PH12015502250B1 - Release film for green sheet production - Google Patents
Release film for green sheet production Download PDFInfo
- Publication number
- PH12015502250B1 PH12015502250B1 PH12015502250A PH12015502250A PH12015502250B1 PH 12015502250 B1 PH12015502250 B1 PH 12015502250B1 PH 12015502250 A PH12015502250 A PH 12015502250A PH 12015502250 A PH12015502250 A PH 12015502250A PH 12015502250 B1 PH12015502250 B1 PH 12015502250B1
- Authority
- PH
- Philippines
- Prior art keywords
- release agent
- green sheet
- agent layer
- release
- producing
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 192
- 239000000463 material Substances 0.000 claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 29
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- -1 (methyl) acryloyl group Chemical group 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 212
- 239000010408 film Substances 0.000 description 154
- 239000000919 ceramic Substances 0.000 description 34
- 235000019592 roughness Nutrition 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000003999 initiator Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000000994 depressogenic effect Effects 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HOKDBMAJZXIPGC-UHFFFAOYSA-N Mequitazine Chemical class C12=CC=CC=C2SC2=CC=CC=C2N1CC1C(CC2)CCN2C1 HOKDBMAJZXIPGC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PTKHNBWCIHXVFS-UHFFFAOYSA-N 4-[2-methyl-1-(4-methylsulfanylphenyl)propan-2-yl]morpholine Chemical compound C1=CC(SC)=CC=C1CC(C)(C)N1CCOCC1 PTKHNBWCIHXVFS-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000006873 Coates reaction Methods 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 206010026865 Mass Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001307210 Pene Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 235000005505 Ziziphus oenoplia Nutrition 0.000 description 1
- 244000104547 Ziziphus oenoplia Species 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/005—Presence of (meth)acrylic polymer in the release coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Laminated Bodies (AREA)
- Producing Shaped Articles From Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
Abstract
A release film for producing a green sheet of the present invention includes a base material and a release agent layer. The release agent layer is formed by irradiating an active energy ray to a coated layer formed by coating a material for forming release agent layer to a first surface. The material for forming release agent layer contains an active energy ray curable compound (A) having at least one reactive functional group selected from the group consisting of a (methyl) acryloyl group, an alkenyl group and a maleimide group, a polyorganosiloxane (B) and a carbon nanomaterial (C). An arithmetic average roughness Ra1 of an outer surface of the release agent layer is 8nm or less and a maximum projection height Rp1 thereof is 50nm or less. According to the present invention, it is possible to provide a release film for producing a green sheet which is capable of producing the green sheet having high reliability and preventing a pinhole and a partial thickness variation in a surface of the green sheet from generating.
Description
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SPECIFICATION “0 o i nv ~
RELEASE FILM FOR GREEN SHEET PRODUCTION Sy ps
The present ipvention relates to a release film for producing a green sheet. o
When manufacturing a ceramic capacitor, a release ” . film for producing |a green sheet is used to form the hy green sheet. -
The release fhm is usually composed of a base material and a release agent layer. The green sheet is manufactured by cohting a ceramic slurry, in which ceramic particles and a binder resin are dispersed and dissolved in an organic solvent, on such a release film and drying it. Further, the green sheet thus manufactured is released from the release film and is used in manufacturing the ceramic capacitor.
In the production of the green sheet using the conventional release film, there is a problem that a pinhole generates in a surface of the green sheet by ] that an irregularity of a surface of the release film is transferred to the green sheet.
Therefore, an |attempt of reducing phenomena that the irregularity affects the green sheet has been made by suppressing the irregularity of the surface of the release film from (generating to the extent possible {see Patent Document] 1).
However, acconding to reduction of the size of the ceramic capacitdr and requirement of a high-density ceramic capacitor in recent years, a further thinned
. ¢ ” ‘ : > . ceramic capacitor| is required. However, the “oo conventional release film has not been fulfilled the ht requirement of the thinned ceramic capacitor. In other words, if an attempt of trying to produce a thin green = sheet is made in the conventional release film, it is iy difficult to prevent the pinhole and the like from " generating due to that the irregularity of the surface = of the release film|is transferred to the green sheet. = -
Further, the release film is usually stored in a a state wound in a roll shape and transported. When the E green sheet is produced, the release film is used by unwinding the release film from the wound state in the roll shape. Conventionally, when this wound release film is unwound, static electricity generates on the surface of the release film, so that there is a problem that foreign matters such as dust and the like adhere to the release film by the generated static electricity. Thereflore, if the green sheet is produced by using the release film, there is a problem that the pinhole generates in the green sheet due to the adhered foreign matters andithe like. In particular, the lower a degree of the irregularity in the surface of the : release film is, the more the static electricity as described above generates conspicuously.
The Patent Document 1 is JP-A 2003-203822.
It 1s an object of the present invention to provide a release |film for producing a green sheet which 1s capable of producing the green sheet having high reliability and preventing a pinhole and a partial thickness wvariation| in a surface of the green sheet from generating.
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The above object is achieved by the inventions = (1) to (5) set forth below. =o a. (1) A release film for producing a green sheet, = comprising: a base material having a first surface and a . second surface; and lo a release agent layer provided on the first oo surface of the base |material, ” wherein the elease agent layer 1s formed by Le ) irradiating an active energy ray to a coated layer = formed by coating a| material for forming release agent layer to the first surface, and the material for forming release agent layer contains an active energy ray curable compoun (A) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl |group, an alkenyl group and a maleimide group, a polyorganosiloxane (B) and a carbon nanomaterial (C), and wherein an arithmetic average roughness Ra; of an outer surface of the release agent layer is 8 nm or less and a maximum |projection height Rp; of the outer surface of the reledse agent layer is 50 nm or less. (2) In the release film for producing the green sheet described in |the above-mentioned invention (1), an average thickness of the release agent layer is in the range of 0.2 to |2 um. (3) In the release film for producing the green sheet described in tlhe above-mentioned invention (1) or (2), a content in| solid content conversion of the polyorganosiloxane |(B) in the material for forming release agent layer {is in the range of 0.5 to 5 mass$. (4) In the release film for producing the green
, | ,
Ca : y sheet described i any one of the above-mentioned = inventions (1) to (3), the polyorganosiloxane (B) is a " polyorganosiloxane | having a straight or branched - molecular chain, and terminals and/or a side chain of > the molecular chain] include silicon atoms, wherein the at least one reactive functional group selected from or the group consisting of the (meth)acryloyl group, the ” alkenyl group and the maleimide group is bonded to the silicon atoms of the molecular chain, either directly ul or through a bivalent linking group. fan oe (5) In the rellease film for producing the green sheet described 1 any one of the above-mentioned inventions (1) tol (4), a content in solid content conversion of the; carbon nanomaterial (C) in the material for forming release agent layer 1s in the range of 0.05 to 10 |mass%.
According to | the present invention, it is possible to provid a release film for producing a green sheet having| excellent antistatic property and releasability with |excellent smoothness in an outer surface of the rellease agent layer. This makes it possible to prevent jan irregularity of a surface of the ’ release film for prjoducing the green sheet from being transferred to the [green sheet. As a result, it is possible to prevent] a pinhole and a partial thickness variation in a surface of the green sheet from generating.
The release film for producing the green sheet of the present invention has suitable conductive property.
Therefore, 1t 1s posible to lower a resistance value of the surface of the release film for producing the green sheet. This mpkes it possible to suppress static electricity from generating when the wound release film
© , ] : 3 for producing the green sheet is unwound. As a result, = since it is possible to prevent foreign matters such as ~ dust and the like from adhering to the surface of the ~ release film for producing the green sheet, it is ” possible to prave]. not only a slurry from being = repelled at the time of coating a ceramic slurry, but oO also the pinhole in the surface of the produced green oO : sheet from generating. In addition, it is possible to 0 prevent a release defect from being generated by charge ~ when the green sheet 1s released, so that it is An possible to prevent| breakage, wrinkle and the like from ~ being generated to the green sheet.
FIG. 1 1s a cross sectional view of a release film for producing] a green sheet according to the present invention.
Hereinafter, the present invention will be described in detail |based on a preferred embodiment. <<Release Film| for Producing Green Sheet>>
A release film for producing a green sheet according to the present invention is used in producing the green sheet. The produced green sheet is used for producing a ceramic |capacitor and the like.
FIG. 1 1s a ross sectional view of a release film for producing] a green sheet according to the present invention. In the following description, the upper side in FIG. 1 will be referred to as “upper” and the lower side thereof willl be referred to as “lower”.
As shown in |Fig. 1, the release film 1 for
* + . ' . . + | . > ' [ES] producing the green sheet includes a base material 11 0 having a first surface 111 and a second surface 112 and @ a release agent layer 12 provided on the first surface 111 of the base material 11. In other words, the Le release film 1 for producing the green sheet is ol constituted from a| two layer structure in which the pd base material 11 and the release agent layer 12 are = laminated to bond fogether in this order as shown in =
FIG. 1. = o
In this specification, in the case where the - green sheet is prodiiced by using the release film 1 for producing the green sheet, the green sheet, for "example, 1s forme by coating a dissolved ceramic 15. slurry onto an outqr surface 121 of the release agent layer 12.
In the present invention, the release film 1 for producing the green| sheet has the base material 11 and the release agent lpyer 12. In the release film 1 for producing the green| sheet, the release agent layer 12 is formed by coating a material for forming release agent layer containing an active energy ray curable compound (A) having|a predetermined reactive functional group, a polyorganosiloxane (B) and a carbon nanomaterial (C) at|a side of the first surface 111 of } the base material 11 and irradiating an active energy ray to it. An arithmetic average roughness Ra; of the outer surface 121 of the release agent layer 12 is 8 nm or less and a maximum projection height Rp; of the ~ outer surface 121 thereof is 50 nm or less.
By having such| features, it is possible to obtain : a release film 1 or producing a. green sheet having excellent antistati property and releasability with excellent smoothness in the outer surface 121 of the
) cu ” release agent layer| 12. If the green sheet is produced = using this releas film 1 for producing the green = sheet, 1t is possiible to prevent a pinhole and a ” partial thickness variation in a surface of the green - sheet from generating. ” bot
In particular, the release agent layer 12 has oo suitable conductiv property due to action of the Rr ~ carbon nanomaterial| (C). Therefore, it is possible to o } lower a resistance |value of a surface of the release . film 1 for producing the green sheet. This makes it possible to suppress static electricity from generating when the wound relgase film 1 for producing the green sheet 1s unwound. As a result, it 1s possible to prevent foreign matters such as dust and the like from adhering to the surface of the release film 1 for ~ producing the green sheet, so that it is possible to ~~ prevent the pinhole| from generating due to the adhered foreign matters.
Further, the (release agent layer 12 exerts the excellent releasability due to action of the polyorganosiloxane |B). Therefore, it is possible for the release agent layer 12 to prevent breakage, wrinkle and the like from being generated to the green sheet by a synergetic effec of the releasability due to the action of the polyorganosiloxane (B) and the antistatic . property due to the action of the carbon nanomaterial (C) when the green |sheet is released from the release film 1 for producing the green sheet.
Further, the aterial for forming release agent layer containing the active energy ray curable compound (A) having the predetermined reactive functional group has suitable fluidity and shape-keeping property.
Therefore, if the release agent layer 12 constituted of
> = the material for tyes release agent layer is used, ws it is possible o easily fill (compensate) the = irregularity of on surface of the base material 11. SG
Further, it is podsible to reliably keep the filled -. 5 state. As a result] it becomes possible to obtain the ~ outer surface 121 of the release agent layer 12 having " the excellent smoothness. Therefore, it is possible to ~ . prevent the pinholejand the like from generating, which oo may generate by transferring the irregularity shape of o outer surface 121 off the release agent layer 12 to the wi green sheet.
Further, the grithmetic average roughness Ra; and the maximum orn height Rp; of the outer surface 121 of the release agent layer 12 fall within the range described above. herefore, even if the green sheet having a thinner thickness than e.g. 1 um is produced, it is possible to prevent the irregularity of the outer surface 121 of the| release agent layer 12 from being transferred to the green sheet. This makes it possible to obtain the green! sheet having the high reliability, which prevents the pinhole in the surface of the green sheet from generating.
Hereinafter, etailed description will now be made on the respective layers that constitute the release film 1 for producing the green sheet according to the present embodiment. <Base Material; 11>
The base material 11 serves to apply physical ~ strength, such as | rigidity or flexibility, to the release film 1 for producing the green sheet (hereinafter, simply referred to as “release film 17).
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The base material 11 includes the first surface = 111 and the second surface 112 as shown in FIG. 1. "
Examples of Ja material constituting the base - material 11 includé, but not limited particularly, a A film made of a plastic, e.g., a polyester resin such as a polybuthylene terephthalate resin, a polyethylene " terephthalate resin, and a polyethylene naphthalate = resin; a polyolefin|resin such as a polypropylene resin os and a polymethylpentene resin; and polycarbonate. The ov base material 11 may be a monolayer film or a multiple dn layer film including two or more layers of the same ~ kind or different kinds. Among them, the film made of the polyester resi is preferable. Moreover, a film made of a biaxially-stretched polyethylene terephthalate resin|is more preferable. In particular, the film made of the polyester resin seldom generates the dust or the ike during the processing or use thereof. It 1s therefore possible to effectively prevent generation of a coating defect of a ceramic slurry by the dust{ or the like in a case where the green sheet is produced by using the release film 1 which 1s produced | by using the film made of the polyester resin. Consequently, it is possible to produce the green sheet having less pinhole.
The base material 11 may include a filler in addition to the matprial as described above. Examples of the filler include silica, titanium oxide, calcium carbonate, kaolin, luminum oxide and the like. These materials may be used singly or in combination of two or more of them. y including such a filler, it is © possible to improve] the smoothness of front and rear surfaces of the |base material 11 while giving mechanical strength) to the base material 11, thereby enabling to suppress| blocking from generating.
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Further, it |is preferred that an arithmetic O average roughness Rap of the first surface 111 of the a) base material 11 is|in the range of 2 to 80 nm.and more = preferably in the nyange of 5 to 50 nm. This makes it os is possible to form|the smoothed release agent layer 12 ~ filling the irregularity of the first surface 111 on bo the first surface | 111 of the base material 11 as = described later. Therefore, if the arithmetic average = roughness Rap falls| within the above range, it becomes - possible to obtain conspicuous smoothing action. =
On the other| hand, if the arithmetic average roughness Rag of he first surface 111 exceeds the upper limit value npted above, there is a case that it 1s required to relatively thicken the release agent layer 12 in order to sufficiently fill the irregularity of the first surface 111, which depends on a constituent material and the like of the material for forming release agent layer.
Further, a maximum projection height Rpg of the first surface 111 ils preferably in the range of 10 to 700 nm and more preferably in the range of 20 to 500 nm. This makes it| is possible to form the smoothed release agent layer|12 filling the irregularity of the ’ first surface 111 om the first surface 111 of the base material 11 as degcribed later. Therefore, if the maximum projection height Rpg falls within the above range, 1t becomes possible to obtain a conspicuous smoothing action.
Further, it is preferred that an arithmetic average roughness Ra, of the second surface 112 of the base material 11 is |in the range of 5 to 40 nm and more preferably in the nange of 10 to 30 nm. Further, a maximum projection height Rp, of the second surface 112
To | . :
Cl _ of the base material 11 is in the range of 60 to 500 = nm. When the release film 1 having such high = smoothness in the (outer surface 121 of the release = agent layer 12 is wound around a paper-made, plastic- we made or metal-made (core member in a roll shape, an air ° is removed well. This makes it possible to effectively o suppress a winding |deviat fon, For that reason, there =z is no need to increase a winding tension. It becomes I. therefore possible to suppress deformation of the core C2 member caused by the winding tension. Further, when . the release film 1 having the roll shape is unwound, it te is possible to prevent the generation of blocking between the rent | and rear surfaces of the wound release film 1. Moreover, when the release film 1 on which the green sheet is formed is wound and stored, it is possible to prevent a surface shape of the second surface 112 of the base material 11 which is in contact : with the green sheet from being transferred to the green sheet, therehy enabling to prevent the pinhole and the partial thickness variation in the surface of the green sheet from generating. Consequently, 1t is possible to form {the green sheet having the high reliability. ’
In contrast, iff the maximum projection height Rp: is smaller than the |lower limit value noted above, when the release film 1 before the green sheet (thin layer) is formed is wound at the time of storing the release film 1 before the green sheet is formed, it is easy to involve the air an generate the winding deviation.
Therefore, it becomes difficult to handle the release : film 1. Further, it becomes difficult to sufficiently prevent the blocking due to the contact between the base material 11 and the release agent layer 12. On the other hand, if | the maximum projection height Rp; exceeds the upper limit value noted above, when the
. | | . . \ . or release film 1 after the green sheet is formed is wound, an irregularfity shape of the second surface 112 - of the base material 11 which is in contact with the w green sheet is ransferred to the green sheet. -
Therefore, there 1 a fear that the pinhole and the = partial thickness [variation may occur to the green oO sheet, so that it | becomes difficult to sufficiently i keep the smoothness |of the green sheet. ey =
As described |above, it 1s preferred that the + maximum projection height Rp; of the second surface 112 - of the base material 11 is preferably in the range of ) 60 to 500 nm, more preferably in the range of 80 to 400 nm and even more preferably in the range of 100 to 300 nm. This makes it possible to obtain the above effects conspicuously. :
In this regard, it is to be noted that the arithmetic average| roughness Rap and the maximum 200 projection height Rpg of the first surface 111 of the base material 11 and the arithmetic average roughness
Ra, and the maximum projection height Rp, of the second surface 112 of the Base material 11 are values obtained by measuring in accordance with JIS B0601-1994 using a surface roughness meter “SVv3000S4” (probe type) made by
Mitsutoyo Corporation in this specification. In this specification, the |“arithmetic average roughness and } maximum projection height” mean the values obtained by measuring as described above, unless otherwise noted.
An average thickness of the base material 11 is not limited particularly, but preferably in the range of 10 to 300 pm and| more preferably in the range of 15 to 200 ym. In this case, a resistance to tear or breaking can be ade particularly superior while ‘keeping proper the fllexibility of the release film 1.
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Pd <Release i. Layer 12> hs -
The release agent layer 12 is formed on the first oe surface 111 of the base material 11. -
The release ajgent layer 12 serves to apply the - releasability and | the antistatic property to the - release film 1. The release agent layer 12 is a layer od which is formed Db curing the material for forming - } release agent Laydr via irradiation of the active = energy ray.
The release algent layer 12 is constituted from the material for orming release agent layer. The material for forming release agent layer includes the active energy ray curable compound (A) having at least one reactive functional group selected from the group consisting of the | (meth)acryloyl group, the alkenyl group and the maleimide group, the polyorganosiloxane (B) and the carbon nanomaterial (C).
The release [agent layer 12 having such a configuration has |the suitable conductive property.
Therefore, it is possible to lower the resistance value : of the outer surface 121 of the release agent layer 12.
This makes it ppssible to suppress. the static electricity from generating when the wound release film for producing the green sheet is unwound. As a result, since it is possiblle to prevent the foreign matters from adhering to the outer surface 121 of the release agent layer 12, it [is possible to prevent the pinhole from generating to the green sheet. Further, since it is. possible to prevent fluctuation and repelling of the ceramic slurry from being generated due to charge of the surface of th release agent layer 12, it is
, > > possible to form he green sheet having more uniformly - thickness. Further, the release agent layer 12 having = such a con iguratioh has the releasability in addition - to the suitable copauctive property. Therefore, when ~ the green sheet is |released, it is possible to prevent the release defect {from being generated by the charge. gy
As a result, it is| possible to prevent the breakage, = the wrinkle and the like from being generated to the CE . green sheet.
Hereinafter, (the respective components of the material for forming release agent layer will now be described in detail
In this regard, it 1s to be noted that the material for forming release agent layer before irradiating the active energy ray exists in an uncured state or a soni-curds state at room temperature.
Further, such| a material for forming release agent layer has the suitable fluidity at the time of coating 1t onto the first surface 111 of the base material 11. Therefore, if the material for forming release agent layer] is used, it is possible to easily } fill the irregularity in the first surface 111 of the base material 11, thereby enabling the filled state to be maintained reliably. As a result, it is possible to prevent the irregularity of the base material 11 from affecting the side| of the outer surface 121 of the release agent layen 12 opposite to the base material 11, thereby enabling the outer surface 121 of the release agent layer 12 to be smoothed. [Active Energy, Ray Curable Compound (A) ]
The active energy ray curable compound (A) is a component that makes contribution to the formation of
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Ce the release agent layer 12 by curing. This makes it = possible to obtain | the release agent layer 12 having = appropriate mechanical strength.
The active engrgy ray curable compound (A) has at ” least one reactive |functional group selected from the ~ group consisting f the (meth)acryloyl group, the en alkenyl group and the maleimide group. Examples of the = alkenyl group include an alkenyl group having a carbon number of 2 to 10| such as a vinyl group, an allyl 1 group, a propenyl group, a hexenyl group and the like. "
In particular, it ids preferred that the active energy ’ ray curable compoun (A) has, in one molecule, two or more (preferably three or more) reactive functional groups. Thus, it |is possible for the release agent layer 12 to obtainy the superior curability, superior solvent resistance| and the superior releasability.
Further, the active |energy ray curable compound (A) has the suitable fluidity and the shape-keeping property.
Therefore, if the material for forming release agent layer containing the active energy ray curable compound (A) 1s coated onto |the first surface 111 of the base material 11, it ils ‘possible to reliably fill the irregularity of th first surface 111 of the base material 11 with the material for forming release agent layer. Further, ity is possible to reliably keep the filled state. As |a result, it becomes possible to : smooth the outer suxpface 121 of the release agent layer 12. :
A content of the reactive functional group in the active energy ray curable compound (A) is preferably an equivalent of 10 or | more per 1 kg of the active energy ray curable compoun (A). In this case, even when the material for forming release agent layer is coated as a thin film on the figst surface 111 of the base material a 11, it is possible] to keep particularly the superior = curability of the jactive energy ray curable compound " (A). -
Specific examples of the active energy curable ” compound (A) may include a multifunctional " (meth)acrylate such as dipentaerythritol = tri(meth)acrylate, dipentaerythritol = tetra{meth)acrylate dipentaerythritol - penta(meth)acrylate dipentaerythritol wl : hexa (meth)acrylate, | pentaerythritol tri(meth)acrylate and pentaerythritol] tetra(meth)acrylate. Among them, it is preferable to use at least one multifunctional acrylate selected from the group consisting of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, ipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and entaerythritol tetraacrylate. In this case, even when the material for forming release agent layer is coated as the thin film on the first surface 111 of the base material 11, it is possible to keep particularly the superior curability of the active energy ray curable gompound (A).
A content in [solid content conversion (content . ratio in the total Isolid components except a solvent) of the active energy ray curable compound (A) in the material for oo release agent layer is preferably in the range of 65 to 98.5 mass% and more preferably in the range of 71 to 96.3 mass$%. rr (B)]
The polyorgangsiloxane (B) 1s a component for developing the releasability in the release agent layer 12.
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Examples of the polyorganosiloxane (B) include a i polyorganosiloxane | having a straight or branched oe molecular chain. articularly, it is preferred that i. 5 silicon atoms ar included in terminals of the molecular chain and/or a side chain of the molecular bod chain and at leaBt one reactive functional group = selected from he group consisting of the = (meth)acryloyl group, an vinyl group and the maleimide 5 group is bonded to |the silicon atoms of the molecular . - chain, either directly or through a bivalent linking group. At least one reactive functional group may be included in one molecule thereof.
Further, examples of the bivalent linking group may include an alkylene group, an alkyleneoxy group, an oXy group, an imino group, a carbonyl group and the combinations thereof.
The carbon number of the bivalent linking group is preferably in (the range of 1 to 30 and more : preferably in the range of 1 to 10.
Further, depending on the necessity, the polyorganosiloxane ((B) may be used in combination of two or more kinds thereof.
A modified polyorganosiloxane substituted by the reactive functiona group 1s incorporated into and fixed to a cress-linking structure of a cured body of the active energy [ray curable compound (A) when the active energy ray curable compound (A) is allowed to . cure by the Hrradiarion of the active energy ray. This makes it possible to prevent the polyorganosiloxane as a component of the release agent layer 12 from migrating to and transferring to the green sheet formed
. at the side of ” outer surface 121 of the release > agent layer 12. ™ =
Further, examples of an organic group other than we the reactive funcfional group that constitutes the = polyorganosiloxane {B) include a monovalent hydrocarbon " group that does not have an aliphatic unsaturated bond. =
The organic group (may be a plurality of monovalent = . hydrocarbon groups (in which the hydrocarbon groups may » be the same kind or|different kinds. Ln
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The carbon he of the hydrocarbon groups is preferably in the rhnge of 1 to 12 and more preferably in the range of 1 to 10.
Specific examples of the hydrocarbon groups may include: an alkyl |group such as a methyl group, an ethyl group and a propyl group; an aryl group such as a phenyl group and a tolyl group; and the like.
It is preferred that 80 mol% or more of the organic group other| than the reactive functional group having the configuration is the methyl group. In this case, the releasability of the release agent layer 12 can be kept particullarly superior.
A content in| solid content conversion of the polyorganosiloxane [(B) in the material for forming ’ release agent layer| is preferably in the range of 0.5 to 5 mass% and more |preferably in the range of 0.7 to 4 mass%. In this case, the ceramic slurry can be coated on the base material 11 without being repelled. This makes it possible 0 keep particularly the superior releasability of the release film 1 for producing the green sheet.
. | : fe ox : : In contrast, 1f the content in the solid content = conversion of th polyorganosiloxane (B) in the ™ material for forming release agent layer 1s smaller ot than the lower limit value noted above, there is a fear > that the release abn layer 12 thus formed cannot show ~ the sufficient releasability, depending on a kind of " the base parish | On the other hand, if the content - in- the solid content conversion of the = polyorganosiloxane |(B} in the material for forming release agent layer exceeds the upper limit value noted LT above, there is a fear that, when the ceramic slurry is > ’ coated on the surfage of the release agent layer 12 to be formed, the ceramic slurry is repelled with ease, depending on the constituent material of the ceramic slurry.
Assuming that lan amount of the active energy ray curable compound (A) is A mass parts and an amount of the polyorganosiloxgne (B) is B mass parts, a mass ratio B/A is preferably in the range of 0.7/99.3 to 5/95 and more preferably in the range of 1/99 to 4.5/95.5. In this case, the aforementioned effects become more 2 [Carbon Nanomaterial (C)]
The carbon pan (C) serves to apply the antistatic property |to the release agent layer 12.
Examples of carbon nanomaterial (C) include fullerene, a carol nanotube, a carbon nanofiber, a carbon nanohorn and the like. These materials may be used singly or in combination of two or more of them.
Among them, the | carbon nanotube is preferable particularly. This| makes 1t possible to apply more . suitable conductive |property to the release agent layer
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Cd 12, thereby ati a surface resistance value of the = outer surface 121 af the release agent layer 12 to be - lowered. For this | reason, it is possible to prevent = the foreign matters| from adhering to the outer surface ha 121 of the retenes pene layer 12. As a result, it is ~ possible to prevent] the pinhole from generating in the ” green sheet formed : the release agent layer 12. =
In particular, the carbon nanotube in the carbon o ’ nanomaterial (C) ; described above is formed into a o fibrous form, which|has a high aspect ratio (short-long degree). Therefore, it is possible to orient the carbon nanotube with ease so that a fiber length in a long axis thereof extends along a surface direction of the release agent layer 12. Therefore, if the carbon nanotube is used, if is possible to obtain the release agent layer 12 having more smoother outer surface 121 with the suitable conductive property.
An average iameter (fiber diameter) of the carbon nanomaterial|(C) is preferably in the range of 1 to 1000 nm, more preferably in the range of 3 to 500 nm, and even more preferably in the range of 5 to 100 nm. :
An average length (fiber length) of the carbon nanomaterial (C) 1s not limited particularly, but preferably in the (range of 10 nm to 200 um, more preferably in the yrange of 50 nm to 100 um, and even more preferably in the range of 100 nm to 50 pm.
An aspect ratio of the carbon nanomaterial (C) is preferably in the range of 10 to 10000, more preferably in the range of 200 to 5000, and even more preferably in the range of 400 to 2000. In this regard, the aspect ratio of the| carbon nancomaterial (C) is a value
{rs measured by observing the carbon nanotube using a = scanning electron microscope (produced by Hitachi High- " ~ Technologies Corporation and sold under a trade name
NSL47007) . © pi
An amount of |the carbon nanomaterial (C) in the : material for forming release agent layer is preferably - in the range of 0.05 to 10 mass%, more preferably in - the range of 0.1 to 5 mass%, and even more preferably 0 in the range of 0.2 to 1 mass%. If the amount of the - carbon nanomateriall (C) is smaller than the lower limit oa value noted above there 1s a case that it is impossible to sufficiently = lower the surface resistivity of the| release agent layer 12. On the ’ other hand, if the] amount of the carbon nanomaterial (C) exceeds the upper limit value noted above, there is a fear that strength of the release agent layer 12 is lowered, thereby eading to deterioration of the solvent resistance. [Photopolymerization initiator (D)]
In order to | allow the material for forming release agent layer] to cure, the material for forming release agent layer may include a photopolymerization initiator (D). I particular, in the case where ultraviolet ray is jused as the active energy ray, the use of the photopolymerization initiator (D) makes it possible to allow |the material for forming release : agent layer to cure |easily and reliably.
The photopolymerization initiator (D) is not particularly limited. For example, it is preferable to use an o-aminocalkylphenone-based photopolymerization initiator. Such an a—-aminoalkylphenone-based photopolymerization initiator is a compound which makes
Pent the active energy ; curable compound (A) be less = : susceptible to the| oxygen inhibition at the time of bd curing of the material for forming release agent layer. =
Thus, the superior |curability can be obtained even if we the release film |1 is manufactured under an air ~ atmosphere. . .
Examples | the a-aminoalkylphenone-based = photopolymerizationjiinitiator may include 2-methyl-1{4- o (mechyLthio) phenyl) 12-morphol inopropane=1-one, 2- o benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butanone- + 1, dine 1-2 sethignary seth) 34 . (4+morpholinyl)phenyl]~-1-butanone and the like. In this case, It is | possible to obtain the superior curability, the suber ior solvent resistance and the superior releasability.
A content in| solid content conversion of the photopolymerization| initiator (D) in the material for forming release agent layer is preferably in the range of 1 to 20 mass% and more preferably in the range of 3 to 15 mass%. In this case, even if the release agent layer 12 has a thickness at which the curability is hardly obtainable due to the oxygen inhibition, it is possible to obtain the superior curability, the superior solvent resistance and the superior releasability. | .
In the i” film 1 as described above, a component derived rom the polyorganosiloxane (B) is segregated near the outer surface 121 of the release agent layer 12. ‘he reason for occurrence of this segregation is as follows. This is because due to the use of the polyorganosiloxane (B) differing in a molecular structure, a polarity, a molecular weight or the like from the energy ray curable compound
: o (A), the polyorganopiloxane (B) 1s pushed up toward the = vicinity of the surface of the coated layer while the hn coated layer of the material for forming release agent - layer is allowed to|cure. oe | pots rf - The material for forming release agent layer may " contain other components in addition to the = aforementioned comppnents. For instance, the material - for forming release agent layer may contain the other w components such as sensitizer, an antistatic agent, a - : hardening agent and|so forth. =
As the sensitiizer, it may be possible to use, e.g., 2,4-diethy thioxanthone or’ isopropyl thioxanthone. This makes it possible to enhance reactivity.
A content in| solid content conversion of the other components in the material for forming release agént layer 1s preferably in the range of 0 to 10 masss. : As described above, the arithmetic average roughness Ra; of the outer surface 121 of the release agent layer 12 thereof is 8 nm or less and the maximum . projection height Rp; thereof is 50 nm or less. Thus, when the green sheef is molded at the side of the outer surface 121 of th release agent layer 12, it is possible to reliably prevent the generation of the pinhole and the partial thickness variation in the green sheet. This makes it possible to keep a highly smooth surface of the green sheet.
An average thickness of the release agent layer 35. 12 is preferably in| the range of 0.2 to 2 um and more preferably in the ange of 0.3 to 1.5 pum. If the
. © yo average thickness lof the release agent layer 12 is ~ smaller than the lower limit value noted above, the - smoothness of the [outer surface 121 of the release - agent layer 12 becomes insufficient. As a result, te there is a fear that, when the green sheet is molded at ~ the side of the outler surface 121 of the release agent " layer 12, the pinhqgle, the partial thickness variation = or the like is generated in the green sheet. On the - other hand, 1f the average thickness of the release ” agent layer 12 exg¢eeds the upper limit value noted o above, a curl is easily generated in the release film 1 ~ due to cure shrinkage of the release agent layer 12.
Furthermore, the blocking is easily generated between the second surface [112 of the base material 11 and the outer surface 121 of the release agent layer 12 which ’ are in contact with each other by winding the release film 1. For that! reason, there 1s a fear that a trouble is generated in winding the release film 1 or that an electric |charge amount 1s increased when unwinding the releage film 1.
A surface resigptivity of the outer surface 121 of the release agent layer 12 is 1.0 x 10 Q/O0 or less and more preferably 1.0 x 10' Q/0O0 or less. If the surface resistivity |falls within the above range, it is possible to reliablly reduce that the foreign matters derived from the generation of the static electricity adhere to the outer surface 121 of the release agent layer 12. | :
In this regard, it is to be noted that the surface resistivity | means a resistance per unit of a surface area in thils specification. Further, an unit of the surface resistivity is used as Q/0 in this specification. oo .
& i
In this regard, the surface resistivity is = measured according to JIS K6911 (1995). = ps <<Method of Producing Release Film for Producing we
Green Sheet>> fod
Next, descrip ion will be made on one preferred on embodiment of a method of producing the release film 1 oo for producing the green sheet as described above. w cr
The method of |producing the release film 1 of the " present embodiment (includes a base material preparing step for preparing the base material 11, a coated layer : forming step for forming a coated layer by coating the material for forming release agent layer containing the predetermined components onto the first surface 111 of the base material Hy and drying it, and a release agent layer forming step for forming the release agent layer +12 by curing the cpated layer via irradiation of the active energy ray.
The respectiv steps will now be described in detail. <Base Material| Preparing Step> ~ First, the base material 11 is prepared.
The first surface 111 of the base material 11 can . be subjected to a surface treatment using an oxidation method and the like. This makes it possible to keep the superior adhesion between the base material 11 and the release agent layer 12 formed at the side of the first surface 111 of the base material 11.
Examples of he oxidation method include: a corona discharge treatment; a plasma discharge
Pat treatment; a chromium oxidation treatment (wet-type); a = flame treatment; |a hot air treatment; an ozone hr treatment; an ultraviolet irradiation treatment; and — the like. The surface treatment using these oxidation be methods can be arbitrary selected depending on a kind - of the base material 11. Among them, the corona " discharge treatment |is particularly preferable from the = aspect of the effects and the operability for the = surface treatment. u - <Coated Layer [Forming Step> ht i
First, in this step, prepared is the material for forming release agent layer.
Prepared is he material for forming release agent layer containing components such as the active energy ray curable compound (A), the polyorganosiloxane (B) and the carbon nanomaterial (C) as described above.
This is dissolved or dispersed with a solvent to obtain the material for forming release agent layer.
Examples of the solvent include methanol, ethanol, toluene, ethyl acetate, © xylene, methylethylketone, methylbuthylketone, isopropylalcohol and the like. ]
Next, the marerial for forming release agent layer in the form of a liquid is coated onto the first surface 111 of the base material 11 to be dried. Thus, the coated layer is |obtained.
By using the material for forming release agent layer containing the components as described above, it 1s possible to fill the irregularity of the first surface 111 of the base material 11. Consequently, it y - is possible to smdoth the outer surface 121 of the © release agent layer|l2. ra =
Examples of the method of coating the material we for forming release agent layer include: a gravure coating method; a bar coating method; a spray coating - method; a spin coating method; an air-knife coating = method; a roll coatjing method; a blade coating method; — a gate roll coating method; a die coating method; and Co the like. o
Lom
Further, examples of the method of drying the material for forming release agent layer include, but not limited particularly, a method of drying with a hot air drying furnace and the like. ]
A drying tpt 3s not limited particularly. A drying temperature fis preferably in the range of 50 to 100°C. A drying ce is preferably in the range of 5 200 seconds to 1 minute. This makes it possible to efficiently form the coated layer particularly while preventing the coated layer from being altered involuntarily. Consequently, it 1s possible to improve the productivity of] the finally obtained release film 1. Further, if the |drying temperature falls within the above range, in the|case where the material for forming release agent layer| contains the solvent and the like, it is possible to reliably prevent warpage and cracks associated with the| evaporation of the solvent at the time of drying from occurring to the coated layer. } <Release Agent| Layer Forming Step>
Next, the release agent layer 12 is formed by irradiating the actlive energy ray to the coated layer obtained in the coated layer forming step and curing.
: . Co : *
Ga ’
In this step the coated layer which fills the ho irregularity of the first surface 111 of the base = material 11 reliably in the coated layer forming step we 1s allowed to cure with keeping the smoothness of the ~ outer surface 121 thereof. As a result, it is possible g to obtain the release agent layer 12 of which outer - surface 121 is suffliciently smooth. By containing the ~ components as desgribed above in the material for w forming release agent layer, it is possible to obtain o the release agent layer 12 having the suitable 1 conductive property
Examples of the active energy ray include: infrared light; visible light: ultraviolet ray; electromagnetic ray) such as X-ray; electron ray; ion beam; neutron ray; particle ray such as o-ray; and the like. Among them, i, ultraviolet ray and the visible light are preferable. The ultraviolet ray 1s more preferable. This akes it possible to easily and reliably form the release agent layer 12.
A wavelength | of the active energy ray (the ultraviolet ray or |the visible light) is not limited 2b particularly, but preferably in the range of 200 to 600 nm and more preferably in the range of 250 to 450 nm.
If the wavelength of the active energy ray falls within the above range, t is possible to be allowed the coated layer to cure uniformly while shortening the ’ time to be allowed the coated layer to cure sufficiently. Farther, means of irradiating the active energy ray are not| limited particularly, but may be various kinds of opnesal means. Examples of a light source to be used include a light source lamp such as a high-pressure mercury lamp, a metal halide lamp, an excimer lamp and the like.
es &
Further, in the case where the active energy ray r- (the ultraviolet |ray or the visible light) is o irradiated, an gccumulated amount of light is we preferably in the range of 50 to 400 mJ/cm?’ and more ~ preferably in the |range of 100 to 300 mJ/cm® as an " irradiance of the Rov energy ray. If the irradiance = of the active energy ray falls within the above range, = it is possible to L allowed the coated layer to cure ” more uniformly and reliably. o
Further, a 0 to idrradiate the active energy ray 1s not limited particularly, but preferably in the range of 5 seconds i’ 1 minute. This makes it possible more efficiently form the release agent layer 12. As a result, it is possible to improve the productivity of the finally aoe release film 1.
According to the steps as described above, it is possible to easily| and reliably produce the release film 1 having th high reliability, the superior smoothness and the superior antistatic property.
Further, 1f the green sheet 1s produced using such a release film 1, it is possible to prevent the pinhole and the like from generating in the surface of the green sheet. ’
Examples of method of producing a ceramic capacitor using the |release film 1 include a method of coating a ceramic owder dispersion slurry onto the surface of the release agent layer of the release film and drying 1t to form the green sheet, thereafter laminating the green sheet released from the release film to obtain a |laminated body, and then forming electrodes on a ceramic sheet obtained by sintering the
CE o . laminated body. Thus, the ceramic capacitor 1s = obtained. In this way, by forming the ceramic ~ capacitor with the green sheet formed by using the - release film 1, it| is possible to obtain the ceramic © capacitor having the high reliability, which prevents a ~ defect from being generated by short circuit. "
While the present invention has been described in = detail based c¢n the preferred embodiment, the present ~ invention is not limited to the aforementioned ox embodiment.
For example, lin the aforementioned embodiment, described has been the release film 1 for producing the green sheet in which the release agent layer 12 is provided on the first surface 111 of the base material } 11. However, the |release film 1 for producing the green sheet 1s not] limited thereto. An intermediate layer may be provided between the base material 11 and 200 the release agent] layer 12. Further, such an intermediate layer may improve the adhesion between the base material 11 and the release agent layer 12.
The a. of the release film for producing the gree sheet according to the present invention may b replaced with an arbitrary configuration hich] has the same function as that of the present invention or add an arbitrary configuration : thereto.
For example, |in the aforementioned embodiment, the base material |has been described as having the single layer structyre. However, the present invention is not limited thereto. For instance, the base material may also {have a multiple layer structure having two or more layers which. may belong to the same
- ob : i]
Wy kind or the wesehen kinds. Further, the release = agent layer has been also described as having the = single layer structlre. However, the present invention foi is not limited thereto. The release agent layer may = also have the multiple layer structure having two or more layers which may belong to the same kind or the - different kinds as well.
Further, . example, in the aforementioned embodiment, the release film for producing the green - sheet has been sencline as providing the release agent oe layer on the first surface of the base material.
However, the rete film for producing the green sheet is not limited thereto. The release agent layer may be ‘ provided at the wick of the second surface of the base material.
The method | producing the release film for producing the od sheet according to the present invention 1s not limited to the aforementioned method.
As necessary, an sritrary step may be added.
Next, description will be made on specific examples of the release film for producing the green sheet according to the present invention. However, the present invention | is not limited to only these examples.
[1] Productio of Release Film for Producing
Green Sheet (Example 1)
First, a biaxially-stretched polyethyleneterephthalate film [having a thickness of
“ : a @ - 31 um, an arithmetic average roughness Rap, of a first = surface of 29 nm, |a maximum projection height Rpe of rr the first surface |of 257 nm, an arithmetic average = roughness Ra; of . second surface of 29 nm, and a a maximum projection height Rp, of the second surface of ps 257 nm] was prepared as a base material. w o
Next, 04.05 mass% of dipentaerythritol _ hexaacrylate (a sdlid content of 100 mass%) as an ol active energy ray curable compound (A), 0.95 mass?% of - polyether modified acryloyl group-containing uo polydimethylsiloxane (produced by BYK-Chemie GmbH, sold : under a trade name “BYK-3500”, and having a solid content of 100 vo as a polyorganosiloxane (B), 0.24 mass% of a multi-layer carbon nanotube (produced by
Filgen, Inc., sold| under a trade name “F-M-ML-1/25", and having a Fives diameter of about 10 nm and an aspect ratio in the range of 500 to 1500) as a carbon nanomaterial (cy, and 4.76 mass$ of an o- aminoalkylphenone-based photopolymerization initiator (produced by BASF! Ltd., sold under a trade name “IRGACURE907", 2-methyl-1[4- (methylthio)phenyl]-2-
Oph OL LAOPIOpEne-140ne, and having a solid content of 100 mass%) as a pndtopolymerizat ion initiator (D) were diluted with a mixed solvent of isopropylalcohol/methylethylketone (mass ratio 3/1) to obtain a material | for forming release agent layer . having a solid content of 20 mass$.
The material I forming release agent layer thus obtained was coate on a first surface of the base material with a bar coater. Next, the material for forming release agent layer was dried at 80°C for 1 minute, and then ultraviolet ray (an accumulated amount of light of 250 mJ/cm®) was irradiated thereto to obtain a release agent layer (thickness of 0.97 um).
: oy " - Thus, obtained was release film for producing a green “ . sheet. no (Examples 2 and 3) c | -
Release films| for producing green sheets were : produced in the samé manner as in Example 1 except that oo the thicknesses o the release agent layers were = + changed as shown in |Table 1. w 10: ~] (Example 4) =
A release film was produced in the same manner as in Example 1 except, that the mass ratio of each of the active energy ray curable compound (A) and the polyorganosiloxane (B) in the material for forming the ] release agent layer |was changed as shown in Table 1. (Examples 5 and 6) :
Release films were produced in the same manner as in Example 1 except|that the mass ratio of each of the + active energy ray curable compound (A) and the carbon nanomaterial (C) was changed as shown in Table 1. (Example 7)
A release ne produced in the same manner as in Example 1 except| that the base material was changed to a biaxially-stretiched polyethyleneterephthalate film ~ [having a thicknes of 38 um, an arithmetic average ~ roughness Rap of a |first surface of 15 nm, a maximum projection height Rpo of the first surface of 98 nm, an arithmetic average roughness Ra; of a second surface of 15 nm, and a maximum projection height Rp, of the second surface of ; nm] .
* i * v | . a : | win . os (Example 8) i : A release Fil was produced in the same manner as ~ in Example 1 crop that the thickness of the release ~ agent layer was changed as shown in Table 1. ”
Pond frets (Example 9) i. -
A release film was produced in the same manner as ~J in Example 1 except! that the base material was changed ~ to a biaxially-stretched polyethyleneterephthalate film [having a thickness of 31 um, an arithmetic average ~ roughness Rag of a| first surface of 7 nm, a maximum projection height Rpg of the first surface of 43 nm, an arithmetic average roughness Rap; of a second surface of 34 nm, and a maximum projection height Rp, of the second surface of 250 nm]. (Comparative Example 1)
A release film was produced in the same manner as in Example 1 except | that the mass ratio of each of the active energy ray, curable compound (A) and the polyorganosiloxane ®) in the material for forming release agent raver es changed as shown in Table 1. (Comparative Examples 2 and 3)
Release films were produced in the same manner as in Example 1 except |that the thicknesses of the release agent layers were as shown in Table 1. (Comparative Example 4) : A Release film| was produced in the same manner as
CL
Co. 2 iy ~ in Example 1 se the mass ratio of each of the = active energy ray curable compound (A) and the carbon M nanomaterial (C) vat changed as shown in Table 1. - rm 5. (Comparative Example 5) = : } fu.) 99.72 mass% off a solid content of a thermosetting pt silicone (produced | by Shin-Etsu Chemical Co., Ltd., = sold under a jt “KS-847H” and having a solid content of 30 mass%|) as a release agent and 0.24 mass$ J of a multi-layer carbon nanotube (produced by Filgen, " Inc., sold under a trade name “F-M-ML-1/25”, and having ) a fiber diameter of| about 10 nm and an aspect ratio in the range of 500 toe 1500) as the carbon nanomaterial (C) were diluted With toluene to obtain a diluted solution. 0.04 op of a solid content of a platinum ~ catalyst (produced | by Shin-Etsu Chemical Co., Ltd., ~ sold under a trade name “CAT-PL-50T” and having a solid ~ content of 2 mass$%) was mixed with the diluted solution to prepare a release agent solution of a solid content of 5.0 mass%.
The obtained delease agent solution was uniformly coated onto one suztace (the first surface) of the same base material as that of the Example 1 so that a thickness of the relene agent layer to be formed after drying was 0.3 um. Thereafter, the release agent } solution was dried| at 140°C for 1 minute to form a release agent layer. Thus, a release film was produced. (Comparative Examples 6 and 7)
Release films vere produced in the same manner as in Comparative Sram 5 except that the thicknesses of © the release agent tqyers were changed as shown in Table
. } oo. : .
Lo = oo oo (Comparative Example 8) =
A Release film for forming a green sheet was ~ produced in the same manner as in Example 1 except that I the following materials were used as the material for - forming release agent layer. : i. 94.05 mass% Jf dipentaerythritol hexaacrylate (a = : solid content of or mass%) as an active energy ray he ‘curable compound (A), 0.95 mass% of polyether modified acryloyl group containing polydimethylsiloxane (produced by BYK-C emie GmbH, sold under a trade name “BYK-3500”, and having a solid content of 100 mass%) as a polyorganosilox ne (B), 0.24 mass% of acicular antimony doped tin| oxide (produced by ISHIHARA SANGYO .
KAISHA, LTD., sold under a trade name “FS-10P”, and having a fiber diameter in the range of ‘10 to 20 nm and an aspect ratio in the range of 20. to 30), and 4.76 mass% of | an a-aminoalkylphenone-based photopolymerization| initiator (produced by BASF Ltd., sold under a trade name “IRGACUREY907”, 2-methyl-1T[4- (methylthio)phenyl]-2-morpholinopropane-1-one, and having a solid content of 100 mass%) as a photopolymerization| initiator (D) were diluted with a mixed solvent of isopropylalcohol/methylethylketone (mass ratio. 3/1) |to obtain a material for forming release agent layer| having a solid content of 20 mass$%. (Comparative Example 9)
A Release film for forming a green sheet was produced in the same manner as in Example 1 except that the following materials were used as the material for forming release agent layer.
‘ . Co . . . — - or 94.05 mass$ | dipentaerythritol hexaacrylate (a : solid content of 100 mass$%) as an active energy ray o curable compound ak 0.95 mass% of polyether modified oe acryloyl group-containing polydimethylsiloxane ~ (produced by avk-chenie GmbH, sold under a trade name - “BYK-3500”, and having a solid content of 100 mass%) as - a ptyersanaes oad (B), 0.24 mass% of an acicular - electrical conducting material in which acicular rutile Co type titanium dioxide was coated with antimony doped = tin oxide (produced by ISHIHARA SANGYO KAISHA, LTD., + sold under a eae [name “FT-1000”, and having a fiber diameter of about 130 nm and an aspect ratio in the range of 10 to (20), and 4.76 mass% of an o- aminoalkylphenone-based photopolymerization initiator ] (produced by BASF| Ltd., sold under a trade name “IRGACURES907”, 2-methyl-1[4- (methylthio)phenyl]-2- morpholinopropane~-l+one, and having a solid content of 100 mass%) as a phdtopolymerization initiator (D) were diluted with | a mixed solvent of isopropylalcohol/methylethylketone (mass ratio 3/1) to obtain a material | for forming release agent layer having a solid content of 20 mass%.
The compositions and the like of the release film for producing the green sheet of each of Examples and
Comparative ranges were shown in Table 1.
In Table 1, the dipentaerythritol hexaacrylate (the solid content |of 100 mass%) as the active energy ray curable compound (A) was represented as “A”, the polyether modi fied acryloyl group-containing polydimethylsiloxane (produced by BYK-Chemie GmbH, sold under the trade na e “BYK-3500”, and having the solid content of 100 mass%) as the polyorganosiloxane (B) was represented as YB”, the multi-layer carbon nanotube
CL
& ; (produced by Filgen, Inc., sold under the trade name = “F-M-ML-1/257, and |having the fiber diameter of about ro 10 nm and the aspect ratio in the range of 500 to o 1,500) as the carbon nanomaterial (C) was represented as “er, the a-aminoalkylphenone~based photopolymerization| initiator (produced by BASF Ltd., ” sold under the wo name “IRGACURE907”, 2-methyl-1[4- (methylthio)phenyl}+2-morpholinopropane-1-one, and i having the solid content of 100 mass%) as the % photopolymerization| initiator (D) was represented as = “D”, the thermosetting silicone (produced by Shin-Etsu 1
Chemical Co., Ltd.,| sold under the trade name “KS-847H” and having the solid content of 30 mass$%) was . represented as “X1”, the platinum catalyst (produced by
Shin-Etsu Chemical do. Ltd., sold under the trade name “CAT-PL-50T” and having the solid content of 2 mass$) was represented as| “y1”, the acicular antimony doped tin oxide (produced by ISHIHARA SANGYO KAISHA, LTD., sold under the trade name Y“FS-10P”, and having the fiber diameter in [the range of 10 to 20 nm and the aspect ratio in the] range of 20 to 30) was represented as “zl”, and th acicular electrical conducting material in which ons acicular rutile type titanium dioxide was coated with the antimony doped tin oxide (produced by ISHIHARA SANGYO KAISHA, LTD., sold under the trade name “FT-1000”, and having the fiber diameter of about 130 nm and|the aspect ratio in the range of 10 to 20) was represented as “227. .
The thicknesses of the base materials and the release agent ese? of the respective Examples and the respective Comparative Examples were measured with a reflection-type film thickness meter “F207” made by
Filmetrics Co, Ltd.! Specifically, the release film for producing the green sheet obtained in each of the
Examples and the Comparative Examples was cut in a size
.
Bh . of 100 x 100 mm. | Thereafter, the release film for ~ producing the green| sheet was set to the film thickness - meter so that a surface opposite to the surface located o ’ at the side to measfire a thickness faced to a side of a we suction stage. The thicknesses of the release agent = layer were measured| in 10 points of the surface thereof - to obtain 10 measurement values. Then, an average - value thereof was dalculated. Thus, the average value oy was regarded as the thickness of the release agent w layer. o : : (7
Further, the arithmetic average roughness Rag and the maximum projectjion height Rpe of the first surface of the base Preleeh the arithmetic average roughness
Ra, and the maximum |projection height Rp; of the second surface of the base material, and the arithmetic average roughness Ra; and the maximum projection height
Rp: of the outer surface of the release agent layer ’ were measured in the following manner. First, a double-side tape was attached to a glass plate. Then, each of the releape films for producing the green sheets obtained in] the respective Examples and the respective Comparatiive Examples was fixed onto the double~-side tape such that the surface to measure the arithmetic average roughness and the maximum projection height was positioned at a side opposite to the double- side tape. Subsequently, the arithmetic average roughnesses Rap, Ray and Ra; and the maximum projection heights Rpg, Rp: and Rp; were measured in accordance with JIS B0601-199 using a surface roughness meter “Sv3000S4” (probe type) made by Mitsutoyo Corporation.
Table 1 :
% = 5 2 5 5 o
Table. 1 Co Ce .
EEE average projection average projection Contentof A | Content of B | Content. of C | Content of D average 3 projection roughness Rao " beight Rpo roughness Raz height Rp2 . find roughness Raz ielght Rp: : ee er my | Tot | Tome | Tin | [Tir | eat roms Toe]
Example] 20 | 257 | 29 | ev [| a | ees | oe | oz4 | am [ - | - | 3 | 17 | 097] pample2] 20 | 257 | 29 | 257 | 31 | eos [ 09s | oea [ ame I -T - 1 5 [ 49 1 085 pemples| 20 | 257 | es | an | om | saos | oes | oo | 4ve | - f - {3 ] we | 1 jampied] 20 | 257 | 28 | a7 [ a1 [ e462 | 048 | 02s [ ave | - FF - 1 3 [| w | owe | :
Exampies| 29 | 257 | 2 | 25 | sw [ ess | 095 | oes | ave | - 1 - 7 4 | 8 | oer — Camples| 29] 257 | —e9 1957 | sf esse 09s | ves) are || —= | 5 | wr | oer
Eom] 5 | ss | 15 | ow |e | sew | om | wa | am | =| = | o | un | ow] famed] 2 | zr | aw | ar | wn | ww | os | om | am | =| = | 5 | & | ow]
Bamiedl 1m | ww | aw | ai | sees | es | oa | am [= | = | a [5 | ow] . TEE | wr | wm | a [a we | oem | aw |] |e [wos] ewes | aw | wm | ew [a | ses | om | am | ew | | = | & | we | ow]
EES er [ww |e [wes | ow | om | aw | =| = | nw | @ | om] [Eom oo | ar | aw | wr | wm | was | ow |= am | | = [5 | © | ow
Ew | ew [ow [ee [a | - | — | em | - [www] ws | wm | ew] oe | mw | ww [wm |= | | am |= |xen|wmen] = | aw | ow ew er [we [a | | | ew |= [xenlmmen] a | we | tw] [mo | a | a | a | a | se | ow | - | aw [zi] om | | sm ou] or] wm | wwe | er | ees | ww | = | am zr] om | 5 | ws [ow]
- "
[2] Evaluation = ~
The following] evaluations were conducted with ol respect to the release films for producing the green Ga sheets thus obtained. [2.1] Surface a ~
Each of the ieee films for producing the green o sheets obtained in] the respective Examples and the respective Comparative Examples was cut in a size of oe 100 mm x 100 mm. This was used as a sample. The sample was left for 24 hours under the condition of a temperature of 23% and humidity condition of 50%.
Thereafter, a surface resistivity at the side of the release agin Lay measured in accordance with JIS
K6911(1995) using “"R12704 Resistivity Chamber” made by ADVANTEST . CORPORATTON and “Digital Electro Meter
R8252” made by ADVANTEST CORPORATION. [2.2] Curability Evaluation of Release Agent
Layer
In each of He release films for producing the green sheets obtained in the respective Examples and the respective Comparative Examples, the surface of the release agent layed was reciprocatively polished ten times at a load of |1 kg/cm? using a waste cloth (made by Ozu Corporation and sold under a trade name “BEMCOT
AP-2") containing 3 ml of methylethylketone.
Thereafter, the surrace of the release agent layer was visually observed. |The curability of the release agent layer was ater under the following evaluation criteria. | :
A: The release agent layer was not dissolved and 41 i
LL | C1 os exfoliated. =
B: The release agent layer was partially h- dissolved. ~ © C: The relepse agent layer was completely oe : dissolved and exfoliated from the base material. ~ [2.3] Curl Evalluation "-
Each of the release films for producing the green 0 sheets obtained in| the respective Examples and the = respective Comparative Examples was cut into a size of w 200 x 200 mm. Thereafter, each cut release film for producing the green sheet was placed on a flat glass plate so that the base material faced to the side of the glass plate. Next, a glass plate having a size of 100 x 100 mm was placed at the center of the release agent layer of the |cut release film for producing the green sheet. Thereafter, measured was a curl height from an upper surface of the flat glass plate to each : edge part of the cut release film. The curl height was evaluated under the (following evaluation criteria.
A: A summation of the curl heights of the edge parts was less than [50 mm. | B: A summation of the curl heights of the edge parts was 50 mm or more but less than 100 mm.
C: A summation of the curl heights of the edge parts was 100 mm or more. | [2.4] Evaluation of Blocking Property
Each of the rellease films for producing the green sheets obtained in| the respective Examples and the respective Comparative Examples was wound in a roll : shape with a width of 400 mm and a length of 5000 m to obtain a release film roll. The release film roll was
.
Co Co : stored for 30 days under the environments of a = temperature of 409C and humidity of 50% or less. I ’
Thereafter, the outward appearance of the release film = roll was visually observed ‘as it is. The blocking we property thereof was evaluated under the following = evaluation criteria - o
A: The outwanyd appearance of the release film - roll after storing was not changed as compared with the 0: outward appearance | of the release film roll before o storing and obtained by winding the release film for = producing the green sheet in the roll shape (Blocking was not generated).
B: In an areal less than half of the roll of the release film for pnoducing the green sheet in a width direction thereof, the hue was changed, which resulted : from the close contact between the films (Blocking was generated slightly)
C: The hue was changed over a half region of the roll of the release] film for producing the green sheet in the width direction, which resulted from the close contact between the films (Blocking was generated). [2.5] Unwinding Electric Charge Amount
Each of the release films for producing the green sheets obtained in] the respective Examples and the respective compartir Examples was wound in a roll shape with a width of 400 mm and a length of 5000 m to obtain a release film roll. The release film roll was . stored for 30 days under the environments of a temperature of 40°C and humidity of 50% or less.
Thereafter, an electric charge amount when the release film was unwound ati a speed of 50 m/min was measured
.
So using “KSD-0103” rhe by KASUGA ELECTRIC WORKS LTD. =
The electric charge| amount was measured at a region of = 100 mm of the just-unwound release film every an ~ unwinding length of] 500 m. - 0
A: The electric charge amount was - 5 kV to + 5 . kVi bt : B: The electric charge amount was - 10 kV to - 5 Ty kVior + 5 kV to + 10 kv. -
C: The electric charge amount was - 10 kV or less 2 or + 10 kV or more. " [2.6] Evaluation of Coatability of Slurry 135 mass parts of a mixed solvent of toluene and ’ ethanol (mass rati of 6:4) were added to 100 mass parts of barium hance powder (BaTios, produced by
Sakai Chemical Industrial Co., Ltd. and sold under a trade name “BT-03") | 8 mass parts of polyvinyl butyral (produced by Sekisull Chemical Co., Ltd. and sold under a trade name “S-LEC| B-K BM-2”) as a binder, and 4 mass parts of dioctyl FE (produced by KANTO CHEMICAL
CO., INC. and sold under a trade name “DIOCTYL
PHTHALATE Cica anor 1”) as a plasticizer. A Ceramic slurry was prepared by mixing and dispersing these substances with a ball mill.
A coated layer was obtained by coating the ceramic slurry, with a die coater, on the surface of the release agent ayer of each of the release films : for producing the green sheets obtained in the respective Example and the respective Comparative
Examples, such that, when dried, the green sheet had a thickness of 1 um, | width of 250 mm and a length of 10 m. Thereafter, the release film for producing the green sheet provided with the ceramic green sheet was
Ww ! . > obtained by coin the coated layer with a drying ~ machine at 80°C for one minute. Then, light of a " fluorescent lamp was irradiated to the release film for } producing the gree sheet provided with the ceramic : green sheet from |a side of the release film for - producing the green sheet. Thus, surfaces of all of = the coated ceramic green sheets were visually observed. pre
The coatability of |the slurry was evaluated under the i following evaluation criteria. The results are shown w in Table 2. | ”
A: No imnold was found in the ceramic green sheet.
B: 1 to 5 shooter were found in the ceramic green sheet.
C: 6 or wore [pinhotes were found in the ceramic green sheet. [2.7] wi of Releasability
A ceramic green sheet was formed on the surface of the release aggnt layer of the release film for producing the green] sheet in the same manner as in the above item [2.6]. he ceramic green sheet was cut into a size of 200 mm x 200 mm so that the release film for producing the green sheet was not cut. Next, the cut ceramic green sheet was adsorbed to a vacuum suction stage using a sheet! peeling machinery of a green sheet lamination machine land released from the release film for producing the green sheet. At this time, the releasability of the ceramic green sheet was evaluated under the following |evaluation criteria.
A: The ceramic¢ green sheet was smoothly released from the release agent layer without being broken, and the ceramic green Bheet was not left on the release
. Ce
Po Co : >
N agent layer. | = ho
B: The green sheet was released from the ~ release agent layer without being broken, while we somewhat lacking § smoothness, and the ceramic green ” sheet was not left on the release agent layer. " ow
C: The ceramic green sheet was broken or the - ceramic green sree} could not be released from the ow release agent layer oe [2.8] soatomcion of Defect of Surface of Release
Agent Layer (Evaluation of Number of Depressed Parts)
A coating hota obtained by dissolving a polyvinyl butyral To in a mixed solvent of toluene } and ethanol (mass [ratio of 6:4) was coated onto the release agent layexrn of each of the release films for producing the green sheets obtained in the respective
Examples and the respective Comparative Examples, such that, when dried, ajpolyvinyl butyral resin layer had a thickness of 1 pm. | Thus, -a coated layer was obtained.
The polyvinyl butyral resin layer was formed by drying the coated layer at | 80°C for one minute. Subsequently, a polyester tape as attached to a surface of the polyvinyl butyral resin layer.
Then, the relkase film for producing the green sheet was released from the polyvinyl butyral resin layer by using the| polyester tape. Counted was the number of depressed parts in the surface . of the polyvinyl butyral rss layer which had been in contact with the release agent layer of the release film for producing the green sheet. Specifically, the surface of the polyvinyl butiyral resin layer was observed using an optical entero type surface profiler (made by
. i
So Co . ho
Veeco Instruments ne. and sold under a trade name = “WYKO-1100") . The |observation was conducted in a PSI "2 mode and at a rekon of 50. The number of the - depressed parts wasi counted on the basis of an image of a surface shape nla region of 91.2 x 119.8 um of the = surface of the polyvinyl butyral resin layer. The - depressed parts had| a depth of 150 nm or greater. The o number of the depressed parts was evaluated under the x following evaluation criteria. Defects of the surface - of the release agent layer were evaluated. In this o regard, it is to be noted that this evaluation was not performed for the release film for producing the green sheet evaluated t be the criterion “C” in the evaluation of releasability as described above since } such a release film for producing the green sheet was not satisfactory to perform this evaluation.
A: The number of the depressed parts was zero.
B: The number of the depressed parts was 1 to 5.
C: The rumbes] of the depressed parts was 6 or more.
In the case fr a capacitor was manufactured using the polyvinyl butyral resin layer (the ceramic green sheet) having the depressed parts as described above, there was L tendency that short was easily generated in the opatned capacitor due to a decrease in breakdown voltage.
These results are shown in Table 2. }
Table 2
& aS > > pe = on
Table. 2 :
To [ema] ee [roe Foe foe pamper | 10x10 | A | a | a | a } a | a | a [Emo oar | a | a | A | a | a | a | a _ fomped] 10x10 | A | a [| a | a [ a | a | a [mmr host | A Ta Ta | a | a | a | a] mapa | oxi’ | oA | oa | 0a | a [ a [| ¢ | - mez | 10x10? ] a | a [| a | a [ a | 0B | cc low [a a [a | a [a [sc comes | 10x10’ |] A | a | 8B [| a 1 B | B | © comes | vox | A | oa [ c¢ | 0B [| ec [ ¢ | - meer | vox’ | oA | oa | ¢ | 0B | ¢ | ec | - [mgs toxi0®] a | a | a | cc | a I BB | c¢
Emel ioxier] a | a [| a | ¢ | a | 8 [| c¢
» , [oi os
As is cpparer in Table 2, the release film for = producing the green sheet according to the present = . invention was superior in the smoothness of the outer " surface thereof. | Further, the release film for - producing the green sheet according to the present invention had a relat ivery low charge amount and the CL excellent blocking property. Further, the release film p for producing the Soe sheet according to the present oo invention was supekios in the releasability to the ov green sheet. Furthermore, no pinhole was confirmed in te the green sheet formed by using the release film for - producing the gree sheet according to the present invention. In contrast, satisfactory results were not obtained in the Comparative Examples.
Cs
The release rim for producing the green sheet of } the present invention includes the base material and the release agent layer. The release agent layer 1s formed by irradiating the active energy ray to the coated layer formed |by coating the material for forming release agent layer (to the first surface. The material for forming releas agent layer contains the active energy ray curable | compound (A) having at least one reactive functional group selected from the group consisting of the (meth) acryloyl group, the alkenyl group and the maleimide group, the polyorganosiloxane (B) and the carbon | nanomaterial (Ch). The arithmetic average roughness a; of the outer surface of the release agent layer| is 8 nm or less and the maximum projection height px: of the outer surface of the release agent layer {is 50 nm or less. According to the present invention, | it is possible to provide the release film for producing the green sheet which is capable of producing the green sheet having the high reliability and preventing the pinhole and the partial
. . & . « .
So thickness variation! in the surface of the green sheet = from generating. roses, the present invention is - industrially applicable. ~ 0
EXPLANATION OF REFERENCE NUMERAL = 1: release film for producing green sheet " 11: base material 111: first suriface of base material = 112: second surface of base material » 12: release aggnt layer i 131: outer i of release agent layer
Claims (5)
1. A release film for producing a green sheet, — comprising: = : a base materlal having a first surface and a ” second surface; and " a release agent layer provided on the first surface of the base material, - wherein the elease agent layer is formed by vo irradiating an active energy ray to a coated layer - formed by coating a material for forming release agent we layer to the first surface, and the material for forming release aggnt layer contains an active energy ray curable compound (A) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl |group, an alkenyl group and a maleimide group, a polyorganosiloxane (B) and a carbon nanomaterial (C), and wherein an arithmetic average roughness Ra; of an . outer surface of the release agent layer is 8 nm or less and a maximum | project ion height Rp; of the outer surface of the relejse agent layer is 50 nm or less.
2. The release film for producing the green sheet as claimed in claim 1, wherein an average thickness of the release agent. layer |is in the range of 0.2 to 2 um.
3. The release film for producing the green sheet as claimed in claim 1,| wherein a content in solid content conversion of the polyorganosiloxane (B) in the material for forming release agent layer is in the range of 0.5 to 5 mass%.
4. The release film for producing the green sheet as © 35 claimed in claim 1, wherein the polyorganosiloxane (B) is a polyorganosiloxane having a straight or branched
“ !
nh . + , ‘ a 0 least one reactive | functional group selected from the > group consisting of |the (meth)acryloyl group, the alkenyl ow group and the maleimide group is bonded to the silicon oO atoms of the molecular chain, either directly or through es ’ 9 a bivalent linking hour. o
5. The release film for producing the green sheet as “ claimed in claim 1, wherein a content in solid content Fu conversion of the Lo nanomaterial (C) in the material ~ for forming release agent layer is in the range of 0.05 = to 10 mass$%. = : - i Nn ot ! Uy ny ; I I LoL & pC 7 VL oo N/ . oS ABSTRACT JR ) Yo = A release fin for producing a green sheet of the vy» present invention |ihcludes a base material and a be Hh release agent layer.
The release agent layer is formed i by irradiating an abtive energy ray to a coated layer - formed by coating a material for forming release agent layer to a first surface.
The material for forming = release agent laye contains an active energy ray = curable. compound (A) having at least one reactive = functional group sellected from the group consisting of a (meth)acryloyl J an alkenyl group and a maleimide group, a polyorganosiloxane (B) and a carbon nanomaterial (C). An arithmetic average roughness Ra; of an outer surface |of the release agent layer is 8 nm ] or less and a wari projection height Rp: thereof is 50 nm or less.
Acc fding to the present invention, it is possible to provide a release film for producing a green sheet which is capable of producing the green sheet having high reliability and preventing a pinhole and a partial thickness variation in a surface of the ) green sheet from generating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013069507A JP6091287B2 (en) | 2013-03-28 | 2013-03-28 | Release film for green sheet manufacturing |
| PCT/JP2013/085206 WO2014155895A1 (en) | 2013-03-28 | 2013-12-27 | Release film for green sheet production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PH12015502250B1 true PH12015502250B1 (en) | 2016-02-01 |
| PH12015502250A1 PH12015502250A1 (en) | 2016-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PH12015502250A PH12015502250A1 (en) | 2013-03-28 | 2015-09-28 | Release film for green sheet production |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP6091287B2 (en) |
| KR (1) | KR102093769B1 (en) |
| CN (1) | CN105102194B (en) |
| MY (1) | MY173627A (en) |
| PH (1) | PH12015502250A1 (en) |
| SG (1) | SG11201507895WA (en) |
| TW (1) | TWI542473B (en) |
| WO (1) | WO2014155895A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107249879A (en) * | 2015-02-18 | 2017-10-13 | 琳得科株式会社 | Mold release film |
| JP6468924B2 (en) * | 2015-03-31 | 2019-02-13 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process and method for manufacturing ceramic green sheet |
| TWI564149B (en) * | 2015-08-05 | 2017-01-01 | Nanya Plastics Corp | Release film and manufacturing method thereof |
| JP6409997B1 (en) * | 2017-03-01 | 2018-10-24 | 東洋紡株式会社 | Release film for producing ceramic green sheet and method for producing the same |
| SG11202003421PA (en) * | 2017-11-02 | 2020-05-28 | Toyo Boseki | Release film for producing ceramic green sheet |
| JP7188536B2 (en) * | 2017-12-27 | 2022-12-13 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7188537B2 (en) * | 2017-12-27 | 2022-12-13 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP6973054B2 (en) * | 2017-12-27 | 2021-11-24 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7188535B2 (en) * | 2017-12-27 | 2022-12-13 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7101553B2 (en) * | 2018-07-10 | 2022-07-15 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| CN112672866B (en) * | 2018-09-03 | 2022-03-15 | 东洋纺株式会社 | Release film for producing ceramic green sheet |
| JP7338359B2 (en) * | 2018-09-26 | 2023-09-05 | 東レ株式会社 | Optical polyester film roll |
| TWI848029B (en) * | 2018-12-20 | 2024-07-11 | 日商東洋紡股份有限公司 | Release film, method for producing release film, method for producing ceramic green body, and method for producing ceramic capacitor |
| CN117325533A (en) | 2019-06-28 | 2024-01-02 | 东洋纺株式会社 | Release film for ceramic green sheet production |
| CN115210052A (en) * | 2020-03-04 | 2022-10-18 | Tdk株式会社 | Release film roll, ceramic member sheet and method for producing same, and ceramic member and method for producing same |
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| JP3735857B2 (en) * | 2001-02-16 | 2006-01-18 | 荒川化学工業株式会社 | Release substrate |
| JP3870785B2 (en) | 2002-01-07 | 2007-01-24 | 株式会社村田製作所 | Manufacturing method of multilayer ceramic electronic component |
| JP2007237496A (en) * | 2006-03-07 | 2007-09-20 | Teijin Dupont Films Japan Ltd | Mold release film |
| JP5008999B2 (en) * | 2007-02-06 | 2012-08-22 | リンテック株式会社 | Dicing tape and method for manufacturing semiconductor device |
| JP5512149B2 (en) * | 2008-02-28 | 2014-06-04 | リンテック株式会社 | Release agent composition and release sheet |
| JP5381860B2 (en) * | 2010-03-29 | 2014-01-08 | Ｔｄｋ株式会社 | Peeling film, ceramic component sheet, method for producing these, and method for producing ceramic component |
| JP5756315B2 (en) * | 2011-03-29 | 2015-07-29 | リンテック株式会社 | Release agent composition and release film for molding ceramic green sheet |
| JP2012224011A (en) * | 2011-04-21 | 2012-11-15 | Lintec Corp | Release film for ceramic green sheet manufacturing process |
-
2013
- 2013-03-28 JP JP2013069507A patent/JP6091287B2/en active Active
- 2013-12-27 SG SG11201507895WA patent/SG11201507895WA/en unknown
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- 2013-12-27 KR KR1020157026162A patent/KR102093769B1/en active IP Right Grant
- 2013-12-27 CN CN201380075174.8A patent/CN105102194B/en active Active
- 2013-12-27 WO PCT/JP2013/085206 patent/WO2014155895A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105102194A (en) | 2015-11-25 |
| JP6091287B2 (en) | 2017-03-08 |
| TW201437036A (en) | 2014-10-01 |
| WO2014155895A1 (en) | 2014-10-02 |
| MY173627A (en) | 2020-02-12 |
| JP2014189007A (en) | 2014-10-06 |
| KR102093769B1 (en) | 2020-03-26 |
| SG11201507895WA (en) | 2015-10-29 |
| PH12015502250A1 (en) | 2016-02-01 |
| CN105102194B (en) | 2017-08-22 |
| KR20150138205A (en) | 2015-12-09 |
| TWI542473B (en) | 2016-07-21 |
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