要是可避免直射日光或高溫之屋內的涼爽平穩場所則無特別限制都可進行保管。也可為調濕環境下或是經過溫度管理之保管場所，只要是濕度為20RH%至90RH%、溫度為-5℃至50℃之範圍即具有本發明之功效。As for the storage environment in the roll state, there are no special restrictions as long as it is a cool and stable place in a room where direct sunlight or high temperature can be avoided. It can also be used in a humidity-controlled environment or a temperature-controlled storage place, as long as the humidity is in the range of 20RH% to 90RH%, and the temperature is in the range of -5°C to 50°C, it will have the effect of the present invention.
本發明中之剝離力，係使用設有離型層與疏水化層之離型膜在輥狀態下於40RH%至50RH%、20℃至25℃之環境下保管3天後，捲出離型膜輥而採集離型膜進行測定所得之值。於設置疏水化層之後，藉由以輥狀來保管而使得離型層之反應完成，獲得具有優異剝離力之離型膜。本發明中之剝離力，係於離型膜表面貼合黏著帶(日東電工(股份有限)公司製之「31B」)，以拉伸速度300m/min進行T型剝離所測定之值。詳細的評價方法如後述。The peeling force in the present invention refers to the use of a release film with a release layer and a hydrophobic layer, which is stored in an environment of 40RH% to 50RH% and 20°C to 25°C for 3 days in a roll state, and then rolled out of the release film Roll the film and collect the release film to measure the value obtained. After the hydrophobization layer was installed, the reaction of the release layer was completed by storing it in a roll shape, and a release film with excellent peeling force was obtained. The peeling force in the present invention is the value measured by T-peeling at a tensile speed of 300m/min by attaching an adhesive tape ("31B" manufactured by Nitto Denko Co., Ltd.) to the surface of the release film. A detailed evaluation method will be described later.
離型層之常態剝離力(I)以100mN/50mm以上至1500mN/50mm以下為佳，以100mN/50mm以上至1300mN/50mm以下為更佳，以100mN/50mm以上至1000mN/50mm以下為甚佳。若為100N/50mm以上，不用擔心樹脂片搬送中出現部分性***或是發生剝離，保持性優異故較佳。若為1500mN/50mm以下，可在樹脂片不受到損害的前提下進行剝離故較佳。The normal peel force (I) of the release layer is preferably from 100mN/50mm to 1500mN/50mm, more preferably from 100mN/50mm to 1300mN/50mm, and more preferably from 100mN/50mm to 1000mN/50mm . If it is 100N/50mm or more, there is no need to worry about partial swelling or peeling during the conveyance of the resin sheet, and the holding property is excellent, so it is preferable. If it is 1500 mN/50 mm or less, it is preferable to peel without damaging the resin sheet.
離型層之加熱後剝離力(II)以150mN/50mm以上至2250mN/50mm以下為佳，以150mN/50mm以上至1950mN/50mm以下為更佳，以150mN/50mm以上至1500mN/50mm以下為甚佳。由於在離型膜上成型出樹脂片之際或是進行剝離之際，離型膜會受熱，故可藉由加熱後剝離力來更詳細地評價離型膜之剝離性。若為150mN/50mm以上，則陶瓷生胚之保持性優異故較佳。若為2250mN/50mm以下，則離型層所含未反應物少，樹脂片之剝離優異故較佳。 雖不應限定於特定的理論來解釋，但本發明中藉由使得離型層含有陽離子硬化型聚二甲基矽氧烷(a)且疏水化層之水接觸角為90°以上至130°以下，可抑制被認為是在基材膜之反離型面側以微量存在之水分的影響所致陽離子硬化型樹脂之經時反應受到阻礙，可解決離型層之硬化不充分之問題。其結果，可將加熱後剝離力(II)導入上述範圍，例如對樹脂片進行成型之步驟中，以30℃以上至120℃以下之條件來加工之際，可良好地保持樹脂片形成組成物，此外，可容易進行所得樹脂片之剝離。 從而，本發明中能以良好的平衡性來進行樹脂片形成組成物之保持與加熱後之剝離。例如，即便是陶瓷生胚具有1.0μm以下此種極薄厚度之態樣，也可發揮此等功效。 The peeling force (II) of the release layer after heating is preferably 150mN/50mm to 2250mN/50mm, more preferably 150mN/50mm to 1950mN/50mm, and 150mN/50mm to 1500mN/50mm good. Since the release film is heated when the resin sheet is formed on the release film or when it is peeled off, the peelability of the release film can be evaluated in more detail by the peel force after heating. If it is 150mN/50mm or more, the holding property of the ceramic green body is excellent, so it is preferable. If it is 2250 mN/50 mm or less, the release layer contains less unreacted substances, and the peeling of the resin sheet is excellent, so it is preferable. Although it should not be limited to a specific theory to explain, in the present invention, by making the release layer contain cation-hardening polydimethylsiloxane (a) and the water contact angle of the hydrophobized layer is 90° or more to 130° Next, it is possible to prevent the reaction of the cation-curable resin from being hindered over time due to the influence of moisture present in a small amount on the anti-release surface side of the base film, and to solve the problem of insufficient hardening of the release layer. As a result, the peeling force (II) after heating can be brought into the above range, for example, in the step of molding the resin sheet, when the resin sheet is processed under the conditions of 30°C or higher and 120°C or lower, the resin sheet forming composition can be well maintained. , In addition, peeling of the obtained resin sheet can be easily performed. Therefore, in the present invention, retention of the resin sheet forming composition and peeling after heating can be performed with good balance. For example, even a ceramic green body having an extremely thin thickness of 1.0 μm or less can exhibit these functions.
常態剝離力(I)與加熱後剝離力(II)之比：(II)/(I)以1.00以上至1.50以下為佳。常態剝離力(I)與加熱後剝離力(II)之比：(II)/(I)若大則暗示了離型層中殘存有未反應物，表示離型層之硬化尚未完全進行。若(II)/(I)為1.50以下，由於以輥狀態保管時離型層係和疏水化層接觸，故不會因水分發生硬化不良，可使得離型層之硬化完全進行故較佳。由於加熱後剝離力(II)相較於常態剝離力(I)通常顯示較大之值，故(I)/(II)以1.0以上為佳。The ratio of normal peeling force (I) to heated peeling force (II): (II)/(I) is preferably more than 1.00 and less than 1.50. The ratio of the normal peeling force (I) to the peeling force after heating (II): (II)/(I) If it is large, it means that there are unreacted substances remaining in the release layer, which means that the hardening of the release layer has not been completed. If (II)/(I) is 1.50 or less, since the release layer is in contact with the hydrophobized layer during storage in a roll state, it is preferable that the hardening of the release layer can be completely progressed without causing poor curing due to moisture. Since the peel force (II) after heating usually shows a larger value than the normal peel force (I), (I)/(II) is preferably 1.0 or more.
(樹脂片) 於一態樣中，本發明之離型膜只要是樹脂片則無特別限定，也可適用於黏著劑、光學膜之製造。於一態樣中，為含有無機化合物之樹脂片成型用離型膜。作為無機化合物可例示金屬粒子、金屬氧化物、礦物等，例如可例示碳酸鈣、二氧化矽粒子、鋁粒子、鈦酸鋇粒子等。 作為樹脂可舉出例如聚乙烯醇縮醛樹脂、聚(甲基)丙烯酸酯樹脂等。 本發明具有平滑性高之離型層以及平滑性、操作性及抗靜電性優異之背面層，故即便為於樹脂片包含這些無機化合物之態樣，亦能夠抑制可能由無機化合物引起之缺陷，例如樹脂片之破損、難以自離型層難以剝離樹脂片之問題。 形成樹脂片之樹脂成分可根據用途適當選擇。 於一態樣中，包含無機化合物之樹脂片為陶瓷生胚。例如，陶瓷生胚可包含鈦酸鋇作為無機化合物。於一態樣中，樹脂片係厚度為0.2μm以上至1.0μm以下。 (resin sheet) In one aspect, the release film of the present invention will not be particularly limited as long as it is a resin sheet, and it can also be applied to the manufacture of adhesives and optical films. In one aspect, it is a release film for forming a resin sheet containing an inorganic compound. Examples of the inorganic compound include metal particles, metal oxides, minerals, and the like, for example, calcium carbonate, silica particles, aluminum particles, barium titanate particles, and the like. Examples of the resin include polyvinyl acetal resins, poly(meth)acrylate resins, and the like. The present invention has a release layer with high smoothness and a back layer with excellent smoothness, handleability, and antistatic properties, so even if the resin sheet contains these inorganic compounds, it can suppress defects that may be caused by inorganic compounds. For example, the damage of the resin sheet, the problem that it is difficult to peel off the resin sheet from the release layer. The resin component forming the resin sheet can be appropriately selected according to the application. In one aspect, the resin sheet including the inorganic compound is a ceramic green body. For example, a ceramic green body may contain barium titanate as an inorganic compound. In one aspect, the thickness of the resin sheet is not less than 0.2 μm and not more than 1.0 μm.
(陶瓷生胚及陶瓷電容器) 一般而言，積層陶瓷電容器具有長方體狀之陶瓷素體。於陶瓷素體之內部係使得第1內部電極與第2內部電極沿著厚度方向交互地設置。第1內部電極係露出於陶瓷素體之第1端面。於第1端面上設有第1外部電極。第1內部電極於第1端面和第1外部電極呈電性連接。第2內部電極係露出於陶瓷素體之第2端面。於第2端面上設有第2外部電極。第2內部電極於第2端面和第2外部電極呈電性連接。 (ceramic green body and ceramic capacitor) In general, a multilayer ceramic capacitor has a rectangular parallelepiped ceramic body. Inside the ceramic body, the first internal electrodes and the second internal electrodes are arranged alternately along the thickness direction. The first internal electrode is exposed on the first end face of the ceramic body. A first external electrode is provided on the first end surface. The first internal electrode is electrically connected to the first external electrode on the first end surface. The second internal electrode is exposed on the second end surface of the ceramic body. A second external electrode is provided on the second end surface. The second internal electrode is electrically connected to the second external electrode on the second end surface.
於一態樣中，本發明之離型膜為陶瓷生胚製造用離型膜，為了製造此種積層陶瓷電容器而使用。 例如，使用本發明之陶瓷生胚製造用離型膜來成型出陶瓷生胚之陶瓷生胚之製造方法，可成型出具有0.2μm至1.0μm之厚度的陶瓷生胚。 更詳細而言，例如採以下方式來製造陶瓷生胚。首先，將本發明之離型膜當作載體膜使用，對其塗布用以構成陶瓷素體的陶瓷漿料並進行乾燥。陶瓷生胚之厚度逐漸要求為0.2μm至1.0μm之極薄品。於經過塗布、乾燥之陶瓷生胚上，印刷用以構成第1內部電極或是第2內部電極之導電層。可藉由將陶瓷生胚、印刷了用以構成第1內部電極之導電層的陶瓷生胚以及印刷了用以構成第2內部電極之導電層的陶瓷生胚加以適宜積層並加壓，獲得母積層體。將母積層體分切為複數個，製作生陶瓷素體。藉由對生陶瓷素體進行燒成來獲得陶瓷素體。之後，可藉由形成第1外部電極以及第2外部電極來完成積層陶瓷電容器。 [實施例] In one aspect, the release film of the present invention is a release film for ceramic green sheet production, and is used for the production of such a multilayer ceramic capacitor. For example, the method of manufacturing ceramic green bodies using the release film for manufacturing ceramic green bodies of the present invention to form ceramic green bodies can form ceramic green bodies with a thickness of 0.2 μm to 1.0 μm. More specifically, ceramic green bodies are produced, for example, as follows. First, the release film of the present invention is used as a carrier film, and a ceramic slurry for constituting a ceramic body is applied and dried. The thickness of the ceramic green body is gradually required to be extremely thin from 0.2 μm to 1.0 μm. On the coated and dried ceramic green body, the conductive layer for forming the first internal electrode or the second internal electrode is printed. The mother body can be obtained by suitably laminating and pressing ceramic green bodies, ceramic green bodies printed with a conductive layer constituting a first internal electrode, and ceramic green bodies printed with a conductive layer constituting a second internal electrode. laminated body. The mother laminated body is divided into plural pieces to produce a green ceramic element body. The ceramic body is obtained by firing the raw ceramic body. Thereafter, a multilayer ceramic capacitor can be completed by forming the first external electrode and the second external electrode. [Example]
以下，使用實施例對本發明加以更詳細說明，但本發明不受這些實施例之任何限定。本發明中所用之特性值係使用下述方法進行評價。Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples at all. The characteristic values used in the present invention were evaluated using the following methods.
(厚度測定) 將所切出之離型膜進行樹脂包埋，使用超薄切片機進行超薄切片。然後，使用日本電子製造之JEM2100穿透式電子顯微鏡進行剖面觀察，根據所觀察之TEM圖像來測定離型層之膜厚。於厚度過薄而於剖面觀察中無法準確評價之情形時，使用反射分光膜厚計(大塚電子公司製造，FE-3000)進行測定。 (thickness measurement) Embed the cut-out release film in resin, and use an ultra-microtome for ultra-thin sections. Then, the section was observed using a JEM2100 transmission electron microscope manufactured by JEOL, and the film thickness of the release layer was measured from the observed TEM image. When the thickness is too thin to be accurately evaluated by cross-sectional observation, it measures using a reflection spectroscopic film thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE-3000).
(區域表面粗糙度Sa、最大突起高度Sp) 使用非接觸表面形狀測量系統(VertScan R550H-M100)，以下述條件進行測定。區域表面平均粗糙度(Sa)係採用5次測定之平均值，最大突起高度(Sp)係測定7次，採用去掉最大值及最小值的5次測定結果之最大值。 [測定條件] ·測定模式：波動(WAVE)模式 ·物鏡：50倍 ·0.5×Tube透鏡 ·測定面積 187μm×139μm [分析條件] ·面校正：四次校正 ·內插處理：完全內插 (area surface roughness Sa, maximum protrusion height Sp) The measurement was performed under the following conditions using a non-contact surface profile measurement system (VertScan R550H-M100). The area surface average roughness (Sa) is the average value of 5 measurements, the maximum protrusion height (Sp) is measured 7 times, and the maximum value of the 5 measurement results with the maximum and minimum values removed is used. [measurement conditions] Measurement mode: WAVE mode · Objective lens: 50 times ·0.5×Tube lens ・Measurement area 187μm×139μm [Analysis conditions] ·Surface correction: four corrections Interpolation processing: fully interpolated
(常態剝離力(I)) 將各實施例以及各比較例所得樹脂片製造用離型膜捲成寬度400mm、長度6000m之輥狀，獲得離型膜輥。此時以捲取張力150N/mm、接觸輥壓700N/m完成捲取。將所得膜輥於20℃至25℃、濕度40RH%至50RH%之環境下保管3日後進行捲出，採集測定用離型膜。於測定用離型膜之離型層表面貼合黏著帶(日東電工(股份有限)公司製「31B」)，裁斷出寬度25mm、長度150mm之短條狀的具黏著帶之離型膜。將裁斷後之具黏著帶之離型膜以5kg之壓接輥進行壓接後，於溫度22℃、濕度60%之條件下放置20小時。之後，固定黏著帶之一端，握持離型膜之一端，將離型膜側以300mm/min之速度作拉伸，以T型剝離進行測定。測定係使用了拉伸試驗機((股份有限)島津製作所製之「AUTOGRAPHAG-X」)。 (Normal peel force (I)) The release film for resin sheet manufacture obtained in each Example and each comparative example was rolled into the roll shape of width 400mm, and length 6000m, and the release film roll was obtained. At this time, the coiling was completed with a coiling tension of 150 N/mm and a touch roll pressure of 700 N/m. The obtained film roll was stored in an environment of 20°C to 25°C and a humidity of 40RH% to 50RH% for 3 days, and then rolled out to collect the release film for measurement. Adhesive tape ("31B" manufactured by Nitto Denko Co., Ltd.) was attached to the surface of the release layer of the release film for measurement, and the release film with the adhesive tape was cut into short strips with a width of 25 mm and a length of 150 mm. After the cut release film with adhesive tape is crimped with a 5kg crimping roller, it is placed at a temperature of 22°C and a humidity of 60% for 20 hours. After that, fix one end of the adhesive tape, hold one end of the release film, stretch the release film side at a speed of 300mm/min, and measure it by T-peeling. For the measurement, a tensile tester ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) was used.
(加熱後剝離力(II)) 與前述常態剝離力(I)同樣地採集評價用離型膜，於離型層表面貼合黏著帶(日東電工(股份有限)製，商品名「31B」)，裁斷成寬度25mm、長度150mm之短條狀的具黏著帶之離型膜。將裁斷後之具黏著帶之離型膜以5kg之壓接輥進行壓接後，以溫度70℃之烘箱加熱20小時。之後，固定黏著帶之一端，握持離型膜之一端，將離型膜側以300mm/min之速度來拉伸而進行剝離，以T型剝離進行測定。測定係使用了拉伸試驗機((股份有限)島津製作所製之「AUTOGRAPHAG-X」)。 (Peel force after heating (II)) The release film for evaluation was collected in the same manner as the above-mentioned normal peel force (I), and an adhesive tape (manufactured by Nitto Denko Co., Ltd., trade name "31B") was attached to the surface of the release layer, and cut into a width of 25 mm and a length of 150 mm. A short strip of release film with an adhesive tape. After the cut-off release film with the adhesive tape was crimped with a 5kg crimping roller, it was heated in an oven at a temperature of 70°C for 20 hours. After that, fix one end of the adhesive tape, hold one end of the release film, pull the release film side at a speed of 300mm/min to peel off, and measure it by T-peel. For the measurement, a tensile tester ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) was used.
(捲出帶電量) 將各實施例以及各比較例所得樹脂片製造用剝離膜捲成寬度400mm、長度6000m之輥狀，獲得離型膜輥。此時以捲取張力150mN/mm、接觸輥壓700N/m完成捲取。將此離型膜輥於20℃至25℃、濕度40RH%至50RH%以下之環境下保管30日之後，使用春日電機公司製「KSD-0103」來測定以100m/min捲出之際之帶電量。帶電量係每捲出長度500M便針對剛捲出後100mm之部位進行測定，算出平均值。 〇：未達±1.0kV ×：±1.0kV以上 (Reel out electrical charge) The peeling film for resin sheet manufacture obtained in each Example and each comparative example was rolled into the roll shape of width 400mm, and length 6000m, and the release film roll was obtained. At this time, the coiling was completed with a coiling tension of 150 mN/mm and a touch roll pressure of 700 N/m. After storing this release film roll at 20°C to 25°C and a humidity of 40RH% to 50RH% or less for 30 days, use "KSD-0103" manufactured by Kasuga Electric Co., Ltd. to measure the charge when it is rolled out at 100m/min quantity. The amount of charge is measured at a position 100mm immediately after unrolling for every roll-out length of 500M, and the average value is calculated. 〇: Less than ±1.0kV ×: ±1.0kV or more
(水接觸角) 使用自動接觸角計(協和界面科學公司製：DM-701)，於22℃、60%RH之條件下測定水相接於離型面之接觸角。水之滴下量為1.8μL，採用滴下後經過60秒後之接觸角之值。 (water contact angle) Using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: DM-701), the contact angle of the water phase on the release surface was measured under the conditions of 22° C. and 60% RH. The amount of water dropped was 1.8 μL, and the value of the contact angle after 60 seconds had elapsed after the drop was used.
(聚對苯二甲酸乙二酯顆粒(PET (I))之製備) 在酯化反應裝置方面使用由具有攪拌裝置、分餾器、原料裝填口以及生成物取出口之3段的完全混合槽所構成之連續酯化反應裝置。將TPA(對苯二甲酸)設定為2噸/小時，將EG(乙二醇)相對於TPA 1莫耳設為2莫耳，將三氧化銻相對於生成PET使得Sb原子成為160ppm的量，將這些漿料連續供給於酯化反應裝置之第1酯化反應罐，在常壓下以平均滯留時間4小時、255℃進行反應。其次，將第1酯化反應罐內之反應生成物連續地取出至系統外而供給至第2酯化反應罐，於第2酯化反應罐內將自第1酯化反應罐所餾除的EG相對於生成PET供給8質量%，進而，添加含有Mg原子相對於生成PET成為65ppm的量的乙酸鎂四水合鹽之EG溶液、以及含有P原子相對於生成PET成為40ppm之量的TMPA(磷酸三甲酯)之EG溶液，在常壓下以平均滯留時間1小時、260℃進行反應。其次，將第2酯化反應罐之反應生成物連續地取出至系統外而供給至第3酯化反應罐，一邊將使用高壓分散機(日本精機公司製)以39MPa(400kg/cm 2)之壓力進行了平均處理次數5路徑的分散處理後之平均粒徑0.9μm之多孔質矽膠0.2質量%、以及聚丙烯酸之銨鹽相對於每單位碳酸鈣附著了1質量%之平均粒徑為0.6μm之合成碳酸鈣0.4質量%分別當作10%之EG漿料來添加，一邊在常壓下以平均滯留時間0.5小時、260℃進行反應。將在第3酯化反應罐內所生成之酯化反應生成物連續地供給至3段之連續縮聚反應裝置來進行縮聚，以95%切面直徑為20μm之不鏽鋼繊維經燒結之過濾器來進行過濾後，進行超過濾而擠出至水中，冷卻後切割為碎片狀，獲得固有黏度0.60dl/g之PET碎片(以下稱為PET(I))。PET碎片中之滑劑含量為0.6質量%。 (Preparation of Polyethylene Terephthalate Granules (PET (I))) As an esterification reaction device, a three-stage complete mixing tank with a stirring device, a fractionator, a raw material charging port, and a product outlet is used. A continuous esterification reaction device. TPA (terephthalic acid) was set to 2 tons/hour, EG (ethylene glycol) was set to 2 moles per 1 mole of TPA, and antimony trioxide was set in such an amount that Sb atoms became 160 ppm with respect to the formed PET, These slurries were continuously supplied to the 1st esterification reaction tank of the esterification reaction apparatus, and it reacted at 255 degreeC with an average residence time of 4 hours under normal pressure. Next, the reaction product in the first esterification reaction tank is continuously taken out of the system and supplied to the second esterification reaction tank, and in the second esterification reaction tank, the EG was supplied in an amount of 8% by mass relative to the resulting PET, and further, an EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms relative to the resulting PET, and TMPA (phosphoric acid) containing 40 ppm of P atoms relative to the resulting PET were added. The EG solution of trimethyl ester) was reacted at 260°C with an average residence time of 1 hour under normal pressure. Next, the reaction product of the second esterification reaction tank was continuously taken out of the system and supplied to the third esterification reaction tank, while using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.) at 39MPa (400kg/cm 2 ) 0.2% by mass of porous silica gel with an average particle size of 0.9 μm after pressure-treated average number of times of dispersion treatment of 5 paths, and an average particle size of 0.6 μm with 1 mass % of ammonium polyacrylic acid attached per unit of calcium carbonate 0.4% by mass of synthetic calcium carbonate was added as 10% EG slurry, and the reaction was carried out at 260° C. with an average residence time of 0.5 hours under normal pressure. The esterification reaction product generated in the third esterification reaction tank is continuously supplied to the three-stage continuous polycondensation reaction device for polycondensation, and 95% of the sintered stainless steel fiber with a cross-sectional diameter of 20 μm is used for filtration. Afterwards, carry out ultrafiltration and extrude into water, cut into fragments after cooling, obtain the PET fragment (hereinafter referred to as PET (I)) of intrinsic viscosity 0.60dl/g. The content of the slip agent in the PET chips was 0.6% by mass.
(聚對苯二甲酸乙二酯顆粒(PET(II))之製備) 另一方面，於上述PET(I)碎片之製造中，獲得了完全不含碳酸鈣、二氧化矽等粒子之固有黏度0.62dl/g之PET碎片(以下稱為PET(II))。 (Preparation of Polyethylene Terephthalate Granules (PET(II))) On the other hand, in the production of the above-mentioned PET (I) chips, PET chips with an intrinsic viscosity of 0.62 dl/g (hereinafter referred to as PET (II)) completely free of particles such as calcium carbonate and silicon dioxide were obtained.
(積層膜X1之製造) 將這些PET碎片乾燥後，以285℃熔融，藉由個別的擠出機以290℃熔融，利用95%切面直徑為15μm之不鏽鋼繊維經燒結之過濾器以及95%切面直徑為15μm之不鏽鋼粒子經燒結之過濾器來進行2段過濾，於進料塊內匯集，以PET(I)成為表面層B(反離型面側層)、PET(II)成為表面層A(離型面側層)的方式來積層，以45m/分鐘鐘的速度擠出(澆鑄)成為片狀，利用静電密接法在30℃之澆鑄轉筒上進行静電密接、冷卻，獲得固有黏度為0.59dl/g之未延伸聚對苯二甲酸乙二酯片。層比率以各擠出機之吐出量計算成為PET(I)/(II)＝60質量%/40質量%的方式進行了調整。其次，將此未延伸片以紅外線加熱器進行加熱後，以輥溫度80℃藉由輥間的速度差在縱向上進行3.5倍延伸。之後，引導至拉幅機，以140℃在橫向進行4.2倍之延伸。其次，於熱固定區以210℃進行熱處理。之後，於橫向以170℃進行2.3%之緩和處理，獲得厚度31μm之雙軸延伸聚對苯二甲酸乙二酯膜X1。所得膜X1之表面層A之Sa為1nm，表面層B之Sa為28nm。 (Manufacture of laminated film X1) After drying these PET flakes, they were melted at 285°C, melted at 290°C by a separate extruder, and sintered filters with 95% stainless steel fibers with a cross-sectional diameter of 15 μm and 95% stainless steel particles with a cross-sectional diameter of 15 μm were passed through The sintered filter is used for 2-stage filtration, which is collected in the feed block, and PET (I) becomes the surface layer B (anti-release surface side layer), and PET (II) becomes the surface layer A (release surface side layer) Laminate by means of extruding (casting) at a speed of 45m/min to form a sheet, and use the electrostatic bonding method to carry out electrostatic bonding and cooling on a casting drum at 30°C to obtain an intrinsic viscosity of 0.59dl/g Unstretched polyethylene terephthalate sheet. The layer ratio was adjusted so that PET(I)/(II)=60% by mass/40% by mass was calculated based on the discharge amount of each extruder. Next, after heating this unstretched sheet with an infrared heater, it stretched 3.5 times in the longitudinal direction at a roll temperature of 80° C. with a speed difference between the rolls. Thereafter, it was guided to a tenter and stretched 4.2 times in the lateral direction at 140°C. Next, heat treatment is performed at 210° C. in a heat-fixing zone. Thereafter, a relaxation treatment of 2.3% was performed at 170° C. in the lateral direction to obtain a biaxially stretched polyethylene terephthalate film X1 with a thickness of 31 μm. The Sa of the surface layer A of the obtained film X1 was 1 nm, and the Sa of the surface layer B was 28 nm.
(積層膜X2之製造) 積層膜X2係使用厚度25μm之E5101(東洋紡酯(註冊商標)膜，東洋紡公司製)。E5101為在表面層A以及表面層B含有粒子之構成。積層膜X2之表面層A之Sa為24nm，表面層B之Sa為24nm。 (Manufacture of laminated film X2) For the laminated film X2, E5101 (Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used. E5101 is a composition that contains particles in surface layer A and surface layer B. The Sa of the surface layer A of the multilayer film X2 is 24 nm, and the Sa of the surface layer B is 24 nm.
(離型層形成組成物Y1) 甲基乙基酮 49.833質量份 甲苯 49.833質量份 陽離子硬化型聚二甲基矽氧烷(a)： 含脂環式環氧基之聚二甲基矽氧烷 0.316質量份 (製品名：SILCOLEASE UV POLY215，荒川化學工業公司製，固形物濃度100%) 酸產生劑(c) 0.018質量份 (製品名：UVCATA211，荒川化學工業公司製，固形物濃度18%) (Release layer forming composition Y1) Methyl ethyl ketone 49.833 parts by mass Toluene 49.833 parts by mass Cationic hardening polydimethylsiloxane (a): Alicyclic epoxy-containing polydimethylsiloxane 0.316 parts by mass (Product name: SILCOLEASE UV POLY215, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 100%) Acid generator (c) 0.018 parts by mass (Product name: UVCATA211, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 18%)
(離型層形成組成物Y2) 甲基乙基酮 47.361質量份 甲苯 47.361質量份 陽離子硬化型聚二甲基矽氧烷(a) 0.250質量份 (製品名：SILCOLEASE UV POLY215，荒川化學工業公司製，固形物濃度100%) 不具聚矽氧骨架之陽離子硬化型樹脂(b)： 2官能脂環式環氧單體 4.750質量份 (製品名：Celloxide2021P，Daicel公司製，固形物濃度100%) 酸產生劑(c) 0.278質量份 (製品名：UVCATA211，荒川化學工業公司製，固形物濃度18%) (Release layer forming composition Y2) Methyl ethyl ketone 47.361 parts by mass Toluene 47.361 parts by mass Cationic hardening polydimethylsiloxane (a) 0.250 parts by mass (Product name: SILCOLEASE UV POLY215, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 100%) Cationic hardening resin (b) without polysiloxane skeleton: 2 functional alicyclic epoxy monomers 4.750 parts by mass (Product name: Celloxide 2021P, manufactured by Daicel Corporation, solid content concentration 100%) Acid generator (c) 0.278 parts by mass (Product name: UVCATA211, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 18%)
(離型層形成組成物Y3) 甲基乙基酮 44.900質量份 甲苯 44.900質量份 二季戊四醇六丙烯酸酯 9.500質量份 (製品名：A-DPH，新中村化學公司製，固形物濃度100%) 含丙烯醯基之聚二甲基矽氧烷 0.500質量份 (製品名：BYKUV3500，BYK公司製，固形物濃度100%) 起始劑 0.200質量份 (製品名：Omnirad907，IGMResins公司製，固形物濃度100%) (Release layer forming composition Y3) Methyl ethyl ketone 44.900 parts by mass Toluene 44.900 parts by mass Dipentaerythritol hexaacrylate 9.500 parts by mass (Product name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 100%) Acryl-containing polydimethylsiloxane 0.500 parts by mass (Product name: BYKUV3500, manufactured by BYK Corporation, solid content concentration 100%) Initiator 0.200 parts by mass (Product name: Omnirad907, manufactured by IGM Resins, solids concentration 100%)
(離型層形成組成物Y4) 甲基乙基酮 47.361 質量份 甲苯 47.361 質量份 陽離子硬化型聚二甲基矽氧烷(a)： 側鏈環氧基改質聚二甲基矽氧烷 0.250質量份 (製品名：KF-101，信越化學工業公司製，固形物濃度100%) 不具聚矽氧骨架之陽離子硬化型樹脂(b)： 3官能環氧樹脂 4.750質量份 (製品名：Denacol EX-421，Nagasechemtex公司製，固形物濃度100%) 酸產生劑(c) 0.278質量份 (製品名：UVCATA211，荒川化學工業公司製，固形物濃度18%) (Release layer forming composition Y4) Methyl ethyl ketone 47.361 parts by mass Toluene 47.361 parts by mass Cationic hardening polydimethylsiloxane (a): Side chain epoxy modified polydimethylsiloxane 0.250 parts by mass (Product name: KF-101, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) Cationic hardening resin (b) without polysiloxane skeleton: 3 functional epoxy resins 4.750 parts by mass (Product name: Denacol EX-421, manufactured by Nagasechemtex Co., Ltd., solid content concentration 100%) Acid generator (c) 0.278 parts by mass (Product name: UVCATA211, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 18%)
(疏水化層形成組成物Z1) 甲基乙基酮 69.766質量份 甲苯 29.900質量份 陽離子硬化型聚二甲基矽氧烷(a)： 含脂環式環氧基之聚二甲基矽氧烷 0.316質量份 (製品名：SILCOLEASE UV POLY200，荒川化學工業公司製，固形物濃度100%) 酸產生劑(c) 0.018質量份 (製品名：UVCATA211，荒川化學工業公司製，固形物濃度18%) (Hydrophobic layer forming composition Z1) Methyl ethyl ketone 69.766 parts by mass Toluene 29.900 parts by mass Cationic hardening polydimethylsiloxane (a): Alicyclic epoxy-containing polydimethylsiloxane 0.316 parts by mass (Product name: SILCOLEASE UV POLY200, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 100%) Acid generator (c) 0.018 parts by mass (Product name: UVCATA211, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 18%)
(疏水化層形成組成物Z2) 甲基乙基酮 71.041質量份 甲苯 23.681質量份 陽離子硬化型聚二甲基矽氧烷(a) 0.250質量份 (製品名：SILCOLEASE UV POLY200，荒川化學工業公司製，固形物濃度100%) 不具聚矽氧骨架之陽離子硬化型樹脂(b)： 2官能脂環式環氧單體 4.750質量份 (製品名：Celloxide2021P，Daicel公司製，固形物濃度100%) 酸產生劑(c) 0.278質量份 (製品名：UVCATA211，荒川化學工業公司製，固形物濃度18%) (Hydrophobic layer forming composition Z2) Methyl ethyl ketone 71.041 parts by mass Toluene 23.681 parts by mass Cationic hardening polydimethylsiloxane (a) 0.250 parts by mass (Product name: SILCOLEASE UV POLY200, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 100%) Cationic hardening resin (b) without polysiloxane skeleton: 2 functional alicyclic epoxy monomers 4.750 parts by mass (Product name: Celloxide 2021P, manufactured by Daicel Corporation, solid content concentration 100%) Acid generator (c) 0.278 parts by mass (Product name: UVCATA211, manufactured by Arakawa Chemical Industry Co., Ltd., solid content 18%)
(疏水化層形成組成物Z3) 甲基乙基酮 47.361質量份 甲苯 47.361質量份 不具聚矽氧骨架之陽離子硬化型樹脂(b)： 2官能脂環式環氧單體 5.000質量份 (製品名：Celloxide2021P，Daicel公司製，固形物濃度100%) 酸產生劑(c) 0.278質量份 (Hydrophobic layer forming composition Z3) Methyl ethyl ketone 47.361 parts by mass Toluene 47.361 parts by mass Cationic hardening resin (b) without polysiloxane skeleton: 2 functional alicyclic epoxy monomers 5.000 parts by mass (Product name: Celloxide 2021P, manufactured by Daicel Corporation, solid content concentration 100%) Acid generator (c) 0.278 parts by mass
(離型層之形成方法) 將離型層形成組成物Y1至離型層形成組成物Y4以乾燥後之膜厚成為預定厚度的方式利用逆向凹版塗布機來塗布於積層膜X1之表面層A上或是積層膜X2之一面。繼而，以90℃之熱風乾燥20秒後，立即以無電極燈(Heraeus公司製H燈泡)進行紫外線照射(100mJ/cm 2)，形成離型層。離型層之形成係以輥對輥方式進行。亦即，捲出輥狀積層膜，依序連續地進行塗布、乾燥、紫外線照射，捲取成輥狀，藉此獲得設置有離型層之離型膜輥。 (Method for forming release layer) Release layer forming composition Y1 to release layer forming composition Y4 are coated on surface layer A of laminated film X1 with a reverse gravure coater so that the film thickness after drying becomes a predetermined thickness or one side of the laminated film X2. Next, after drying with hot air at 90° C. for 20 seconds, ultraviolet irradiation (100 mJ/cm 2 ) was immediately performed with an electrodeless lamp (H bulb manufactured by Heraeus Co., Ltd.) to form a release layer. The release layer is formed in a roll-to-roll manner. That is, a roll-shaped laminated film is unwound, coated, dried, and ultraviolet ray irradiated sequentially and continuously, and wound up into a roll to obtain a release film roll provided with a release layer.
(疏水化層之形成方法) 將疏水化層形成組成物Z1至疏水化層形成組成物Z3以乾燥後之膜厚成為預定厚度的方式利用逆向凹版塗布機來塗布於基材膜之未設置離型層之面。繼而，以90℃之熱風乾燥20秒之後，立即以無電極燈 (Heraeus公司製H燈泡)進行紫外線照射(100mJ/cm 2)，形成疏水化層。疏水化層之形成係以輥對輥方式進行。亦即，捲出設置有離型層之離型膜輥，依序連續地進行塗布、乾燥、紫外線照射，捲取成輥狀，藉此獲得設置有離型層與疏水化層之離型膜輥。 (Method for forming a hydrophobized layer) The hydrophobized layer-forming composition Z1 to the hydrophobized layer-forming composition Z3 are coated on the substrate film without a release layer using a reverse gravure coater so that the film thickness after drying becomes a predetermined thickness. The surface of the type layer. Subsequently, after drying with hot air at 90° C. for 20 seconds, ultraviolet irradiation (100 mJ/cm 2 ) was immediately performed with an electrodeless lamp (H bulb manufactured by Heraeus Co., Ltd.) to form a hydrophobized layer. The formation of the hydrophobized layer is carried out in a roll-to-roll manner. That is, the release film roll provided with the release layer is rolled out, coated, dried, and irradiated with ultraviolet rays sequentially and continuously, and wound into a roll shape, thereby obtaining a release film provided with a release layer and a hydrophobic layer roll.
(實施例1) 於積層膜X1之表面層A上塗布離型層形成組成物Y1，形成離型層之後，於表面層B上塗布疏水化層形成組成物Z1，形成疏水化層，藉此獲得樹脂片成型用離型膜輥。離型層、疏水化層之厚度係以成為表1所示數值的方式來形成。從所得之離型膜輥捲出並採集離型膜樣品，實施各評價。膜構成、各種物性值係表示於表1A。 (Example 1) Coating the release layer forming composition Y1 on the surface layer A of the laminated film X1 to form a release layer, coating the hydrophobic layer forming composition Z1 on the surface layer B to form a hydrophobic layer, thereby obtaining resin sheet molding Release film roll. The thicknesses of the release layer and the hydrophobized layer were formed so as to be the values shown in Table 1. The release film sample was unwound from the obtained release film roll, and each evaluation was implemented. The film constitution and various physical property values are shown in Table 1A.
(實施例2至實施例11) 以成為表1所示基材膜、離型層、疏水化層之組合的方式，以和實施例1同樣的方法來獲得樹脂片成型用離型膜輥。從所得之離型膜輥捲出並採集離型膜樣品，實施各評價。膜構成、各種物性值係表示於表1A或是表1B。 (Example 2 to Example 11) The release film roll for resin sheet molding was obtained by the method similar to Example 1 so that it may become the combination of the base film, release layer, and hydrophobization layer shown in Table 1. The release film sample was unwound from the obtained release film roll, and each evaluation was implemented. The film composition and various physical property values are shown in Table 1A or Table 1B.
本案發明由於在基材膜當中和離型層為相反側之面設置有疏水化層，故以輥狀態保管離型膜時，離型層與疏水化層會接觸，而不用擔心水分所致離型層之硬化不良，具有優異之剝離性。此外，由於在離型層與疏水化層之兩面含有陽離子硬化型聚二甲基矽氧烷，故可抑制從輥狀態捲出時之帶電。因此，本發明例如可抑制步驟中之極微小環境異物、分切時所產生之膜屑等因静電而附著，可抑制樹脂片之污染。此外，對於例如厚度為0.2μm以上至1.0μm以下之樹脂片可抑制剝離帶電，能以低剝離力進行剝離。In the invention of this case, since a hydrophobic layer is provided on the side opposite to the release layer in the base film, when the release film is stored in a roll state, the release layer and the hydrophobic layer will be in contact, and there is no need to worry about separation caused by moisture. The hardening of the type layer is poor, and it has excellent peelability. In addition, since the release layer and the hydrophobizing layer contain cation-curing polydimethylsiloxane on both sides, it can suppress the electrification when it is unwound from the roll state. Therefore, the present invention, for example, can suppress the adhesion of very small environmental foreign matter in the process, film scraps generated during slitting, etc. due to static electricity, and can suppress the pollution of the resin sheet. In addition, for a resin sheet having a thickness of, for example, 0.2 μm or more and 1.0 μm or less, peeling electrification can be suppressed, and peeling can be performed with a low peeling force.
(比較例1至比較例5) 以成為表1所示基材膜、離型層、疏水化層之組合的方式，以和實施例1同樣的方法來獲得樹脂片成型用離型膜。比較例1至比較例4係使用未設置疏水化層而設置有離型層之離型膜輥來實施各評價。膜構成、各種物性值係表示於表1B。 (Comparative Example 1 to Comparative Example 5) A release film for resin sheet molding was obtained in the same manner as in Example 1 so as to be a combination of the base film, the release layer, and the hydrophobization layer shown in Table 1. In Comparative Examples 1 to 4, each evaluation was implemented using a release film roll provided with a release layer instead of a hydrophobizing layer. The film constitution and various physical property values are shown in Table 1B.
比較例1中，由於離型層中不含陽離子硬化型聚二甲基矽氧烷(a)，而為使用了自由基硬化型樹脂之離型層，故發生了氧阻礙所致硬化不良，加熱後剝離力(II)與常態剝離力(I)之比(II)/(I)大，出現剝離性之惡化。此外，捲出帶電也高。比較例2至比較例4由於不具疏水化層(水接觸角為90°以上至130°以下之疏水化層)，故以輥狀態保管離型膜之時會因為水分之影響使得離型層之經時反應受到阻礙而成為硬化不良，出現剝離性之惡化。此外，捲出帶電也高。比較例5中，由於疏水化層之水接觸角為90℃以下，故離型膜以輥狀態保管時，離型層之硬化阻礙抑制功效不充分，出現剝離性與捲出帶電之惡化。In Comparative Example 1, since the release layer did not contain cation-curable polydimethylsiloxane (a), but used a free-radical-curable resin, poor curing occurred due to oxygen barrier. The ratio (II)/(I) of the peeling force (II) after heating to the normal peeling force (I) is large, and the peelability deteriorates. In addition, unwinding electrification is also high. Comparative Examples 2 to 4 do not have a hydrophobized layer (a hydrophobized layer with a water contact angle of more than 90° and less than 130°), so when the release film is stored in a roll state, the release layer will be affected by moisture. The reaction over time is hindered, resulting in poor hardening and deterioration of peelability. In addition, unwinding electrification is also high. In Comparative Example 5, since the water contact angle of the hydrophobized layer was 90°C or less, when the release film was stored in a roll state, the hardening inhibition suppression effect of the release layer was insufficient, and the detachability and roll-out electrification deteriorated.
依據本發明，於基材膜之一面具有離型層，於基材膜之反離型面設置疏水層，藉此，可提供一種剝離性優異、捲出帶電低之離型膜，可在不用擔心發生不良的前提下製造出厚度為1μm以下之超薄層樹脂片。According to the present invention, there is a release layer on one side of the substrate film, and a hydrophobic layer is provided on the opposite release surface of the substrate film, whereby a release film with excellent peelability and low roll-out charge can be provided, which can be used without On the premise of worrying about defects, ultra-thin resin sheets with a thickness of 1 μm or less are manufactured.
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021108802 | 2021-06-30 | ||
| JP2021-108802 | 2021-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW202304715A true TW202304715A (en) | 2023-02-01 |
| TWI827104B TWI827104B (en) | 2023-12-21 |
Family
ID=84691426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW111123149A TWI827104B (en) | 2021-06-30 | 2022-06-22 | Release film for resin sheet molding and method for manufacturing ceramic green embryo |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2023276892A1 (en) |
| KR (1) | KR20230164151A (en) |
| CN (1) | CN117561165A (en) |
| TW (1) | TWI827104B (en) |
| WO (1) | WO2023276892A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013073700A (en) * | 2011-09-27 | 2013-04-22 | Mitsubishi Plastics Inc | Double-sided mold release film for fuel cell |
| US20150037536A1 (en) | 2012-03-28 | 2015-02-05 | Lintec Corporation | Release film for ceramic green sheet production process |
| JP2017002254A (en) * | 2015-06-16 | 2017-01-05 | 三菱樹脂株式会社 | Laminated polyester film |
| KR20190062423A (en) | 2016-10-27 | 2019-06-05 | 린텍 가부시키가이샤 | Peeling sheet |
| JP7035441B2 (en) * | 2017-10-12 | 2022-03-15 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| KR102518776B1 (en) * | 2017-12-27 | 2023-04-10 | 도요보 가부시키가이샤 | Release Film for Ceramic Green Sheet Manufacturing |
| JP7334416B2 (en) * | 2019-02-12 | 2023-08-29 | 三菱ケミカル株式会社 | release film |
| JP7434800B2 (en) * | 2019-10-29 | 2024-02-21 | 東洋紡株式会社 | Polyester film for laser processing supports and release film for manufacturing wiring boards |
-
2022
- 2022-06-22 TW TW111123149A patent/TWI827104B/en active
- 2022-06-24 JP JP2023531907A patent/JPWO2023276892A1/ja active Pending
- 2022-06-24 CN CN202280045293.8A patent/CN117561165A/en active Pending
- 2022-06-24 KR KR1020237037517A patent/KR20230164151A/en unknown
- 2022-06-24 WO PCT/JP2022/025370 patent/WO2023276892A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023276892A1 (en) | 2023-01-05 |
| CN117561165A (en) | 2024-02-13 |
| TWI827104B (en) | 2023-12-21 |
| KR20230164151A (en) | 2023-12-01 |
| JPWO2023276892A1 (en) | 2023-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6414424B2 (en) | Release film for ceramic sheet production | |
| CN110312602B (en) | Release film for producing ceramic green sheet and method for producing same | |
| WO2012144366A1 (en) | Releasing film for ceramic green sheet production processes | |
| TWI811907B (en) | Release film for resin sheet molding | |
| CN112672866B (en) | Release film for producing ceramic green sheet | |
| JP7409465B2 (en) | Laminated film and method for manufacturing laminated film | |
| JP7006710B2 (en) | Release film for manufacturing ceramic green sheets | |
| KR101600104B1 (en) | Mould release film | |
| JP7144715B2 (en) | Release film roll for manufacturing ceramic green sheets | |
| TW202112924A (en) | Biaxially oriented polyester film | |
| JP7306516B2 (en) | Release film for manufacturing ceramic green sheets | |
| TW202304715A (en) | Release film for molding resin sheets | |
| TWI799022B (en) | Manufacturing method of release film for resin sheet molding and manufacturing method of ceramic green body | |
| JP7106912B2 (en) | Release film for manufacturing ceramic green sheets | |
| WO2020261910A1 (en) | Release film for manufacturing ceramic green sheet | |
| TWI845217B (en) | Release film for resin sheet molding | |
| JP7327554B2 (en) | Release film for manufacturing ceramic green sheets | |
| JP7306514B2 (en) | Release film for manufacturing ceramic green sheets | |
| JP7306515B2 (en) | Release film for manufacturing ceramic green sheets | |
| TW202231489A (en) | Mold release film for resin sheet molding | |
| KR20120139190A (en) | Release film for making multilayer ceramic capacitor and manufacturing method thereof |