CN116635160A - Method for producing release film for molding resin sheet - Google Patents
Method for producing release film for molding resin sheet Download PDFInfo
- Publication number
- CN116635160A CN116635160A CN202180086596.XA CN202180086596A CN116635160A CN 116635160 A CN116635160 A CN 116635160A CN 202180086596 A CN202180086596 A CN 202180086596A CN 116635160 A CN116635160 A CN 116635160A
- Authority
- CN
- China
- Prior art keywords
- release layer
- release
- film
- layer
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 112
- 239000011347 resin Substances 0.000 title claims abstract description 112
- 238000000465 moulding Methods 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 239000010410 layer Substances 0.000 claims abstract description 291
- 238000001035 drying Methods 0.000 claims abstract description 150
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 142
- 239000011254 layer-forming composition Substances 0.000 claims abstract description 102
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 81
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 81
- 239000002344 surface layer Substances 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 229920006267 polyester film Polymers 0.000 claims abstract description 35
- 239000010954 inorganic particle Substances 0.000 claims abstract description 19
- 238000000016 photochemical curing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims description 91
- 239000003960 organic solvent Substances 0.000 claims description 26
- 150000002484 inorganic compounds Chemical class 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- 239000010408 film Substances 0.000 description 177
- 125000002091 cationic group Chemical group 0.000 description 69
- 239000002245 particle Substances 0.000 description 50
- 238000001723 curing Methods 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 33
- 229920000139 polyethylene terephthalate Polymers 0.000 description 24
- 239000005020 polyethylene terephthalate Substances 0.000 description 24
- 125000003700 epoxy group Chemical group 0.000 description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- 238000012545 processing Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 125000002723 alicyclic group Chemical group 0.000 description 19
- 238000004220 aggregation Methods 0.000 description 18
- 230000002776 aggregation Effects 0.000 description 18
- 230000007547 defect Effects 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000003746 surface roughness Effects 0.000 description 10
- 239000008188 pellet Substances 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
- 239000007788 liquid Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 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
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000004931 aggregating effect 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
- 238000007611 bar coating method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 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 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 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
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100029848 Arabidopsis thaliana PIP1-2 gene Proteins 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000003917 TEM image 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001454 anthracenes Chemical class 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007667 floating 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
- 238000009998 heat setting Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 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
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 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
- 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
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- 125000002524 organometallic group Chemical group 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
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 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
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
Abstract
The purpose of the present invention is to provide a release film having a release layer that is particularly excellent in smoothness and peelability. A method for producing a release film for molding a resin sheet, comprising the steps of: a coating step of coating a release layer forming composition on the surface layer a of a polyester film having the surface layer a, wherein the surface layer a is a layer substantially free of inorganic particles, and the release layer forming composition comprises at least a cationically curable polydimethylsiloxane (a); a drying step of heating and drying the polyester film coated with the release layer forming composition, wherein the heating and drying comprises a 1 st drying step and a 2 nd drying step, and the drying temperature T1 in the 1 st drying step is higher than the drying temperature T2 in the 2 nd drying step; and a photo-curing step of irradiating the release layer-forming composition with active energy rays after the drying step.
Description
Technical Field
The present invention relates to a method for producing a release film for molding resin sheets, and more particularly to a method for producing a release film used for molding ultra-thin resin sheets.
Background
Conventionally, a release film having a release layer laminated thereon is used as a process film for molding a resin sheet such as an adhesive sheet, a cover film, a polymer film, or an optical lens, using a polyester film as a base material.
The release film is also used as a process film for molding ceramic green sheets, such as multilayer ceramic capacitors and ceramic substrates, which require high smoothness. In recent years, along with miniaturization and increase in capacity of multilayer ceramic capacitors, the thickness of ceramic green sheets tends to be thin. The ceramic green sheet is formed by applying a slurry containing a ceramic component such as barium titanate and a binder resin to a release film and drying the same. The multilayer ceramic capacitor is manufactured by laminating, pressing, firing, and coating external electrodes on a ceramic green sheet obtained by printing electrodes on a molded ceramic green sheet and peeling from a release film.
When a ceramic green sheet is molded on the surface of a release layer of a polyester film base material, the molded ceramic green sheet is affected by minute protrusions on the surface of the release layer, and there is a disadvantage that shrinkage holes, pinholes, and the like are easily generated. In recent years, with the progress of thinning of ceramic green sheets, ceramic green sheets having a thickness of 1.0 μm or less, more specifically, 0.2 μm to 1.0 μm have been demanded. The requirements relating to the smoothness of the release layer surface become higher. Further, extremely small protrusions and foreign matters on the release layer cause deformation of the molded ceramic green sheet, and there are technical problems such as occurrence of pinholes and sheet breakage during peeling.
In addition, with the progress of thinning of ceramic green sheets, the releasability at the time of releasing ceramic green sheets from a release film becomes more important. If the peeling force is large and uneven, there are the following problems: in the peeling step, the ceramic green sheet is damaged, sheet defects and uneven thickness occur, and defects such as pinholes and sheet breakage occur. Therefore, it is also required to peel the ceramic green sheet with a lower uniform force. That is, in order to produce an ultra-thin resin sheet, particularly a ceramic green sheet, without defects, a release film having extremely high smoothness and excellent releasability is required.
The following patent documents are cited as release films having excellent smoothness and peelability. For example, patent document 1 proposes a release film having a release layer containing a radical curable resin as a main component. Patent document 2 proposes a release film having a structure in which a smoothing layer and a release layer are laminated. Patent document 3 proposes a release film having a release layer containing a cationic curable epoxy resin as a main component. Patent document 4 proposes a release film having a release layer containing a cationic curable polydimethylsiloxane as a main component.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5492352
Patent document 2: japanese patent application laid-open No. 2015-164762
Patent document 3: international publication No. 2018/079337
Patent document 4: japanese patent laid-open publication 2016-079349
Disclosure of Invention
Problems to be solved by the invention
However, in the release film of patent document 1, since the release layer is provided for the base film having insufficient smoothness, there is a problem that the smoothness of the release layer is insufficient. Further, as a result of intensive studies, the present inventors have found that a radically curable resin causes poor curing due to oxygen inhibition, and therefore the solvent resistance of the surface of the release layer is poor, and there is a problem that the release layer is corroded by an organic solvent used when forming a ceramic green sheet or when printing an internal electrode, and the releasability is poor.
In the solution of patent document 2, a thermosetting melamine resin is used for the smoothing coat layer and the release coat layer, and a high temperature is required to promote the curing reaction. Therefore, the flatness of the release film may be impaired by heat during processing. Further, since a plurality of processes for smoothing the coating layer and the release coating layer are required, not only may foreign matters be mixed into the release film, but also scratches may be generated in the release layer, and the foreign matters and scratches may be transferred to the ceramic green sheet molded on the release layer, and thus, defects may be generated.
Patent documents 3 and 4 propose release layers using a cationic curable resin, respectively, in order to improve curing failure due to oxygen inhibition and plane failure due to processing heat. However, in the release film of patent document 3, the smoothness of the base film is poor, and thus there is a problem that the smoothness of the release layer surface is poor. In addition, the release agent disclosed in patent document 3 lacks reactivity, has poor solvent resistance, and has a problem in releasability.
In the release film of patent document 4, since the release layer is provided with a liquid cationic curable polydimethylsiloxane resin as a main component, the resin may be accumulated in the irregularities of the base film or protrusions of an oligomer or the like present on the surface of the base film, and thus there is a possibility that the flatness may be problematic. In addition, the release layer has a low crosslinking density and has a problem in releasability.
The present invention has been completed in view of these prior art problems. That is, an object of the present invention is to provide a method for producing a release film, which can provide a release film having a release layer that is particularly excellent in smoothness and releasability, and which can further form an ultra-thin resin sheet, particularly an ultra-thin ceramic green sheet, without defects.
Further, the present invention provides a method for producing a release film, which can suppress curing failure due to oxygen inhibition and can improve plane failure due to processing heat in the release film that solves the above-described problems.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned object can be achieved by a method for producing a release film having the following structure, and have completed the present invention.
That is, the present invention includes the following constitution.
[1] The invention provides a method for manufacturing a release film for molding a resin sheet.
The method for producing a release film for molding a resin sheet comprises the following steps:
a coating step of coating a release layer forming composition on the surface layer A of a polyester film having the surface layer A, wherein,
the surface layer a is a layer substantially free of inorganic particles,
the release layer forming composition comprises a cationically curable polydimethylsiloxane (a);
a drying step of heating and drying the polyester film coated with the release layer forming composition,
the heat drying includes a 1 st drying step and a following 2 nd drying step,
The drying temperature T1 in the 1 st drying procedure is higher than the drying temperature T2 in the 2 nd drying procedure;
and a photo-curing step of irradiating the release layer-forming composition with active energy rays after the drying step.
[2] In one embodiment, the release layer forming composition comprises an organic solvent having an SP value (delta) of 14 or more and 17 or less,
the release layer-forming composition contains an organic solvent having an SP value (delta) of 14 to 17 in an amount of 10 mass% or more with respect to 100 mass parts of the total weight of the release layer-forming composition,
the coating amount of the release layer-forming composition in the coating step was 10g/m 2 The following is given.
[3] In one embodiment, a method for producing a release film for producing a resin sheet containing an inorganic compound is provided.
[4] In one embodiment, a method for producing a release film for molding a resin sheet is provided, wherein the resin sheet containing an inorganic compound is a ceramic green sheet.
[5] In one embodiment, a method for producing a ceramic green sheet is provided, which further comprises a step of forming a ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less in the method for producing a release film for molding a resin sheet.
[6] In one embodiment, a method for producing a release film for molding a resin sheet is provided, which comprises a step of molding a resin sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
ADVANTAGEOUS EFFECTS OF INVENTION
The release film obtained by the method for producing a release film for molding a resin sheet of the present invention can improve the smoothness and peelability of the release layer, and further can suppress the occurrence of defects in an ultra-thin resin sheet, particularly in a ceramic green sheet.
Further, according to the method for producing a release film for molding a resin sheet of the present invention, the deterioration of the flatness of the release film due to heat during processing can be suppressed. Further, the production method of the present invention can suppress aggregation of the release layer forming composition in the coating step and the drying step, and can form a release layer having extremely high smoothness.
Detailed Description
The present invention will be described in detail below.
The present invention can produce a release film having the following constitution.
A release film for molding a resin sheet, comprising a polyester film as a base material and a release layer,
the polyester film has a surface layer a substantially free of inorganic particles,
a release layer is provided on the surface layer a,
the release layer is a layer formed by curing the release layer forming composition,
The release layer forming composition comprises a cationically curable polydimethylsiloxane (a),
the surface roughness (Sa) of the area of the release layer is below 2nm,
the number of protrusions having a height of 10nm or more and present on the surface of the release layer was 200/mm 2 The following is given.
The release film produced by the present invention having such a constitution is excellent in smoothness and peelability of the release layer, and therefore, for example, a resin sheet having a thickness of 0.2 μm to 1.0 μm or less can provide a uniform thickness without defects, and can suppress pinholes and the like.
In addition, the release film produced by the present invention can have the following effects. In the present invention, since the release layer is provided on the base film having sufficient smoothness, the smoothness of the release layer can be ensured. Further, the present invention can suppress curing failure due to oxygen inhibition in the release layer, and can exhibit high crosslinking of the release layer. The present invention exhibiting 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, the release layer can be prevented from being corroded by the organic solvent used in the formation of the ceramic green sheet and in the internal electrode printing, and can have high releasability.
In the present invention, for example, a high temperature for accelerating the curing reaction is not required compared with a release layer of a melamine resin having thermosetting properties. Therefore, the flatness of the release film can be prevented from being impaired by heat during processing. In addition, in the production method of the present invention, aggregation of the release layer forming composition can be suppressed by the coating step and the drying step of the present invention, and a release film having a release layer with extremely high smoothness can be obtained.
More specifically, a release layer having extremely high smoothness can be obtained by applying a release layer-forming composition containing a predetermined amount of a cationically curable polydimethylsiloxane (a) to a surface layer a of a base film that is substantially free of inorganic particles and curing the composition.
Further, by controlling the content of the cationic curable polydimethylsiloxane (a) in the release layer to a predetermined amount or less, it is possible to suppress aggregation of the cationic curable polydimethylsiloxane (a) to very small foreign matters and fine protrusions derived from the oligomer existing in the base film at the time of processing the release layer. Although not limited to a specific theory, the aggregation of the component (a) to fine protrusions caused by the roll can be prevented by increasing the 1 st drying temperature (by enhancing the drying).
In addition, by suppressing curing failure due to oxygen polymerization inhibition, improving solvent resistance of the surface of the release layer, suppressing the mixing of foreign matters into the release layer, and suppressing scratches of the release layer, it is possible to prevent deformation of the sheet due to damage to the release object such as a ceramic green sheet, scratches, transfer of foreign matters, and the like at the time of peeling. As a result, a release layer excellent in smoothness, hardness, peelability, and stain resistance to the release layer can be obtained.
In addition, in the drying of the organic solvent contained in the release layer forming composition, the cationic curable polydimethylsiloxane (a) becomes less likely to aggregate, and a release layer excellent in smoothness can be produced. Details will be described later.
The present invention also provides a method for producing a release film for molding a resin sheet, comprising the following steps.
A coating step of coating a release layer forming composition on the surface layer A of a polyester film having the surface layer A, wherein,
the surface layer a is a layer substantially free of inorganic particles,
the release layer forming composition comprises at least a cationically curable polydimethylsiloxane (a);
a drying step of heating and drying the polyester film coated with the release layer forming composition,
The heat drying comprises a 1 st drying process and a following 2 nd drying process, wherein the drying temperature T1 in the 1 st drying process is higher than the drying temperature T2 in the 2 nd drying process;
and a photo-curing step of irradiating the release layer-forming composition with active energy rays after the drying step.
In the production method of the present invention, particularly, by setting the production conditions in processing the release layer to a predetermined method, a release layer having high smoothness can be formed, and examples thereof include controlling the coating amount, organic solvent component, drying time, drying temperature, and the like of the release layer forming composition. By producing the release film under the conditions of the present invention, aggregation of the cationic curable polydimethylsiloxane (a) contained in the composition for forming a release layer can be suppressed, and a release layer excellent in smoothness can be obtained. Details will be described later.
(polyester film)
The polyester constituting the polyester film used as the base material of the present invention is not particularly limited, and a polyester obtained by film-molding a polyester which is generally used as a base material for a release film can be used. Crystalline linear saturated polyesters composed of an aromatic dibasic acid and a diol component are preferable, and for example, polyethylene terephthalate, polyethylene 2, 6-naphthalate, polybutylene terephthalate, polypropylene terephthalate, or a copolymer composed mainly of the constituent components of these resins is more preferable, and particularly a polyester film composed of polyethylene terephthalate is preferable. The repeating unit of polyethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and other dicarboxylic acid component and diol component may be copolymerized in a small amount, and from the viewpoint of cost, polyethylene terephthalate produced from only terephthalic acid and ethylene glycol is preferable. In addition, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents, and the like may be added within a range that does not hinder the effects of the film of the present invention. The polyester film is preferably a biaxially oriented polyester film from the viewpoint of the high or low elastic modulus in both directions.
The intrinsic viscosity of the polyester film is preferably 0.50 to 0.70dl/g, more preferably 0.52 to 0.62dl/g. When the intrinsic viscosity is 0.50dl/g or more, a large amount of breakage does not occur in the stretching step, and therefore, it is preferable. In contrast, if the ratio is 0.70dl/g or less, the cutting property is good when the sheet is cut into a predetermined product width, and no dimensional defect occurs, so that it is preferable. In addition, the raw material pellets are preferably sufficiently vacuum-dried.
In the present specification, the term "polyester film" refers to a polyester film having (laminated with) a surface layer a. In the present invention, the polyester film has a surface layer a substantially free of inorganic particles, and the release layer is provided on the surface layer a.
In the case of the description, a polyester film further having (laminated with) a surface layer B is sometimes simply referred to as a "polyester film".
The method for producing the polyester film of the present invention is not particularly limited, and a conventionally generally used method can be used. For example, the polyester may be melted in an extruder, extruded into a film shape, cooled by a rotary cooling drum to obtain an unstretched film, and the unstretched film is stretched. The stretching is preferably biaxial stretching in view of mechanical properties and the like. The biaxially stretched film may be obtained by a method of biaxially stretching a uniaxially stretched film in the machine direction or the transverse direction in order in the transverse direction or a method of biaxially stretching an unstretched film simultaneously in the machine direction and the transverse direction.
In the present invention, the stretching temperature at the time of stretching the polyester film is preferably equal to or higher than the second transition point (Tg) of the polyester. The stretching is preferably performed in each of the longitudinal direction and the transverse direction by 1 to 8 times, particularly by 2 to 6 times.
The thickness of the polyester film is preferably 12 to 50. Mu.m, more preferably 15 to 38. Mu.m, and still more preferably 19 to 33. Mu.m. If the film thickness is 12 μm or more, it is preferable that the film is not deformed by heat during the film production, the processing step of the release layer, the molding of the ceramic green sheet, etc. On the other hand, if the film thickness is 50 μm or less, the amount of the film to be discarded after use does not become extremely large, and it is preferable in terms of reducing the environmental load.
The polyester film may be a single layer or a plurality of layers of 2 or more layers. The polyester film has a surface layer a substantially free of inorganic particles. For example, the surface layer a may be a single layer, or a multilayer structure including the surface layer a and another layer, for example, a surface layer B described later.
In the case of a laminated polyester film having a multilayer structure of 2 or more layers, it is preferable that the surface layer B which may contain particles or the like is provided on the opposite side of the surface layer a which does not substantially contain inorganic particles. In the laminated structure, when the layer on the side where the release layer is applied is the surface layer a, the layer on the opposite side is the surface layer B, and the core layer other than the surface layer is the layer C, the laminated structure such as the release layer/a/B, the release layer/a/C/B, and the like can be given as the layer structure in the thickness direction. Of course, the layer C may have a plurality of layers. The surface layer B may not contain particles. In this case, in order to impart slidability for winding the film into a roll, it is preferable to provide the surface layer B with a coating layer containing particles and a binder.
In the polyester film of the present invention, the surface layer a located on the surface of the coating release layer is substantially free of inorganic particles. In the present invention, the surface layer a is substantially free of inorganic particles, and thus can exhibit the following area surface average roughness.
In the present invention, the surface average roughness (Sa) of the surface layer A is the surface average roughness (Sa) of the surface where the release layer is disposed, and the surface average roughness (Sa) of the surface where the release layer is disposed is 7nm or less. When Sa is 7nm or less, the release layer laminated on the surface layer a can exhibit high smoothness, and pinholes and the like are less likely to occur when the ultra-thin ceramic green sheet laminated on the release layer is molded. Further, when the release layer is formed, the protrusion of the release layer component onto the surface layer a can be suppressed, and deterioration of the smoothness of the release layer surface can be prevented.
The smaller the area surface average roughness (Sa) of the surface layer a is, the more preferably, 0.1nm or more. In one embodiment, the surface layer a has a region surface average roughness (Sa) of 0.1nm to 7nm, for example, 0.5nm to 5nm, 0.5nm to 4 nm. By having such a range, smoothness of the release layer can be improved, and occurrence of pinholes and the like can be suppressed at the time of molding the laminated ultrathin ceramic green sheet. Further, when forming the release layer, the protrusion of the release layer component onto the surface layer a can be suppressed, and deterioration of the smoothness of the release layer surface can be prevented.
In the present invention, "substantially free of inorganic particles" means a content of 50ppm or less, preferably 10ppm or less, and most preferably a content of a detection limit or less when inorganic elements are quantified by fluorescent X-ray analysis. This is because, even if inorganic particles are not actively added to the film, there are cases where contamination components from foreign matters, contamination adhering to the raw material resin or the production line in the process of producing the film, and contamination on the device are mixed into the film.
In the polyester film base material of the present invention, the surface layer B may be provided on the surface opposite to the surface on which the release layer is provided. The surface layer B preferably contains particles. By containing the particles, the slidability of the film and the ease of air discharge are excellent, and excellent transportability and windability can be obtained. Particularly preferably comprising silica particles and/or calcium carbonate particles.
The amount of particles contained in the surface layer B is 1000 to 15000ppm in total. At this time, the area surface average roughness (Sa) of the thin film of the surface layer B is, for example, 1nm to 40 nm. More preferably from 5nm to 35 nm. When the total amount of silica particles and/or calcium carbonate particles is 1000ppm or more and Sa is 1nm or more, air can be uniformly released when the film is wound into a roll shape, and the winding posture can be made good, so that the flatness can be improved. According to such a feature, for example, in the case of manufacturing a resin sheet having an ultrathin layer of 0.2 μm or more and 1.0 μm or less, for example, a ceramic green sheet, wrinkling and positional displacement of the ceramic green sheet to be wound can be prevented, and a release film excellent in transportability, winding and storage properties can be provided.
In addition, even when the total amount of silica particles and/or calcium carbonate particles is 15000ppm or less and Sa is 40nm or less, particles functioning as a lubricant are less likely to aggregate and coarse protrusions (for example, protrusions having a height of 1 μm or more) cannot be formed, so that, for example, in the case of producing an ultra-thin resin sheet such as a ceramic green sheet, pinholes due to winding can be suppressed, and a resin sheet with stable quality can be provided.
As the particles contained in the surface layer B, inactive inorganic particles and/or heat-resistant organic particles, etc. may be used in addition to silica and/or calcium carbonate. Silica particles and/or calcium carbonate particles are preferably used from the viewpoint of transparency and cost. Examples of other usable inorganic particles include alumina-silica composite oxide particles and hydroxyapatite particles. Examples of the heat-resistant organic particles include crosslinked polyacrylic acid particles, crosslinked polystyrene particles, and benzoguanamine particles. In addition, in the case of using silica particles, porous colloidal silica is preferable. In the case of using calcium carbonate particles, light calcium carbonate surface-treated with a polyacrylic polymer compound is preferable from the viewpoint of preventing particle fall-off.
The average particle diameter of the particles added to the surface layer B is preferably 0.1 μm or more and 2.0 μm or less, particularly preferably 0.5 μm or more and 1.0 μm or less. If the average particle diameter of the particles is 0.1 μm or more, the release film is preferable because of good sliding properties. In addition, if the average particle diameter is 2.0 μm or less, deformation of the surface layer a is suppressed, and occurrence of unevenness in thickness and pinholes of the ceramic green sheet can be suppressed.
The surface layer B may contain 2 or more kinds of particles different from each other. The present invention may also contain particles of the same kind having different average particle diameters. In addition, 2 or more different kinds of particles may have different average particle diameters within the above-described range. By containing 2 different types of particles, the irregularities formed in the surface layer B can be highly controlled, and both slidability and smoothness can be achieved, which is preferable.
In the surface layer a, which is a layer on the side where the release layer is provided, it is preferable not to use a recycling material or the like in order to prevent the mixing of particles or impurities from the viewpoint of reducing pinholes.
The thickness ratio of the surface layer a of the layer on the release layer side is preferably 20% to 50% of the total layer thickness of the base film. If it is 20% or more, it is difficult to receive the influence of particles contained in the surface layer B or the like from the inside of the film, and the area surface average roughness Sa can satisfy the above range, so that it is preferable. If the thickness of the entire layer of the base film is 50% or less, the use ratio of the recycled raw material in the surface layer B and the intermediate layer C by coextrusion can be increased, and the environmental load is preferably reduced.
In addition, from the viewpoint of economy, 50 to 90 mass% of film scraps and a recycled material of a plastic bottle may be used for the layer other than the surface layer a (the surface layer B or the intermediate layer C). In this case, the kind, amount, particle diameter, and area surface average roughness (Sa) of the lubricant contained in the surface layer B preferably satisfy the above ranges.
In order to improve the adhesion of a release layer or the like to be applied later, to prevent electrification, etc., a coating layer may be provided on the surface of the surface layer a and/or the surface layer B before stretching or after uniaxial stretching in the film-forming step, or corona treatment may be performed. In the case where a coating layer is provided on the surface layer a, the coating layer is preferably substantially free of particles.
(Release layer)
In the present invention, a release layer is laminated on the surface layer a. In the present invention, the release layer is a layer obtained by curing a release layer-forming composition, the release layer and the release layer-forming composition at least contain a cationic curable polydimethylsiloxane (a), the surface roughness (Sa) of the release layer is 2nm or less, and the number of protrusions present on the surface of the release layer at a height of 10nm or more is 200/mm 2 The following is given.
By providing the release layer with such a feature, occurrence of pinholes in an ultra-thin film resin sheet, for example, a ceramic green sheet, which requires high smoothness, can be suppressed, and a resin sheet having a uniform film thickness can be formed.
More specifically, the present invention can suppress curing failure due to oxygen inhibition in the release layer, and can exhibit high crosslinking of the release layer. The present invention exhibiting 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, the release layer can be prevented from being corroded by the organic solvent used in the formation of the ceramic green sheet and in the internal electrode printing, and can have high releasability.
In addition, the present invention does not require a high temperature of 130 ℃ or higher in order to promote the curing reaction. Therefore, the deterioration of the flatness of the release film due to heat during processing can be suppressed. In addition, the occurrence of scratches on the release film and the release layer for molding the resin sheet can be suppressed, and the occurrence of damage to the body to be removed such as a ceramic green sheet caused by transfer of the impurities and scratches can be suppressed.
The surface roughness (Sa) of the mold release layer is 2nm or less. In addition, the number of protrusions having a height of 10nm or more and existing on the surface of the release layer was 200 protrusions/mm 2 The following is given. The surface of the release layer of the release film has a predetermined condition for the surface average roughness (Sa) of the region and the number of protrusions of 10nm or more so as not to cause defects in the ceramic sheet coated and molded thereon.
The number of protrusions having a surface roughness (Sa) of 2nm or less and a height of 10nm or more is 200/mm 2 In the following, the ceramic sheet is preferable because the ceramic sheet does not have defects such as pinholes and the like during the molding of the ceramic sheet, and the yield is good.
The area surface roughness (Sa) is more preferably 1.7nm or less, for example, 1.6nm or less, or may be 1.5nm or less. In one embodiment, the area surface roughness (Sa) is 1.3nm or less. The area surface roughness (Sa) may be 0.1nm or more, or may be 0.2nm or more.
On the other hand, in one embodiment, the number of protrusions having a height of 10nm or more is 180/mm 2 Hereinafter, for example, 170 pieces/mm 2 Below, 160 pieces/mm may be used 2 The following is given. In one embodiment, the number of protrusions having a height of 10nm or more may be 120/mm 2 Hereinafter, 100 pieces/mm may be used 2 The following is given. In addition, the number of protrusions having a height of 10nm or more may be 1/mm 2 The number of the above may be, for example, 10 pieces/mm 2 The above.
When the number of protrusions having a height of 10nm or more is within the above range, the ceramic sheet does not have the disadvantage of pinholes, and the like, and can have more uniform and excellent releasability.
Further preferably, the number of protrusions having a surface roughness (Sa) of 1.0nm or less and a height of 10nm or more is 100 protrusions/mm 2 The following is given.
The release layer having the area surface average roughness (Sa) and the number of protrusions of the present invention can exhibit extremely excellent smoothness.
In one embodiment, the maximum protrusion height (Sp) of the release layer is 20nm or less. By setting the maximum protrusion height within such a range, defects of the ceramic sheet can be further suppressed. More preferably, the maximum protrusion height (Sp) is 15nm or less, still more preferably 10nm or less.
In one embodiment, the total of the number of protrusions having a height of 5nm or more and less than 10nm and the number of protrusions having a height of 10nm or more, which are present on the surface of the release layer, is 1500 pieces/mm 2 The following is given. By making the total of the number of protrusions with a height of 5nm or more and less than 10nm and the number of protrusions with a height of 10nm or more present on the release layer 1500 pieces/mm 2 Hereinafter, it is preferable to further suppress defects in the ceramic sheet and obtain a release layer having high smoothness.
More preferably, the total of the number of protrusions having a height of 5nm or more and less than 10nm and the number of protrusions having a height of 10nm or more is 1000 pieces/mm 2 Hereinafter, for example, 500 pieces/mm are more preferable 2 The following is given.
The release layer of the release film for molding a resin sheet of the present invention is a layer obtained by curing a release layer-forming composition containing at least a cationically curable polydimethylsiloxane (a). The cationic curable polydimethylsiloxane (a) undergoes a crosslinking reaction by a cationic curing reaction, and thus, curing failure due to oxygen inhibition does not occur, and a release layer excellent in solvent resistance is obtained. Therefore, the release layer is not corroded by the organic solvent used in the molding of the ceramic green sheet, the internal electrode printing, and the like, and the release layer having excellent releasability can be obtained.
Further, the present inventors have found that, in the release layer containing the cationic curable polydimethylsiloxane (a), the amount of the cationic curable polydimethylsiloxane (a) is important for realizing a release layer having high smoothness.
The cationic curable polydimethylsiloxane (a) is preferably present in the release layer at 90mg/m 2 Below, for example 60mg/m 2 Below, 50mg/m 2 The following is included, more preferably 40mg/m 2 The concentration of the above-mentioned components is more preferably 30mg/m 2 The following is given. In addition, for example, the cationic-curable polydimethylsiloxane (a) may be 20mg/m 2 The following is given.
If the content of the cationically curable polydimethylsiloxane (a) in the release layer is 50mg/m 2 Hereinafter, the occurrence of aggregation of the polydimethylsiloxane (a) in the step of forming the release layer, for example, in the drying step, can be suppressed, and the effect of the present invention can be achieved without producing a large amount of protrusions out of the scope of the present invention.
In one embodiment, the release layer and the release layer forming composition may contain components other than the cationic curable polydimethylsiloxane (a). In this case, too, the judgment should not be made based on a specific theory, but in the present invention, the polydimethylsiloxane (a) can be segregated on the surface of the release layer at the time of processing the release layer, and the content is 50mg/m 2 The release layer having high smoothness can be formed because of the difficulty in aggregation as described below.
The content of the polydimethylsiloxane (a) of the invention is smaller and more difficult to aggregate, but if it is 0.1mg/m in the release layer 2 As described above, the leveling property of the release layer can be maintained, and a release layer having excellent coating appearance and high smoothness can be obtained. In addition, if it is 0.1mg/m 2 The above is preferable because the peelability is excellent. For example, the content of polydimethylsiloxane (a) may also be 0.5mg/m 2 The above.
In the present invention, the release layer forming composition contains a cationically curable polydimethylsiloxane (a). In addition, in the release layer formed by curing the release layer forming composition, there is a compound (cured product) derived from the cationic curable polydimethylsiloxane (a). In the present specification, the compound derived from (a) present in the release layer is sometimes simply referred to as a cationic curable polydimethylsiloxane (a).
In the present invention, the cationically curable polydimethylsiloxane (a) means a polydimethylsiloxane having a cationically curable functional group. The cation-curable functional group means a reactive functional group exhibiting cation-curability, and specifically, vinyl ether groups, oxetane groups, epoxy groups, and alicyclic epoxy groups can be exemplified. Among them, from the viewpoint of reactivity, it is preferable to have at least one functional group selected from oxetanyl group, epoxy group, alicyclic epoxy group, and most preferable is an alicyclic epoxy group. The release layer having such a functional group is preferably a release layer having excellent solvent resistance and excellent releasability, because a crosslinked structure is formed by a cationic curing reaction.
The number of the cationically curable functional groups of the cationically curable polydimethylsiloxane (a) may be 1 or more. For example, a release layer having 2 or more cationically curable functional groups is preferable because the cationic curing reaction proceeds more easily and the crosslinking density is high. The site of introducing the cation-curable functional group is not particularly limited, and is usually located at the side chain or terminal of polydimethylsiloxane. The polydimethylsiloxane may have a linear structure or a branched structure, and may be used without any problem even if it has a functional group other than the cationically curable functional group.
The cationic curable polydimethylsiloxane (a) can be used as appropriate. Examples of the "UV POLY 200", UV POLY201 ", UV POLY215, UV RCA 200", UV RCA251 ", and" UV9440E, UV9430 "manufactured by Xinyue chemical industries, inc. include Silcolease (registered trademark) manufactured by Silcolase chemical industries, inc. and the like.
The weight average molecular weight of the cationically curable polydimethylsiloxane (a) is preferably 1000 to 500000, more preferably 5000 to 100000. When the weight average molecular weight is 1000 or more, the cationic curing reaction is easy to proceed and the releasability is excellent, so that it is preferable. When the viscosity is 500000 or less, the viscosity is not excessively high, and the release layer is preferably a release layer having excellent coatability and high planarity.
The release layer-forming composition of the present invention may contain other resins in addition to the cationic curable polydimethylsiloxane (a). The release layer is preferably one comprising a cationic curable polydimethylsiloxane (a) as a main component and cured. In this case, the film thickness of the release layer can be made thin. In the present invention, since the release layer is provided on the surface layer a of the base film substantially free of inorganic particles, even if the film thickness of the release layer is thin, the release layer having extremely high smoothness can be formed. In addition, since the film thickness of the release layer is small, the curing reaction is easy to proceed, and the processing can be performed at a higher speed, so that the release layer can be economically obtained.
Further, when the film thickness is small, very small foreign matters and the like existing in the base film, the mold release processing step and the like are not mixed into the mold release layer. Therefore, no protrusion due to foreign matter is generated on the surface of the release layer, and a release layer having a smooth surface as described above can be obtained.
In the case of a release layer obtained by curing a composition containing a cationically curable polydimethylsiloxane (a) as a main component, the film thickness of the release layer is preferably 0.001 μm or more and less than 0.050 μm. When the particle diameter is 0.001 μm or more, the releasability is excellent, and thus it is preferable. When the particle size is less than 0.050. Mu.m, aggregation of the release layer forming composition can be prevented, and a smooth release layer can be obtained.
In the present invention, in the case where the cationic curable polydimethylsiloxane (a) is used as the main component, the composition contains at least 50 parts by mass, for example, more than 50 parts by mass, preferably 70 parts by mass or more, for example, 80 parts by mass or more, and in one embodiment 90 parts by mass or more, based on 100 parts by mass of the resin solid content of the release layer. The cationic curable polydimethylsiloxane (a) may be contained in substantially all of the resin solid components of the release layer.
The release layer forming composition of the present invention may contain a cationic curable resin (b) in addition to the cationic curable polydimethylsiloxane (a). In this case, (b) is a resin different from (a), and the resin (b) is a material having no polydimethylsiloxane structure. Specifically, the cationic curable compounds (b-1) having no organosilicon skeleton and the cyclic siloxane compounds (b-2) having an alicyclic epoxy group are roughly classified into 2 types.
In one embodiment, the release layer-forming composition further contains a cationic curable compound (b-1) having no silicone skeleton in addition to the cationic curable polydimethylsiloxane (a). Examples of the cation-curable compound (b-1) having no silicone skeleton include polymers and monomers having 2 or more cation-curable functional groups in the molecule and having no silicone skeleton. Among them, a resin having 2 or more epoxy groups or alicyclic epoxy groups is preferable, and a resin having 2 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 proceeds by a cationic curing reaction, and a release layer excellent in solvent resistance is obtained. In addition, since the polydimethylsiloxane (a) contained in the release layer is crosslinked, the release property is excellent, and the transfer of the polydimethylsiloxane (a) to the ceramic green sheet can be suppressed, which is preferable.
In one embodiment, since the release layer forming composition contains both the cation-curable resin (b-1) having no silicone skeleton and the polydimethylsiloxane (a), a release layer having high smoothness can be realized. By forming the release layer containing the compound (b-1), fine irregularities, protrusions derived from very fine foreign matters or oligomers, and the like existing in the base film can be buried, and an ultra-smooth release layer can be obtained. In addition, since the curing reaction is performed by ultraviolet rays, a release layer having high smoothness is obtained. While not being limited to a particular theory, it is speculated that in the drying step in the release layer forming composition at the time of release layer processing, (b-1) and (a) are uniformly leveled and cured after the planarity is improved, and a release layer having high smoothness can be obtained. In the present invention, since the polydimethylsiloxane (a) contained simultaneously segregates on the surface of the release layer in the drying step, a release layer excellent in releasability can be obtained.
The cation curable compound (b-1) having no organosilicon skeleton is preferably a low molecular weight monomer. Specifically, the number average molecular weight is preferably 200 or more and less than 5000, more preferably 200 or more and less than 2500, still more preferably 200 or more and less than 1000. When the number average molecular weight is 200 or more, the boiling point is not lowered, and the cation curable compound (b-1) is not volatilized in the drying step of the release layer forming composition at the time of the release layer processing, so that it is preferable. When the crosslinking density of the release layer is less than 5000, the crosslinking density is improved, and the solvent resistance is excellent, so that it is preferable. In addition, since the resin composition can be present in a liquid state having fluidity in the drying step, it is preferable that the resin composition has excellent leveling property and becomes an ultra-smooth release layer.
The cation curable compound (b-1) having no silicone skeleton can be used as a commercially available product. Examples of the compound having an alicyclic epoxy group include CELLOXIDE 2021P, CELLOXIDE 2081, EPOLEAD GT401, EHPE3150, hiREM-1, and THI-DE, DE-102, DE-103, both manufactured by ENEOS Co., ltd. Of Daicel Corporation. Examples of the epoxy group-containing resin include DENACOL (registered trademark) EX-611, EX-313, EX-321, etc. manufactured by DIC Co., ltd., EPICLON (registered trademark) 830, 840, 850, 1051-75M, N-665, N-670, N-690, N-673-80M, N-690-75M, nagase ChemteX Corporation, and the like.
The content of the cationic curable compound (b-1) having no silicone skeleton is preferably 80 mass% or more, more preferably 85 mass% or more, and still more preferably 90 mass% or more, based on 100 parts by mass of the total of the cationic curable polydimethylsiloxane (a) and the cationic curable compound (b-1) in the release layer.
The content of the cationic curable compound (b-1) is preferably 80 mass% or more as a main component in the release layer, because the release layer has a high crosslinking density and excellent releasability. In addition, the content of the cationic curable polydimethylsiloxane (a) contained in the release layer can be reduced, and aggregation of the component derived from the polydimethylsiloxane (a) on the surface of the release layer in the drying step can be suppressed, and the planarity is not deteriorated, so that it is preferable. The content of the cation-curable compound (b-1) is larger to form a release layer having more excellent smoothness, but the cation-curable compound (b-1) is preferably 99.9 mass% or less in order to contain the cation-curable polydimethylsiloxane (a) and ensure releasability.
In the present invention, in the release layer formed by curing the release layer forming composition, there is a compound (cured product) derived from the cationic curable compound (b-1) having no silicone skeleton. In the present specification, the compound derived from (b-1) present in the release layer may be simply referred to as a cationic curable compound (b-1) having no silicone skeleton.
When the release layer-forming composition contains the cationic curable polydimethylsiloxane (a) and the cationic curable compound (b-1), the release layer has a high crosslinking density and is excellent in solvent resistance and has excellent release force, which is preferable. In addition, when the cationic curable compound (b-1) is contained, the film thickness of the release layer can be made thicker while the content of the cationic curable polydimethylsiloxane (a) is set to a predetermined range, which is preferable. The thickness of the release layer is preferably increased because the damage and the minute irregularities existing in the base film can be buried, and the release layer can be obtained smoothly as described above.
When the release layer-forming composition contains the cationic curable polydimethylsiloxane (a) and the cationic curable compound (b-1), the film thickness of the release layer is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. When the thickness is 0.05 μm or more, a smooth release layer is formed, which is preferable. When the thickness is 1.0 μm or less, a release film excellent in flatness without curling can be obtained, and is preferable.
In one embodiment, the release layer-forming composition may further contain a cyclic siloxane compound (b-2) having an alicyclic epoxy group. Cyclic siloxane compound having alicyclic epoxy group Examples of (b-2) include a substance represented by the following structural formula (formula 1) (R in formula 1) 2 Alkyl groups having 1 to 4 carbon atoms). The cation curable compound (b-2) having a cyclic siloxane skeleton preferably has at least 2 or more alicyclic epoxy groups. If there are 2 or more alicyclic epoxy groups, the cationic curing reaction proceeds to form a release layer having a high crosslinking density, which is preferable.
[ chemical formula 1]
The use of the cyclic siloxane compound (b-2) having an alicyclic epoxy group is preferable because it is an ultra-smooth release layer for the same reason as in the case of using the above-mentioned cation-curable compound (b-1). That is, fine irregularities existing in the base film, projections derived from very fine foreign matters or oligomers, and the like can be buried. In addition, since the curing reaction is performed by ultraviolet rays, in the drying step of the release layer forming composition at the time of the release layer processing, the compound (b-2) and the polydimethylsiloxane (a) are uniformly leveled and cured after the planarity is improved, so that an ultra-smooth release layer can be obtained. Further, in the present invention, since the polydimethylsiloxane (a) contained simultaneously segregates on the surface of the release layer in the drying step, a release layer excellent in releasability can be obtained.
Since the alicyclic epoxy group-containing cyclic siloxane compound (b-2) has good compatibility with the cationic curable polydimethylsiloxane (a), the cyclic siloxane compound (b-2) is appropriately mixed in the release layer and undergoes a crosslinking reaction with each other. Therefore, a release layer having excellent solvent resistance and excellent releasability is preferable. In addition, the cyclic siloxane compound (b-2) has a cyclic siloxane structure, and thus has a rigid molecular skeleton, and the film hardness at the time of curing is preferably improved. By increasing the film hardness, the release layer becomes less likely to deform when the resin sheet, for example, a ceramic green sheet is peeled off, and good peelability can be exhibited. Further, the release layer is preferably less likely to cause scratches, since scratches of the release layer are not transferred to a resin sheet, for example, a ceramic green sheet, and cause defects.
When the cyclic siloxane compound (b-2) is contained in the release layer-forming composition, the adhesion of the release layer to the base film is improved, and thus it is preferable. The improvement of the adhesion of the release layer is preferable because the occurrence of scratches during the transfer step can be suppressed, and the release layer is not transferred when the resin sheet is peeled off.
In one embodiment, the cyclic siloxane compound (b-2) has 2 or more alicyclic epoxy groups in the molecule. By having 2 or more alicyclic epoxy groups in the molecule, a crosslinking reaction proceeds by a cationic curing reaction, and a release layer excellent in solvent resistance is obtained. In addition, since the crosslinking reaction is also performed with the polydimethylsiloxane (a) contained in the release layer, the release property is excellent, and the transfer of the polydimethylsiloxane (a) to the ceramic green sheet can be suppressed, which is preferable.
For example, the cyclic siloxane compound (b-2) has 6 or less alicyclic epoxy groups in the molecule.
As the cyclic siloxane compound (b-2) having an alicyclic epoxy group, commercially available ones can be used. Examples of the "X-40-2670" and "X-40-2678" are those manufactured by Kagaku Kogyo Co., ltd.
The content of the cyclic siloxane compound (b-2) is preferably 80 mass% or more, more preferably 85 mass% or more, and still more preferably 90 mass% or more, based on 100 parts by mass of the total of the cationic curable polydimethylsiloxane (a) and the cyclic siloxane compound (b-2) in the release layer. The content of the cyclic siloxane compound (b-2) is preferably 80 mass% or more as a main component in the release layer, because the release layer has a high crosslinking density and excellent releasability. In addition, the content of the cationic curable polydimethylsiloxane (a) contained in the release layer can be reduced, and in the present invention, the cationic curable polydimethylsiloxane (a) can be suppressed from aggregating on the surface of the release layer in the drying step, and the planarity is not deteriorated, so that it is preferable. The more the content of the cyclic siloxane compound (b-2), the more excellent the smoothness of the release layer, for example, the cyclic siloxane compound (b-2) is preferably 99.9 mass% or less in order to contain the cationically curable polydimethylsiloxane (a) and ensure the releasability.
In the present invention, a compound (cured product) derived from the cyclic siloxane compound (b-2) is present in the release layer obtained by curing the release layer-forming composition. In the present specification, the compound derived from the cyclic siloxane compound (b-2) present in the release layer is also sometimes simply referred to as the cyclic siloxane compound (b-2).
When the release layer-forming composition contains the cationically curable polydimethylsiloxane (a) and the cyclic siloxane compound (b-2), the film thickness of the release layer is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. When 0.05 μm or more, a smooth release layer is preferable. When the thickness is 1.0 μm or less, a release film excellent in flatness without curling can be obtained, and is preferable.
In one embodiment, the release layer may contain both the cationic curable resin (b-1) and the cyclic siloxane compound (b-2), and the total amount of these cationic curable resin (b-1) and cyclic siloxane compound (b-2) may be 80 mass% or more and 99.9 mass% or less with respect to 100 parts by mass of the total of the cationic curable polydimethylsiloxane (a) and cationic curable compound (b-1) and cyclic siloxane compound (b-2) in the release layer.
In the present invention, in order to form the release layer, a cationic curing reaction is required. Thus, the release layer forming composition preferably contains an acid generator (c). In addition, a compound derived from the acid generator (c) may be present in the release layer. Here, the compound derived from the acid generator (c) present in the release layer is also sometimes simply referred to as the acid generator (c).
The acid generator is not particularly limited, and a general acid generator can be used, but a photoacid generator that generates an acid under irradiation of ultraviolet rays is preferably used because heat during processing can be suppressed and a mold release layer excellent in flatness can be obtained.
As the photoacid generator, a salt composed of an onium ion and a non-nucleophilic anion is suitably used from the viewpoint of reactivity. In addition, an organometallic complex typified by an iron aromatic hydrocarbon complex, a carbocation salt typified by a tropylium (tropylum), an anthracene derivative, a phenol substituted with an electron withdrawing group, for example, pentafluorophenol, may be used.
In the case of using the above-mentioned salt composed of an onium ion and a non-nucleophilic anion as the photoacid generator, for example, iodonium, sulfonium, and ammonium can be used as the onium ion. As the organic group of the onium ion, triaryl, diaryl (monoalkyl), monoaryl (dialkyl), or trialkyl may be used, and benzophenone or 9-fluorene may be introduced, or other organic groups may be used. As non-nucleophilic anions, use is suitably made of hexafluorophosphate, hexafluoroantimonate, hexafluoroborate, tetrakis (pentafluorophenyl) borate. In addition, tetrakis (pentafluorophenyl) gallium ions, anions obtained by replacing some of fluorine anions with perfluoroalkyl groups or organic groups may be used, and other anionic components may be used.
The amount of the photoacid generator to be added is 0.1 to 10 mass%, more preferably 0.5 to 8 mass% based on 100 mass% of the total of the cationic curable polydimethylsiloxane (a) and the cationic curable compound (b-1) and/or the cyclic siloxane compound (b-2) in the release layer. Further preferably 1 to 5% by mass. When the amount is 0.1 mass% or more, the amount of the generated acid is preferably not insufficient, since insufficient curing is not caused. Further, the amount of acid generated is preferably 10 mass% or less, since the amount of acid transferred to the ceramic green sheet to be molded can be suppressed.
In the present specification, 100 parts by mass of the total of the cationic curable polydimethylsiloxane (a) and the cationic curable compound (b-1) and/or the cyclic siloxane compound (b-2) in the release layer means the total of the solid content of the cationic curable polydimethylsiloxane (a) and the solid content of the cationic curable resin (b). In the mode in which the release layer does not contain the cationic curable resin (b), the weight of the cationic curable polydimethylsiloxane (a) corresponds to 100 parts by mass of the resin solid content in the release layer.
In one embodiment, the release layer-forming composition contains an organic solvent having an SP value (δ) of 14 to 17, and the release layer-forming composition contains the organic solvent having an SP value (δ) of 14 to 17 in an amount of 10 mass% relative to 100 mass parts of the total weight of the release layer-forming composition.
The organic solvent having an SP value (δ) of 14 to 17 shows excellent solubility to the cationically curable polydimethylsiloxane (a). Therefore, in the drying step after the coating step, even if the concentration of (a) in the release layer forming composition increases due to drying of the organic solvent, the release layer can be kept in a uniformly dissolved state, and leveling can be performed cleanly without aggregation, thereby obtaining a smooth release layer.
In addition, if the content is 10 mass% or more, the cation-curable polydimethylsiloxane (a) can remain in a dissolved state for a long period of time during drying, and thus it is preferable that the smoothness is not deteriorated due to aggregation during drying.
The organic solvent having an SP value (δ) of 14 or more and 17 or less will be described in detail below.
In the present invention, additives such as an adhesion improving agent and an antistatic agent may be added to the release layer within a range that does not inhibit the effect of the present invention. In order to improve the adhesion to the substrate, it is also preferable to perform pretreatment such as anchor coating, corona treatment, plasma treatment, and atmospheric pressure plasma treatment on the surface of the polyester film before providing the release coating layer.
The release film obtained by the present invention preferably has a peel force of 0.01mN/mm or more and 2.0mN/mm or less when the ceramic green sheet is peeled. More preferably from 0.05 to 1.0 mN/mm. When the peeling force is 0.01mN/mm or more, the ceramic green sheet does not float during transportation, and is preferable. When the peeling force is 2.0mN/mm or less, the ceramic green sheet is preferably peeled without being damaged.
Since the release film obtained by the present invention uses a highly planarized base film, the surface of the release layer can be smoothed even when the thickness of the release layer is 1.0 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. Therefore, the amount of the solvent and the amount of the resin used can be reduced, and the method is environmentally friendly, and a release film for molding an ultrathin ceramic green sheet can be produced at low cost.
(method for producing Release film)
In another embodiment, the present invention provides a method for producing a release film for molding a resin sheet, comprising the steps of:
a coating step of coating a release layer forming composition on the surface layer A of a polyester film having the surface layer A, wherein,
the surface layer a is a layer substantially free of inorganic particles,
the release layer forming composition comprises a cationically curable polydimethylsiloxane (a);
a drying step of heating and drying the polyester film coated with the release layer forming composition,
the heat drying has a 1 st drying process and a following 2 nd drying process,
the drying temperature T1 in the 1 st drying procedure is higher than the drying temperature T2 in the 2 nd drying procedure;
And a photo-curing step of irradiating the release layer-forming composition with an active energy ray after the drying step.
The production method of the present invention can prevent aggregation of the resin constituting the release layer by enhancing the 1 st drying condition (by enhancing drying), and can obtain a release layer having high smoothness.
Further, by setting the SP value of the solvent in the release layer forming composition to a predetermined value, aggregation of the resin constituting the release layer can be prevented, and a release layer having high smoothness can be obtained.
In this way, the drying step 1 of the present invention has predetermined conditions, and in one embodiment, a release layer having high smoothness can be obtained by using a specific solvent.
The method for producing a release film of the present invention comprises the steps of: a coating step of coating a release layer-forming composition containing at least a cationically curable polydimethylsiloxane (a) onto a surface layer A of a polyester film that is substantially free of inorganic particles; a drying step of heating and drying the film after coating using, for example, a drying furnace; and a photo-curing step of curing the cured product by using active energy rays after the heated and dried product. Particularly, a method in which the coating step, the drying step, and the photo-curing step are performed in this order is preferable.
According to the production method of the present invention, it has been found that by studying the production conditions in the coating step, a release layer having high smoothness can be achieved. Specifically, by containing an organic solvent having an SP value (δ) of 14 to 17 in the release layer forming composition, aggregation of the cationic curable polydimethylsiloxane (a) can be suppressed, and an excellent release layer can be obtained. The SP value (δ) can be used for the prediction of the solubility of a substance, and an organic solvent having an SP value (δ) of 14 to 17 exhibits excellent solubility to the cationically curable polydimethylsiloxane (a). Therefore, in the drying step after the coating step, even if the concentration of (a) in the release layer forming composition increases due to drying of the organic solvent, the release layer can be kept in a uniformly dissolved state, and leveling can be performed cleanly without aggregation, thereby obtaining a smooth release layer.
The content of the organic solvent having an SP value (δ) of 14 to 17 contained in the release layer-forming composition is preferably 10 mass% or more, and more preferably 15 mass% or more, relative to 100 parts by mass of the release layer-forming composition. If it is 10 mass% or more, the cation-curable polydimethylsiloxane (a) can remain dissolved for a long period of time during drying, and thus it is preferable that it does not aggregate during drying and deteriorate the smoothness. For example, the content of the organic solvent having an SP value (δ) of 14 to 17 may be 80 mass% or less, for example 65 mass% or less, or may be less than 50 mass% relative to 100 parts by mass of the release layer forming composition.
The SP value (delta) in this specification uses the Hildebrand solubility parameter. Hildebrand solubility parameters can be experimentally calculated from Hansen solubility parameters (Hansen Solubility Parameters, HSP values) as in equation 1.
SP value (δ) = ((δ) d ) 2 +(δ p ) 2 +(δ h ) 2 ) 1/2 (formula 1)
Here (delta) D ) Is dispersion force term (delta) P ) Is a polar term, (delta) H ) The idea of decomposing the Hildebrand solubility parameter into 3 components is the hansen solubility parameter, which is the hydrogen bonding force term.
The value described in the present specification can also be calculated using computer software HSPiP (Hansen Solubility Parameters in Practice) or the like, and the value calculated according to expression 1 using the HSP value described in the database in hsPIP ver4.0 is used.
Examples of the organic solvent having an SP value (δ) of 14 to 17 include n-hexane (δ: 14.9), n-heptane (δ: 15.3), n-octane (δ: 15.5), isopropyl ether (δ: 15.8), 1-diethoxyethane (δ: 15.9), methylcyclohexane (δ: 16.0), cyclopentane (δ: 16.5), and cyclohexane (δ: 16.8).
The release layer-forming composition is preferably applied in an amount of 10g/m 2 Hereinafter, more preferably 8g/m 2 The following is given. If the coating weight is 10g/m 2 Hereinafter, for example, when coating is performed by gravure coating, it is preferable that a liquid disorder is less likely to occur at the nip between the film and the gravure roll, and a release layer having excellent smoothness can be obtained.
In the present invention, the solvent contained in the release layer forming composition is preferably 2 or more, preferably at least 1 of them is a solvent having an SP value (δ) of 14 to 17 as described above, and at least 1 is a solvent having a boiling point of 100 ℃ or more. By adding a solvent having a boiling point of 100 ℃ or higher, the flash during drying can be prevented, the coating film can be leveled, and the smoothness of the surface of the dried coating film can be improved.
The amount of the additive is preferably about 10 to 70% by mass based on the entire composition of the release layer. Examples of the solvent having a boiling point of 100℃or higher include toluene, xylene, n-octane, cyclohexanone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, isobutyl acetate, and n-butanol.
In the present invention, it is preferable to perform filtration before applying the coating liquid of the release layer forming composition. The filtration method is not particularly limited, and a known method can be used, but a cartridge filter of a surface type, a depth type, or an adsorption type is preferably used. The use of a cartridge filter is preferable because it can be used when the coating liquid is continuously transported from the tank to the coating section, and thus the filtration can be performed with good productivity and high efficiency. As the filtration accuracy of the filter, a filter that removes 99% or more of substances having a size of 1 μm is preferably used, and a filter that can filter 99% or more of substances having a size of 0.5 μm is more preferably used. The use of the filter having the above-described filtration accuracy is preferable because foreign matters mixed in the coating liquid for forming the release layer can be removed, and foreign matters adhering to the release film of the present invention can be reduced, and a release layer having excellent smoothness can be obtained.
As a coating method of the coating liquid, any known coating method can be used, and conventionally known methods such as a roll coating method such as a gravure coating method or a reverse roll coating method, a bar coating method such as a bar coating method, a die coating method, a spray coating method, and an air knife coating method can be used.
As a method of applying the release layer forming composition to the base film and drying it, there are known hot air drying, an infrared heater, and the like, but hot air drying with a high drying speed is preferable. The drying is preferably performed in a drying furnace, but is not particularly limited, and a known drying furnace may be used. The drying furnace may be either a roll support type or a floating type, but the roll support type is preferable because the range of the air volume during drying can be widely adjusted, and the air volume can be adjusted in accordance with the type of the release layer.
The drying process may be divided into 2 drying processes, i.e., a constant-speed drying process (hereinafter referred to as a 1 st drying process) and a deceleration drying process (hereinafter referred to as a 2 nd drying process) in the initial drying process. The 2 steps are preferably performed continuously in the order of the 1 st drying step and the 2 nd drying step, and can be distinguished by dividing the drying furnace into regions, wherein the 1 st (initial) drying step may be performed using the 1 st drying furnace, and the 2 nd (later) drying step may be performed using the 2 nd drying furnace.
The inventors of the present invention found that it is important that the drying temperature T1 in the 1 st drying step is higher than the drying temperature T2 in the 2 nd drying step in order to improve the smoothness of the release layer. The 1 st drying furnace temperature and the 2 nd drying furnace temperature are preferably set to the ranges described below. By performing the production under such conditions, the constant-speed drying time in the 1 st drying step can be shortened, the deceleration drying time in the 2 nd drying step can be prolonged, and a release layer excellent in planarity can be obtained, which is preferable.
Further, the present inventors have found that it is important to increase the temperature in the 1 st drying furnace and shorten the constant-speed drying time.
More specifically, the drying temperature T1 is preferably 90 ℃ to 180 ℃, and preferably 100 ℃ to 150 ℃. The cation curable polydimethylsiloxane (a) contained in the release layer-forming composition can be prevented from aggregating by increasing the temperature in the 1 st drying furnace and shortening the constant-speed drying time, and is therefore preferable. Although it is preferable that the higher the temperature of the 1 st drying furnace is, the shorter the constant-speed drying time is, if it is too high, deterioration of the flatness of the film due to heat occurs, and therefore, it is preferable to be 180 ℃ or lower. When the temperature is 90℃or higher, the drying ability becomes sufficient, and it is preferable.
The temperature in the 2 nd drying furnace is preferably 60 ℃ to 140 ℃, more preferably 80 ℃ to 120 ℃. In the 2 nd drying step, it is preferable to reduce the drying time, because drying can be performed without roughening the surface of the release layer before photo-curing, and smoothness of the release layer can be improved.
For example, the constant-speed drying time in the 1 st drying step is preferably shorter than the deceleration drying time in the 2 nd drying step. This can prevent deterioration of the flatness of the film, and can dry the release layer without roughening the surface of the release layer before photo-curing, thereby improving the smoothness of the release layer.
After the application, the time until entering the 1 st drying furnace is preferably 0.1 seconds or more and 2.5 seconds or less, more preferably 0.1 seconds or more and 2.0 seconds or less, and the shorter the time is, the more preferable. The drying time in the 1 st drying step can be shortened by accelerating the time until the mixture enters the 1 st drying furnace, and aggregation of the cationic curable polydimethylsiloxane (a) can be suppressed, so that a release layer excellent in smoothness can be obtained. The time until entering the drying oven can be calculated from the processing speed and the structure of the processing machine.
The method for producing the present invention includes a photocuring step of curing the release layer-forming composition by irradiation of active energy rays after the drying step.
In the photocuring step, the dried release layer-forming composition undergoes a cationic curing reaction by irradiation with active energy rays. As the active energy ray to be used, known techniques such as ultraviolet rays and electron beams can be used, and ultraviolet rays are preferably used. The cumulative light amount when ultraviolet rays are used can be represented by the product of illuminance and irradiation time. For example, it is preferably 10 to 500mJ/cm 2 . When the lower limit is not less than the above lower limit, the release layer can be sufficiently cured, which is preferable. When the upper limit is less than or equal to the above, thermal damage to the film by heat during irradiation can be suppressed, and smoothness of the surface of the release layer can be maintained, which is preferable.
When the active energy beam is irradiated, the back surface of the film is preferably held by a support roller. The provision of the support roller is preferable because the distance from the active energy source can be kept constant, and uniform irradiation is possible. Further, it is preferable to irradiate active energy rays while cooling the surface of the support roller and cooling the film. By cooling, even when active energy rays are irradiated, the film is less likely to be damaged by heat, and the smoothness of the surface of the release layer can be maintained, which is preferable.
In one embodiment, the manufacturing method of the present invention provides a method of manufacturing a release film for manufacturing a resin sheet containing an inorganic compound.
(resin sheet)
The resin sheet in the present invention is not particularly limited as long as it contains a resin. In one embodiment, the release film of the present invention is a release film for molding a resin sheet containing an inorganic compound. Examples of the inorganic compound include metal particles, metal oxides, minerals, and the like, and examples thereof include calcium carbonate, silica particles, aluminum particles, and barium titanate particles. The present invention has a release layer having high smoothness, and therefore, even in an embodiment in which the inorganic compound is contained in the resin sheet, defects that may be caused by the inorganic compound, such as breakage of the resin sheet and difficulty in peeling of the resin sheet from the release layer, can be suppressed.
The resin component forming the resin sheet may be appropriately selected according to the use. In one embodiment, the resin sheet containing an inorganic compound is a ceramic green sheet. For example, the ceramic green sheet may contain barium titanate as an inorganic compound. The resin component may include, for example, a polyvinyl butyral resin.
In one embodiment, the thickness of the resin sheet is 0.2 μm or more and 1.0 μm or less.
For example, the present invention can provide a method for producing a release film for producing such a resin sheet containing an inorganic compound. The method for producing a release film for molding a resin sheet according to the present invention may include a step of molding a resin sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
(ceramic green sheet and ceramic capacitor)
In general, a multilayer ceramic capacitor has a ceramic matrix in a rectangular parallelepiped shape. Inside the ceramic substrate, the 1 st internal electrode and the 2 nd internal electrode are alternately arranged along the thickness direction. The 1 st internal electrode is exposed at the 1 st end face of the ceramic substrate. The 1 st external electrode is arranged on the 1 st end face. The 1 st internal electrode is electrically connected to the 1 st external electrode at the 1 st end face. The 2 nd internal electrode is exposed at the 2 nd end face of the ceramic substrate. The 2 nd external electrode is arranged on the 2 nd end face. The 2 nd internal electrode is electrically connected to the 2 nd external electrode in the 2 nd end face.
In one embodiment, the release film of the present invention is a release film for producing ceramic green sheets, and is used for producing such multilayer ceramic capacitors.
For example, the method for producing a ceramic green sheet by molding a ceramic green sheet using the release film for producing a ceramic green sheet of the present invention can mold a ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
In more detail, for example, a ceramic green sheet is manufactured as follows. First, the release film of the present invention is used as a carrier film, and ceramic slurry for constituting a ceramic matrix is applied and dried. The thickness of the ceramic green sheet is required to be an extremely thin product of 0.2 to 1.0 μm. And printing a conductive layer for forming the 1 st or 2 nd internal electrode on the coated and dried ceramic green sheet. The ceramic green sheet, the ceramic green sheet printed with the conductive layer for constituting the 1 st internal electrode, and the ceramic green sheet printed with the conductive layer for constituting the 2 nd internal electrode were laminated appropriately and pressed, whereby a mother laminate was obtained. The mother laminate was divided into a plurality of pieces to prepare a green ceramic substrate. The ceramic matrix is obtained by firing a green ceramic matrix. After that, by forming the 1 st and 2 nd external electrodes, the multilayer ceramic capacitor can be completed.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The characteristic values used in the present invention were evaluated by the following methods.
(thickness of mold Release layer)
The cut release film was resin-embedded, and ultrathin slicing was performed using an ultrathin slicer. Then, cross-sectional observation was performed using a JEM2100 transmission electron microscope, manufactured by japan electronics, and the film thickness of the release layer was measured from the observed TEM image. If the thickness was too small and the evaluation could not be performed accurately in the cross-sectional view, the measurement was performed using a reflectance spectrometer film thickness meter (FE-3000 manufactured by Otsuka electronics Co., ltd.).
(weight of release layer)
In the present specification, the weight per 1 μm of the thickness of the release layer is 1g/m 2 Calculated weight value. For example, in the case where the thickness of the release layer measured by the above method is 0.2. Mu.m, the total weight of the release layer is 0.2g/m 2 . The weight of the cationic curable polydimethylsiloxane (a), the weight of the cationic curable resin (b), and the weight of the acid generator (c) contained in the release layer were calculated from the blending ratio of the components contained in the release layer-forming composition and the total weight of the release layer. For example, the thickness of the release layer is 0.2 μm and the positive electrode isWhen the weight ratio of the release layer of the ion-curable polydimethylsiloxane (a) was 5 parts by mass, the weight of (a) contained in the release layer was 0.01g/m 2 . The weight ratio (mass%) of the release layer was calculated based on 100 parts by mass of the total of the component (a) and the component (b).
(coating amount of release layer Forming composition)
The values calculated from the liquid consumption weight and the processing area of the release layer forming composition used in the coating step were used.
(time from coating to the 1 st drying oven)
The values calculated from the film travel distance from the coating section to the 1 st drying furnace and the processing speed were used.
(area surface roughness Sa, maximum protrusion height Sp)
The measurement was carried out using a non-contact surface shape measuring system (VertScan R550H-M100) under the following conditions. The area surface average roughness (Sa) was an average value of 5 measurements, and the maximum protrusion height (Sp) was the maximum value of 5 measurements after 7 measurements and excluding the maximum value and the minimum value.
(measurement conditions)
Measurement mode: WAVE mode
Objective lens: 50 times of
0.5 x tube lens
Measurement area 187. Mu.m.times.139. Mu.m
(analysis conditions)
Horizontal correction: correction for 4 times
Interpolation processing: complete interpolation
(number of protrusions having a height of 10nm or more and number of protrusions having a height of 5nm or more)
Among all the 7 measured values in which the maximum protrusion height was measured, particle analysis was performed using the measured data indicating the value of the center. Particle analysis was performed using analysis software of Vertscan R550H-M100 under the following conditions. Particle analysis was performed with a measurement area equal to the measurement area of the surface roughness and the maximum protrusion height of the above-mentioned region, and the number of protrusions having a maximum height of 10nm or more or the number of protrusions having a maximum height of 5nm or more was calculated. Projection(s)The starting number is converted into 1mm 2 And (3) a converted value.
(conditions for particle analysis)
Horizontal correction: correction for 4 times
Preservation process: complete interpolation
Collision analysis
Reference height: zero plane
(ceramic sheet peeling force)
Slurry composition I containing the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads having a diameter of 0.5mm for 10 minutes using a bead mill, to obtain a primary dispersion. Thereafter, a slurry composition II comprising the following materials was added to the primary dispersion so as to be (slurry composition I): (slurry composition II) =3.4: 1.0, and the resultant slurry was twice dispersed with zirconia beads having a diameter of 0.5mm for 10 minutes using a bead mill.
(slurry composition I)
(slurry composition II)
Then, the release film with a ceramic green sheet was obtained by applying the slurry obtained after drying to a release surface of the obtained release film sample with an applicator so that the slurry became 1.0 μm and drying at 60℃for 1 minute. The obtained release film with a ceramic green sheet was subjected to static electricity elimination by a motor (SJ-F020, manufactured by Kihn Co., ltd.) and then peeled off by a peeling tester (VPA-3, load cell load 0.1N, manufactured by Kyowa Co., ltd.) at a peeling angle of 90℃and a peeling temperature of 25℃and a peeling speed of 10 m/min. As the direction of peeling, a double-sided adhesive tape (No. 535A, manufactured by ridong electric Co., ltd.) was adhered to the SUS plate attached to the peeling tester, and the release film was fixed to the double-sided adhesive tape so as to adhere the ceramic green sheet side to the double-sided adhesive tape, and peeled in a form of stretching the release film side. The average value of the peel force of the measured values from 20mm to 70mm was calculated and used as the peel force. The measurement was performed 5 times in total, and the average value of the peel force was used for evaluation. The determination was made based on the values of the peeling force obtained as follows.
O: 0.1mN/mm or more and less than 1.0mN/mm
X: 1.0mN/mm or more
(pinhole evaluation of ceramic green sheet)
In the same manner as in the above-described evaluation of releasability of the ceramic slurry, a ceramic green sheet having a thickness of 1 μm was molded on the release surface of the release film. Then, the release film was peeled off from the molded release film with a ceramic green sheet to obtain a ceramic green sheet. In the central region of the obtained ceramic green sheet in the film width direction, 25cm 2 Within the range (2), light was irradiated from the surface opposite to the coated surface of the ceramic slurry, and the occurrence of pinholes, which were visible through the light transmission, was observed, and visual determination was performed according to the following criteria.
O: no pinholes are generated
X: generating more than 1 pinhole
(preparation of polyethylene terephthalate pellets (PET (I))
As the esterification reaction apparatus, a continuous esterification reaction apparatus comprising a stirring apparatus, a dephlegmator, and a three-stage complete mixing tank having a raw material inlet and a product outlet was used. The slurry was continuously supplied to the 1 st esterification reactor of the esterification reactor, where TPA (terephthalic acid) was 2 tons/hr, EG (ethylene glycol) was 2 moles per 1 mole of TPA, antimony trioxide was 160ppm of Sb atoms per 160ppm of PET produced, and reacted at an average residence time of 4 hours and 255℃under normal pressure. Then, the reaction product in the 1 st esterification reaction vessel was continuously taken out of the system and supplied to the 2 nd esterification reaction vessel, EG distilled off from the 1 st esterification reaction vessel was supplied to the 2 nd esterification reaction vessel in an amount of 8 mass% relative to the produced PET, and EG solution containing magnesium acetate tetrahydrate in an amount of 65ppm relative to the produced PET of Mg atoms and TMPA (trimethyl phosphate) in an amount of 40ppm relative to the produced PET of P atoms were further added EG solution was reacted at 260℃with an average residence time of 1 hour at normal pressure. Next, the reaction product of the 2 nd esterification reaction vessel was continuously taken out of the system and fed to a third esterification reaction vessel, and was subjected to a high-pressure dispersing machine (manufactured by Nippon Seiki Co., ltd.) under 39MPa (400 kg/cm 2 ) Under the pressure of (2) a 10% EG slurry was formed and added to 0.2 mass% of a porous colloidal silica having an average particle diameter of 0.9 μm, which had been subjected to a dispersion treatment for an average treatment number of 5 passes, and 0.4 mass% of a synthetic calcium carbonate having an average particle diameter of 0.6 μm, which had been obtained by adhering 1 mass% of an ammonium salt of polyacrylic acid to calcium carbonate, respectively, and reacted at 260℃at normal pressure for an average residence time of 0.5 hours. The esterification reaction product produced in the third esterification reactor was continuously fed to a three-stage continuous polycondensation reaction apparatus for polycondensation, and after filtration by a filter obtained by sintering stainless steel fibers having a 95% cutoff particle diameter of 20 μm, the resultant was ultrafiltered and extruded into water, and after cooling, the resultant was cut into pellets to obtain PET pellets having an intrinsic viscosity of 0.60dl/g (hereinafter, abbreviated as PET (I)). The lubricant content in the PET pellets was 0.6% by mass.
(preparation of polyethylene terephthalate pellets (PET (II))
On the other hand, in the production of the PET (I) pellets, PET pellets having an intrinsic viscosity of 0.62dl/g (hereinafter, abbreviated as PET (II)) which do not contain particles such as calcium carbonate and silica at all were obtained.
(production of laminated film X1)
These PET pellets were dried, melted at 285℃and then melted at 290℃by another melt extruder, and a filter obtained by sintering stainless steel fibers having a 95% cutoff particle diameter of 15 μm and a filter obtained by sintering stainless steel particles having a 95% cutoff particle diameter of 15 μm were combined in a feed block, laminated so that PET (I) became a surface layer B (reverse die side layer) and PET (II) became a surface layer A (die side layer), extruded (cast) at 45 m/min into a sheet shape, and then electrostatically sealed and cooled on a casting drum at 30℃by an electrostatic sealing method to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g. The layer ratio was adjusted so that the discharge amount of each extruder was PET (I)/(II) =60 mass%/40 mass%. Then, the unstretched sheet was heated by an infrared heater and stretched in the longitudinal direction by a speed difference between rolls at a roll temperature of 80 ℃. Thereafter, the resultant was introduced into a tenter frame, and stretched at 140℃in the transverse direction by a factor of 4.2. Then, in the heat-setting zone, heat treatment was performed at 210 ℃. Thereafter, a relaxation treatment of 2.3% was performed at 170℃in the transverse direction to obtain a biaxially stretched polyethylene terephthalate film X1 having a thickness of 31. Mu.m. The Sa of the surface layer A of the obtained film X1 was 1nm, and the Sa of the surface layer B was 28nm.
(production of laminated film X2)
As the laminated film X2, E5101 (TOYOBOESTER (registered trademark) film, manufactured by Toyobo Co., ltd.) having a thickness of 25 μm was used. E5101 has a structure including particles in the surface layer a and the surface layer B. The Sa of the surface layer A of the laminated film X2 was 24nm, and the Sa of the surface layer B was 24nm.
(cationically curable polydimethylsiloxane (a))
(a) -1: UV POLY215 (100% solids, manufactured by Sichuan chemical Co., ltd.)
(cation-curable resin (b))
(b) -1: celoxide 2021P (manufactured by Daicel Corporation, solid content 100%)
(b) -2: x-40-2670 (100% solid content, made by Xinyue chemical Co., ltd.)
(acid generator (c))
(c) -1: CPI-101A (manufactured by SAN-APRO Co., ltd., solid content: 50%)
Example 1
The release layer-forming composition 1, which was prepared by passing the release layer-forming composition through a filter capable of removing 99% or more of foreign matters of 0.5 μm or more on the surface layer A of the laminated film X1, was then applied to a coating weight of 5.0g/m using a reverse gravure plate 2 Is coated by way of (a) a coating. Then, the processing speed was adjusted so as to enter the 1 st drying furnace after 0.5 seconds, and the drying was continuously performed at the 1 st drying furnace temperature of 120℃and the 2 nd drying furnace temperature of 90 ℃. After the drying step, an ultraviolet irradiator (SAN-apo corporation, H valve) was used for the cooling roll ) The cumulative light quantity of irradiation was 100mJ/cm 2 The release layer is cured by ultraviolet rays, thereby obtaining a release film for molding a resin sheet. Further, the smoothness, peelability and pinhole evaluation of the obtained release film were carried out, and as a result, good results as shown in table 1 were obtained.
The thus obtained release film for molding a resin sheet is, for example, a release film which can produce a resin sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
The weights (mg/m) of the components (a), (b), and (c) shown in the tables 2 ) The content ratio of each solid component (weight of each component relative to the total weight of the release layer) is shown.
(Release layer-forming composition 1)
Examples 2 to 4
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the composition and the production method of the release layer described in table 1 were changed.
Example 5
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 2 was used as the following components.
(Release layer-forming composition 2)
Example 6
Except that n-heptane in the releasing layer-forming composition was changed to cyclohexane (SP value (delta): 16.8, (delta) D )：16.8、(δ P )：0.0、(δ H ): 0.2 A release film for molding a resin sheet was obtained in the same manner as in example 2).
Examples 7 and 8
A release film for molding a resin sheet was obtained in the same manner as in example 2, except that the coating amount and the solid content ratio were changed as described in table 1. At this time, the same organic solvent ratio as that of the release layer forming composition 1 was prepared.
Example 9
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the composition 3 for forming a release layer was changed to the following composition.
(composition for Forming Release layer 3)
Examples 10 to 12
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the composition and the production method of the release layer described in table 1 were changed.
Example 13
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 4 was used as described below.
(Release layer-forming composition 4)
Example 14
Except that n-heptane in the releasing layer-forming composition was changed to cyclohexane (SP value (delta): 16.8, (delta) D )：16.8、(δ P )：0.0、(δ H ): 0.2 A release film for molding a resin sheet was obtained in the same manner as in example 2).
Example 15 and 16
A release film for molding a resin sheet was obtained in the same manner as in example 2, except that the coating amount and the solid content ratio were changed as described in table 1. At this time, the same organic solvent ratio as that of the release layer forming composition 3 was prepared.
Example 17
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 5 was used.
(composition for Forming Release layer 5)
Example 18
A release film for molding a resin sheet was obtained in the same manner as in example 1, except that the solid content concentration shown in table 1 was changed and the organic solvent ratio was further changed to be the same as that of the release layer-forming composition 5.
Example 19
A release film for molding a resin sheet was obtained in the same manner as in example 17, except that the production method described in table 1 was changed.
Example 20
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 6 was changed.
(composition for Forming Release layer 6)
Example 21
Except that the heptane in the release layer-forming composition 5 was changed to cyclohexane (SP value (delta): 16.8, (delta) D )：16.8、(δ P )：0.0、(δ H ): 0.2 With the same exception of example 1The method of (2) to obtain a release film for molding a resin sheet.
Example 22 and 23
A release film for molding a resin sheet was obtained in the same manner as in example 17, except that the coating amount and the solid content concentration were changed as described in table 1. At this time, the same organic solvent ratio as the release layer forming composition 5 was prepared.
Comparative example 1
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 7 was changed to the following composition.
(Release layer-forming composition 7)
Comparative example 2
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 10, except that the film was applied to the laminated film X2.
Comparative examples 3 and 4
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 10, except that the production method described in table 1 was changed.
Comparative example 5
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 17, except that the production method described in table 1 was changed.
Comparative example 6
A release film for molding an ultrathin layer resin sheet was obtained in the same manner as in example 1, except that the release layer-forming composition 8 was used as the following components.
(Release layer-forming composition 8)
[ Table 1A ]
[ Table 1B ]
[ Table 1C ]
[ Table 2A ]
[ Table 2B ]
[ Table 2C ]
In comparative example 1, since the cationic curable polydimethylsiloxane (a) was not contained, the ceramic sheet had a large peeling force and could not be peeled off. In comparative example 2, the number of protrusions having a height of 10nm or more exceeded 200/mm 2 Pinholes are generated in a green sheet as a release object. Further, in comparative example 2, inorganic particles were present in the entire base material, and the smoothness of the release film was significantly deteriorated, and breakage of the green sheet, pinholes, and the like were generated.
In comparative example 3, the 1 st drying temperature T1 is lower than the 2 nd drying temperature T2, and the constant-speed drying time is longerThus, aggregation of the release layer forming composition occurs, sa is more than 2nm, and the number of protrusions having a height of 10nm or more exceeds 200/mm 2 . In comparative examples 4 and 5, the 1 st drying temperature T1 was low, aggregation of the release layer-forming composition occurred, sa was more than 2nm, and the number of protrusions having a height of 10nm or more exceeded 200 pieces/mm 2 . In comparative example 6, since the release layer-forming composition did not contain an organic solvent having an SP value (δ) of 14 to 17, the release layer-forming composition was coagulated during drying, and the release layer was lacking in smoothness.
Industrial applicability
According to the present invention, by improving the smoothness and peelability of the release layer, a release film is provided that can form a resin sheet having few defects even in an ultrathin layer having a thickness of 1 μm or less, whereby the resin sheet can be produced without causing defects.
Claims (6)
1. A method for producing a release film for molding a resin sheet, comprising the steps of:
a coating step of coating a release layer forming composition on the surface layer A of a polyester film having the surface layer A, wherein,
the surface layer a is a layer substantially free of inorganic particles,
The release layer forming composition comprises a cationically curable polydimethylsiloxane (a);
a drying step of heating and drying the polyester film coated with the release layer forming composition,
the heat drying includes a 1 st drying step and a following 2 nd drying step,
the drying temperature T1 in the 1 st drying procedure is higher than the drying temperature T2 in the 2 nd drying procedure;
and a photo-curing step of irradiating the release layer-forming composition with active energy rays after the drying step.
2. The method for producing a release film for molding a resin sheet according to claim 1, wherein the release layer-forming composition comprises an organic solvent having an SP value (delta) of 14 or more and 17 or less,
the release layer-forming composition contains an organic solvent having an SP value (delta) of 14 to 17 in an amount of 10 mass% or more with respect to 100 mass parts of the total weight of the release layer-forming composition,
the release layer-forming composition in the coating step was applied in an amount of 10g/m 2 The following is given.
3. The method for producing a release film for molding a resin sheet according to claim 1 or 2, which is a method for producing a release film for producing a resin sheet containing an inorganic compound.
4. The method for producing a release film for molding a resin sheet according to claim 3, wherein the resin sheet containing an inorganic compound is a ceramic green sheet.
5. A method for producing a ceramic green sheet, wherein the method for producing a release film for molding a resin sheet according to claim 4 further comprises a step of forming a ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
6. The method for producing a release film for molding a resin sheet according to claim 3 or 4, comprising the step of molding a resin sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
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| JP2020-213851 | 2020-12-23 | ||
| JP2020213851 | 2020-12-23 | ||
| PCT/JP2021/046721 WO2022138485A1 (en) | 2020-12-23 | 2021-12-17 | Method for producing mold release film for resin sheet molding |
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| CN116635160A true CN116635160A (en) | 2023-08-22 |
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| JP (1) | JPWO2022138485A1 (en) |
| KR (1) | KR20230101888A (en) |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11156825A (en) * | 1997-11-25 | 1999-06-15 | Toyo Metallizing Co Ltd | Release film for producing ceramic green sheet |
| JP2010260315A (en) * | 2009-05-11 | 2010-11-18 | Teijin Dupont Films Japan Ltd | Release film |
| JP2013233760A (en) * | 2012-05-10 | 2013-11-21 | Teijin Dupont Films Japan Ltd | Mold release film for anisotropic conductive film |
| CN107405909A (en) * | 2015-03-28 | 2017-11-28 | 三菱化学株式会社 | Mold release film |
| WO2018159247A1 (en) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | Mold releasing film for manufacturing ceramic green sheet and method for manufacturing mold releasing film |
| CN110382602A (en) * | 2017-03-01 | 2019-10-25 | 东洋纺株式会社 | The manufacturing method of polyester film with furandicarboxylic acid unit |
| WO2020050081A1 (en) * | 2018-09-03 | 2020-03-12 | 東洋紡株式会社 | Mold release film for ceramic green sheet production |
| CN111051061A (en) * | 2017-09-21 | 2020-04-21 | 三菱化学株式会社 | Mold release film and laminate |
| JP2020153022A (en) * | 2019-03-18 | 2020-09-24 | リンテック株式会社 | Process paper for synthetic leather, and manufacturing method of synthetic leather |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101997310B1 (en) | 2012-03-28 | 2019-07-05 | 린텍 가부시키가이샤 | Peeling film for step for producing ceramic green sheet |
| JP6208047B2 (en) | 2014-02-28 | 2017-10-04 | リンテック株式会社 | Peeling film for producing green sheet, method for producing peeling film for producing green sheet, method for producing green sheet, and green sheet |
| JP6400430B2 (en) | 2014-10-21 | 2018-10-03 | リンテック株式会社 | Curable composition for silicone coating layer and silicone coating sheet |
| JP6644534B2 (en) * | 2015-12-08 | 2020-02-12 | リケンテクノス株式会社 | Hard coat laminated film |
| JP7466270B2 (en) | 2016-10-27 | 2024-04-12 | リンテック株式会社 | Release sheet |
| JP6593371B2 (en) * | 2017-03-01 | 2019-10-23 | 東洋紡株式会社 | Method for producing release film for producing ceramic green sheet |
-
2021
- 2021-12-17 JP JP2022571401A patent/JPWO2022138485A1/ja active Pending
- 2021-12-17 WO PCT/JP2021/046721 patent/WO2022138485A1/en active Application Filing
- 2021-12-17 CN CN202180086596.XA patent/CN116635160A/en active Pending
- 2021-12-17 KR KR1020237019190A patent/KR20230101888A/en unknown
- 2021-12-22 TW TW110148039A patent/TWI799022B/en active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11156825A (en) * | 1997-11-25 | 1999-06-15 | Toyo Metallizing Co Ltd | Release film for producing ceramic green sheet |
| JP2010260315A (en) * | 2009-05-11 | 2010-11-18 | Teijin Dupont Films Japan Ltd | Release film |
| JP2013233760A (en) * | 2012-05-10 | 2013-11-21 | Teijin Dupont Films Japan Ltd | Mold release film for anisotropic conductive film |
| CN107405909A (en) * | 2015-03-28 | 2017-11-28 | 三菱化学株式会社 | Mold release film |
| WO2018159247A1 (en) * | 2017-03-01 | 2018-09-07 | 東洋紡株式会社 | Mold releasing film for manufacturing ceramic green sheet and method for manufacturing mold releasing film |
| CN110312602A (en) * | 2017-03-01 | 2019-10-08 | 东洋纺株式会社 | Ceramic green sheet release film for manufacture and its manufacturing method |
| CN110382602A (en) * | 2017-03-01 | 2019-10-25 | 东洋纺株式会社 | The manufacturing method of polyester film with furandicarboxylic acid unit |
| CN111051061A (en) * | 2017-09-21 | 2020-04-21 | 三菱化学株式会社 | Mold release film and laminate |
| WO2020050081A1 (en) * | 2018-09-03 | 2020-03-12 | 東洋紡株式会社 | Mold release film for ceramic green sheet production |
| JP2020153022A (en) * | 2019-03-18 | 2020-09-24 | リンテック株式会社 | Process paper for synthetic leather, and manufacturing method of synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022138485A1 (en) | 2022-06-30 |
| TWI799022B (en) | 2023-04-11 |
| TW202231478A (en) | 2022-08-16 |
| JPWO2022138485A1 (en) | 2022-06-30 |
| KR20230101888A (en) | 2023-07-06 |
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