CN116963887A - Release film for ceramic green sheet production process - Google Patents
Release film for ceramic green sheet production process Download PDFInfo
- Publication number
- CN116963887A CN116963887A CN202280019947.XA CN202280019947A CN116963887A CN 116963887 A CN116963887 A CN 116963887A CN 202280019947 A CN202280019947 A CN 202280019947A CN 116963887 A CN116963887 A CN 116963887A
- Authority
- CN
- China
- Prior art keywords
- ceramic green
- release film
- green sheet
- release
- release agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 123
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 104
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 77
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 77
- 229920003180 amino resin Polymers 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 239000003377 acid catalyst Substances 0.000 claims abstract description 21
- -1 polyol compound Chemical class 0.000 claims description 59
- 238000006460 hydrolysis reaction Methods 0.000 claims description 40
- 230000007062 hydrolysis Effects 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 32
- 238000013508 migration Methods 0.000 abstract description 23
- 230000005012 migration Effects 0.000 abstract description 23
- 229920001296 polysiloxane Polymers 0.000 abstract description 21
- 230000001629 suppression Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 156
- 239000000047 product Substances 0.000 description 58
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 33
- 238000012360 testing method Methods 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- 238000000576 coating method Methods 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000002002 slurry Substances 0.000 description 17
- 229920000877 Melamine resin Polymers 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000006482 condensation reaction Methods 0.000 description 15
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 239000004640 Melamine resin Substances 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 150000007974 melamines Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical class 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HBOSQVFEPQCBNL-UHFFFAOYSA-N 4-propyloctane-3,3-diol Chemical compound CCCCC(CCC)C(O)(O)CC HBOSQVFEPQCBNL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- LSXYDFJMOZPOSF-UHFFFAOYSA-N [(4-amino-6-diazenyl-1,3,5-triazin-2-yl)amino]methanol Chemical compound N=NC1=NC(=NC(=N1)N)NCO LSXYDFJMOZPOSF-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Polymers 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005702 oxyalkylene group Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- FGKCGMMQJOWMFW-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CC(=C)C(=O)OCC[N+](C)(C)C FGKCGMMQJOWMFW-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
A release film for a ceramic green sheet production process, comprising a substrate and a release agent layer provided on one side of the substrate, wherein the release agent layer is formed from a release agent composition containing an amino resin (A), a hydroxyl-containing acrylic resin (B), a polyorganosiloxane (C) and an acid catalyst (D). According to the release film for the ceramic green sheet manufacturing process, both light releasability and suppression of migration of the silicone component can be achieved.
Description
Technical Field
The present invention relates to a release film used in a process for producing a ceramic green sheet (ceramic green sheet).
Background
Conventionally, in order to manufacture a laminated ceramic product such as a laminated ceramic capacitor (hereinafter, sometimes referred to as "MLCC") or a multilayer ceramic substrate, a step of molding ceramic green sheets, laminating a plurality of obtained ceramic green sheets, and firing the laminated ceramic green sheets has been performed. The ceramic green sheet is formed by coating a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film.
As the release film, a release film having a base material and a release agent layer provided on one side of the base material is generally widely used. Such a release film is required to have light releasability such as being capable of releasing a thin ceramic green sheet molded on the release film from the release film without breaking the release film. Therefore, as the release agent layer, a release agent layer containing a polyorganosiloxane such as polydimethylsiloxane is widely used.
For example, patent document 1 proposes a release film having a release agent layer containing a thermosetting amino resin and a hydroxyl group-containing polyorganosiloxane as materials.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6395011
Disclosure of Invention
Technical problem to be solved by the invention
However, the silicone component in the release agent composition easily migrates to the surface of the ceramic green sheet in contact with the release agent layer. If the silicone component migrates to the surface of the ceramic green sheet, the adhesiveness and the adhesiveness of the surface are reduced. When a ceramic green sheet is produced using such a release film having an easily removable silicone component, and a laminated ceramic product is produced using the ceramic green sheet, peeling is likely to occur between layers of the laminated ceramic product due to changes over time and environmental acceleration conditions. In addition, in a laminated ceramic product obtained by using a ceramic green sheet having reduced adhesion, positional accuracy of an electrode or the like is lowered, and desired product performance cannot be obtained. Therefore, a release film having less migration of an organosilicon component into a ceramic green sheet is desired.
In the conventional release film described in patent document 1, further improvement is required in order to satisfy both light releasability and suppression of migration of silicone components.
The present invention has been made in view of such a practical situation, and an object thereof is to provide a release film for a ceramic green sheet production process which can achieve both light releasability and suppression of migration of silicone components.
Technical means for solving the technical problems
In order to achieve the above object, in a first aspect, the present invention provides a release film for a ceramic green sheet production process comprising a base material and a release agent layer provided on one side of the base material, wherein the release agent layer is formed from a release agent composition containing an amino resin (a), a hydroxyl group-containing acrylic resin (B), a polyorganosiloxane (C) and an acid catalyst (D) (invention 1).
The hydroxyl-containing acrylic resin (B) is excellent in compatibility with the amino resin (a), while it is poor in compatibility with the polyorganosiloxane (C). In the invention (invention 1) above, by using the hydroxyl-containing acrylic resin (B) and the amino resin (a) together, the polyorganosiloxane (C) is likely to segregate on the surface of the release agent layer. Therefore, light peelability can be expressed with a small amount of polyorganosiloxane (C). Since the range of maintaining the light releasability is widened and the adjustment of the blending amount of the polyorganosiloxane (C) is facilitated, the migration amount of the silicone component to the ceramic green sheet can be reduced, and the migration of the silicone component can be suppressed.
In the above invention (invention 1), the content of the hydroxyl group-containing acrylic resin (B) in the stripper composition is preferably 5 parts by mass or more and 200 parts by mass or less (invention 2) with respect to 100 parts by mass of the amino resin (a).
In the above inventions (inventions 1 and 2), the polyorganosiloxane (C) preferably has at least 1 hydroxyl group in 1 molecule (invention 3).
In the above inventions (inventions 1 to 3), the polyorganosiloxane (C) preferably has at least 1 organic group selected from the group consisting of a polyester group, a polyether group and a methanol group (invention 4).
In the above inventions (inventions 1 to 4), the weight average molecular weight of the polyorganosiloxane (C) is preferably 500 to 20000 (invention 5).
In the above inventions (inventions 1 to 5), the content of the polyorganosiloxane (C) in the stripper composition is preferably 0.05 parts by mass or more and 10 parts by mass or less (invention 6) per 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B).
In the above inventions (inventions 1 to 6), the release agent composition preferably contains an alkoxysilane hydrolysis polycondensate (E) having a siloxane bond (si—o—si) as a skeleton (invention 7).
In the above inventions (inventions 1 to 7), the acid catalyst (D) preferably contains at least 1 kind of the sulfonic acid catalyst and the phosphoric acid catalyst (invention 8).
In the above inventions (inventions 1 to 8), the stripping agent composition preferably contains a polyol compound (F) having a molecular weight or weight average molecular weight of 50 to 10000 (invention 9).
In the above inventions (inventions 1 to 9), the thickness of the release agent layer is preferably 0.02 μm or more and 0.5 μm or less (invention 10).
In the above inventions (inventions 1 to 10), it is preferable that: the surface of the substrate on the release agent layer side has an arithmetic average roughness (Ra) of 1nm to 50nm, and the maximum protrusion height (Rp) of the surface is 10nm to 1000nm (invention 11).
In the above inventions (inventions 1 to 11), it is preferable that: the surface of the substrate opposite to the release agent layer has an arithmetic average roughness (Ra) of 10nm to 50nm, and the maximum protrusion height (Rp) of the surface is 100nm to 1000nm (invention 12).
Effects of the invention
According to the release film for a ceramic green sheet production process of the present invention, both light releasability and suppression of migration of silicone components can be achieved.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
The release film for the ceramic green sheet production process of the present embodiment (hereinafter, may be simply referred to as "release film") is composed of a base material and a release agent layer provided on one side of the base material. Hereinafter, the surface of the release agent layer opposite to the base material may be referred to as a "release surface".
1. Substrate material
The substrate in this embodiment is not particularly limited as long as the release agent layer can be laminated. Examples of the substrate include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonates and plastics such as polyvinyl acetate, and the films may be single-layered or may be multi-layered of 2 or more layers of the same type or different types. Among them, a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is further preferable. Since the polyethylene terephthalate film is less likely to generate dust or the like during processing, use or the like, for example, poor coating of ceramic slurry or the like due to dust or the like can be effectively prevented.
In addition, in order to improve adhesion to the release agent layer provided on the surface of the substrate, one or both surfaces may be subjected to a surface treatment by an oxidation method, a concavity and convexity method, or a primer treatment, as required. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet type), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like, and examples of the relief method include sand blasting and thermal spraying. These surface treatments may be appropriately selected depending on the kind of the base film, but in view of the effect and the handleability, a corona discharge treatment is generally preferably used.
The surface of the base material on the release agent layer side has an arithmetic average roughness (Ra) of preferably 50nm or less, particularly preferably 40nm or less, and further preferably 30nm or less. By setting the arithmetic average roughness (Ra) to 50nm or less, the arithmetic average roughness (Ra) and the maximum protrusion height (Rp) of the release surface can be easily made to fall within the ranges described later, and thus occurrence of defects in the molded ceramic green sheet can be effectively suppressed. The lower limit of the arithmetic average roughness (Ra) of the surface of the base material on the release agent layer side is not particularly limited, and may be, for example, 1nm or more, particularly 3nm or more, and further 5nm or more.
The maximum protrusion height (Rp) of the surface of the substrate on the release agent layer side is preferably 1000nm or less, particularly preferably 700nm or less, and further preferably 500nm or less. When the maximum protrusion height (Rp) is 1000nm or less, the arithmetic average roughness (Ra) and the maximum protrusion height (Rp) of the release surface can be easily made to fall within the ranges described later, whereby occurrence of defects in the molded ceramic green sheet can be effectively suppressed. The lower limit of the maximum protrusion height (Rp) of the surface of the substrate on the release agent layer side is not particularly limited, and may be, for example, 10nm or more, particularly 30nm or more, and further 50nm or more.
The arithmetic average roughness (Ra) of the surface of the substrate opposite to the release agent layer is preferably 10nm or more, particularly preferably 15nm or more, and further preferably 18nm or more. When the arithmetic average roughness (Ra) is 10nm or more, winding variation in winding the release film to produce a roll body can be easily suppressed. Further, when forming the roll body, it is possible to suppress an excessive increase in the effective contact area between the surface of the base material opposite to the release agent layer and the release surface in contact therewith, whereby blocking (blocking) can be effectively suppressed, and the charge amount of the release film unreeled from the roll body can be reduced. On the other hand, the arithmetic average roughness (Ra) of the surface of the substrate opposite to the release agent layer is preferably 50nm or less, particularly preferably 40nm or less, and further preferably 30nm or less. When the arithmetic average roughness (Ra) is 50nm or less, transfer of the surface shape (particularly, the concave-convex shape) of the surface of the base material opposite to the release agent layer to the surface of the ceramic green sheet in contact with the surface can be effectively suppressed when the release film and the ceramic green sheet molded on the release film are wound into a roll shape and conveyed, stored, or the like. As a result, the smoothness of the ceramic green sheet is easily maintained.
The maximum protrusion height (Rp) of the surface of the substrate opposite to the release agent layer is preferably 100nm or more, particularly preferably 200nm or more, and further preferably 300nm or more. When the maximum protrusion height (Rp) is 100nm or more, the occurrence of rolling variation and blocking of the roll body can be easily suppressed, and the charge amount of the release film can be reduced, similarly to the case where the arithmetic average roughness (Ra) is 10nm or more. The maximum protrusion height (Rp) of the surface of the substrate opposite to the release agent layer is preferably 1000nm or less, particularly preferably 700nm or less, and further preferably 500nm or less. By setting the maximum protrusion height (Rp) to 1000nm or less, the smoothness of the ceramic green sheet can be easily maintained as in the case of setting the arithmetic average roughness (Ra) to 50nm or less.
The surface roughness of the substrate may be measured by a known method using a surface roughness measuring instrument, and may be measured in the same manner as the method for measuring the surface roughness of the release surface in the test example described later.
The thickness of the base material is not particularly limited, and is preferably 10 μm or more, particularly preferably 15 μm or more, and further preferably 20 μm or more, for example. The thickness of the base material is preferably 300 μm or less, particularly preferably 200 μm or less, and further preferably 125 μm or less.
2. Stripper layer
The release agent layer of the present embodiment is formed from a release agent composition containing an amino resin (a), a hydroxyl group-containing acrylic resin (B), a polyorganosiloxane (C), and an acid catalyst (D).
In the release agent layer of the present embodiment, the use of the amino resin (a) and the hydroxyl group-containing acrylic resin (B) together makes it easy for the polyorganosiloxane (C) to segregate on the surface of the release agent layer. The reason for this is that the hydroxyl-containing acrylic resin (B) is excellent in compatibility with the amino resin (a), and poor in compatibility with the polyorganosiloxane (C). In this way, if the polyorganosiloxane (C) is likely to segregate on the surface of the release agent layer, light releasability can be expressed with a small amount of the polyorganosiloxane (C). If a large amount of polyorganosiloxane (C) is used to express light releasability, the reactivity thereof is poor, and thus, there is a problem that the migration amount of silicone is increased. In this embodiment, since the range of maintaining light releasability is widened and the blending amount of the polyorganosiloxane (C) becomes easy to adjust, the migration amount of the silicone component to the ceramic green sheet can be reduced, and migration of the silicone component can be suppressed. This can improve the adhesion force of the ceramic green sheets obtained.
(1) Amino resin (A)
In the release film of the present embodiment, the release agent composition contains an amino resin (a). In the case of forming the release agent layer from the release agent composition, since the amino resin (a) undergoes a condensation reaction in the presence of the acid catalyst (D), a three-dimensional structure based on the amino resin (a) can be formed in the resulting release agent layer. In addition, since the amino resin (a) also reacts with hydroxyl groups, the amino resin (a) also reacts with the hydroxyl group-containing acrylic resin (B), and the acrylic resin (B) is also added to the above three-dimensional structure. The above reaction may occur, for example, by heating. The release agent layer has the three-dimensional structure and thus exhibits sufficient elasticity, and thus the release film of the present embodiment can exhibit excellent releasability. In the present specification, the term "amino resin" refers to a component that can undergo a condensation reaction, and may not necessarily be a polymer compound. Here, the component may be a component in which no condensation reaction occurs at all, or may be a component in which a partial condensation reaction occurs.
As the above-mentioned amino resin (a), known amino resins can be used, and for example, melamine resin, urea resin, melamine resin (guanamine resin) or aniline resin can be used. Among them, melamine resins having a very high condensation reaction rate are preferably used. In the present specification, the term "melamine resin" refers to an aggregate of 1 melamine compound or a mixture containing a plurality of melamine compounds and/or polynuclear bodies obtained by condensing the melamine compounds.
Specifically, the melamine resin preferably contains a melamine compound represented by the following general formula (a), or a polynuclear product obtained by condensing 2 or more melamine compounds.
[ chemical formula 1]
In formula (a), X preferably represents-H, -CH 2 -OH or-CH 2 -O-R. These groups constitute reactive groups in the condensation reaction of the above melamine compounds with each other. Specifically, the-NH group formed by taking X as H may be in the form of-N-CH 2 -OH groups and-N-CH 2 Condensation reaction between the R groups. In addition, by making X be-CH 2 -N-CH formed by-OH 2 -OH groups, by making X-CH 2 -N-CH formed by-O-R 2 the-O-R groups can be-NH, -N-CH groups 2 -OH groups and-N-CH 2 Condensation reaction between the-O-R groups.
At the above-mentioned-CH 2 In the group-O-R, R preferably represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms is preferably 1 to 6, particularly preferably 1 to 3. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and the like, and methyl is particularly preferred.
The X's may be the same or different. The R's may be the same or different from each other.
Melamine compounds are generally present in the following categories: all X are-CH 2 -a full ether of O-R; at least 1X is-CH 2 Imino-hydroxymethyl form of-OH and at least 1X is H; at least 1X is-CH 2 -OH and no hydroxymethyl form of X being H; and at least 1X is H and is absent as-CH 2 Imino form of X of-OH. The release film of the present embodiment may use any of the types of melamine compounds described above.
In the stripping agent composition for forming the stripping agent layer, the weight average molecular weight of the amino resin (a) is preferably 150 or more, particularly preferably 300 or more, and further preferably 500 or more. This stabilizes the crosslinking speed and forms a smoother release surface. The weight average molecular weight is preferably 10000 or less, particularly preferably 5000 or less, and further preferably 4000 or less. Thus, the viscosity of the release agent composition is moderately low, and the coating liquid of the release agent composition is easily coated on the substrate. The weight average molecular weight in the present specification is a value in terms of standard styrene measured by Gel Permeation Chromatography (GPC).
(2) Hydroxyl-containing acrylic resin (B)
In the release film of the present embodiment, the release agent composition contains the hydroxyl group-containing acrylic resin (B).
The hydroxyl group-containing acrylic resin (B) may be formed only from hydroxyl group-containing acrylic monomers (hereinafter referred to as "hydroxyl group-containing monomers"), or may be preferably produced by copolymerizing a hydroxyl group-containing monomer with other copolymerizable monomers. The production method includes known methods, for example, bulk polymerization, solution polymerization in an organic solvent, emulsion polymerization in water, and the like.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono (meth) acrylate, polycaprolactone-modified hydroxyalkyl (meth) acrylate, and polycaprolactone-modified poly (oxyalkylene) (meth) acrylate. The hydroxyl group-containing monomer may be used alone in an amount of 1 or in an amount of 2 or more. In the present specification, (meth) acrylate means both acrylate and methacrylate. Other similar terms are also the same.
Examples of other copolymerizable acrylic monomers include alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, and stearic (meth) acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate; acrylamide, methacrylamide or derivatives thereof; quaternary ammonium salt-containing monomers such as 2- (methacryloyloxy) ethyltrimethylammonium chloride and 2- (methacryloyloxy) ethyltrimethylammonium bromide; (meth) acrylic acid sulfoalkyl esters such as 2-acrylamido-2-methylpropanesulfonic acid and the like, (meth) acrylic acid sulfoalkyl esters such as 2-sulfoethyl (meth) acrylate; acrylonitrile, methacrylonitrile, and the like. Examples of the monomer other than the copolymerizable acrylic monomer include vinyl acetate, styrene, vinyl toluene, and α -methylstyrene. They may be used alone or in combination of 1 or more than 2.
The hydroxyl value of the hydroxyl-containing acrylic resin (B) is preferably 10mgKOH/g or more, particularly preferably 15mgKOH/g or more, and further preferably 20mgKOH/g or more. Thus, the amino resin (A) and the hydroxyl-containing acrylic resin (B) can be reacted well and cured. The hydroxyl value is preferably 200mgKOH/g or less, particularly preferably 150mgKOH/g or less, and further preferably 100mgKOH/g or less. Thus, the amino resin (A) and the hydroxyl-containing acrylic resin (B) can be reacted and cured well, and the stability of the mixed coating liquid can be maintained sufficiently. In the present specification, the hydroxyl value of the acrylic resin is a value measured by the neutralization titration method (JIS K0070).
The glass transition temperature Tg of the hydroxyl group-containing acrylic resin (B) is preferably-20℃or higher, particularly preferably 30℃or higher, and further preferably 50℃or higher. Thus, the coating film cured by reaction with the amino resin (a) has high elasticity, and exhibits light releasability to the ceramic green sheet more easily. The glass transition temperature Tg is preferably 150 ℃ or less, particularly preferably 120 ℃ or less, and further preferably 100 ℃ or less. Thus, the amino resin (A) and the hydroxyl-containing acrylic resin (B) are moderately compatible, and sufficient reactivity can be ensured. In addition, the glass transition temperature was measured using a differential scanning calorimeter (DSC: differential Scanning Calorimetry).
The weight average molecular weight of the hydroxyl group-containing acrylic resin (B) is preferably 500 or more, particularly preferably 3000 or more, and further preferably 5000 or more. Thus, the coating film which is cured by reaction with the amino resin (a) has high elasticity and poor compatibility with the polyorganosiloxane (C), and thus the polyorganosiloxane (C) is likely to segregate on the surface of the release agent layer, and light releasability is more likely to be expressed in the ceramic green sheet. The weight average molecular weight is preferably 200000 or less, particularly preferably 150000 or less, and further preferably 100000 or less. Thus, the polyorganosiloxane (C) is more difficult to be compatible with the hydroxyl-containing acrylic resin (B), the polyorganosiloxane (C) is likely to segregate on the surface opposite to the substrate, and the ceramic green sheet is more likely to exhibit light releasability.
The hydroxyl group-containing acrylic resin (B) of the present embodiment is preferably substantially not subjected to silicone modification. This makes it easier for the polyorganosiloxane (C) to segregate on the surface of the release agent layer. Specifically, the amount of the modified silicone is preferably 0.50mmol/g or less, particularly preferably 0.20mmol/g or less, further preferably 0.10mmol/g or less, and most preferably 0mmol/g.
The content of the hydroxyl-containing acrylic resin (B) in the stripper composition is preferably 5 parts by mass or more, particularly preferably 15 parts by mass or more, and further preferably 25 parts by mass or more, relative to 100 parts by mass of the amino resin (a). The content is preferably 200 parts by mass or less, particularly preferably 150 parts by mass or less, and further preferably 120 parts by mass or less, based on 100 parts by mass of the amino resin (a). By setting the content of the hydroxyl group-containing acrylic resin (B) within the above range, the polyorganosiloxane (C) having poor compatibility with the hydroxyl group-containing acrylic resin (B) is more likely to segregate on the surface of the release agent layer, and light releasability can be more effectively expressed with a small amount of the polyorganosiloxane (C).
(3) Polyorganosiloxane (C)
In the release film of the present embodiment, the release agent composition contains a polyorganosiloxane (C). By containing the polyorganosiloxane (C) in the release agent composition, the surface free energy of the release agent layer formed is moderately reduced. Thus, the peeling force when peeling the release film from the ceramic green sheet formed on the peeling surface of the release film is moderately reduced, and good peelability can be achieved. As described above, in the present embodiment, since good releasability can be achieved even when the polyorganosiloxane (C) is small, migration of the silicone component to the ceramic green sheet can be suppressed.
The polyorganosiloxane (C) is not particularly limited as long as the desired peelability can be imparted to the peeling agent layer. In the release film of the present embodiment, the polyorganosiloxane (C) preferably has at least 1 hydroxyl group in 1 molecule. By providing the polyorganosiloxane (C) with hydroxyl groups, the polyorganosiloxane (C) can undergo a condensation reaction with the amino resin (a) or the hydroxyl group-containing acrylic resin (B), and as a result, migration of the polyorganosiloxane (C) from the release agent layer to the ceramic green sheet is easily suppressed.
The structure other than the above hydroxyl groups in the polyorganosiloxane (C) is not particularly limited as long as the peelability is not hindered, or the reaction between the amino resins (a), the reaction between the amino resins (a) and the hydroxyl group-containing acrylic resins (B), and the reaction between the hydroxyl group-containing acrylic resins (B) are not hindered. As the polyorganosiloxane (C), a polymer containing a silicon compound represented by the following general formula (b) can be used.
[ chemical formula 2]
In the formula (b), m is an integer of 1 or more. In addition, R 1 ～R 8 Each independently represents a hydroxyl group, an organic group (including an organic group having a hydroxyl group), or a group other than these groups. Here, at R 1 ～R 8 When at least 1 of them is a hydroxyl group or an organic group having a hydroxyl group, R is preferably 3 ～R 8 At least 1 of which is the above-mentioned group. That is, when the polyorganosiloxane (C) has a hydroxyl group or an organic group having a hydroxyl group, the group is preferably present at the terminal of the polyorganosiloxane (C). By having hydroxyl groups at the terminal, the polyorganosiloxane (C) is easily condensed with the amino resin (a) or the hydroxyl group-containing acrylic resin (B) and fixed to a three-dimensional structure, and therefore migration of the polyorganosiloxane (C) is effectively suppressed.
Examples of the organic group include a polyester group, a polyether group and a methanol group, and the polyorganosiloxane (C) of the present embodiment particularly preferably has at least 1 of a polyester group, a polyether group and a methanol group. By providing the polyorganosiloxane (C) with at least 1 of a polyester group, a polyether group and a methanol group, the polyorganosiloxane (C) is easily and favorably mixed with the amino resin (A) and the hydroxyl-containing acrylic resin (B) in the stripping agent composition.
Here, the polyorganosiloxane (C) is more compatible with the amino resin (a) than the hydroxyl-containing acrylic resin (B), and by mixing both the amino resin (a) and the hydroxyl-containing acrylic resin (B), it is possible to produce a state in which the polyorganosiloxane (C) is likely to segregate while suppressing extreme phase separation at the time of curing the coating film. Thus, the condensation reaction of the polyorganosiloxane (C) with the amino resin (A) or the hydroxyl-containing acrylic resin (B) as described above proceeds well, and migration of the polyorganosiloxane (C) is effectively suppressed. In the present specification, the term "organic group" does not include an alkyl group described later.
Examples of the group other than the hydroxyl group and the organic group (including an organic group having a hydroxyl group) include an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and the like, and methyl is particularly preferred.
R 1 ～R 8 May be the same or different. In addition, there are a plurality of R 1 R is R 2 When R is 1 R is R 2 The two may be the same or different.
The weight average molecular weight of the polyorganosiloxane (C) is preferably 20000 or less, particularly preferably 10000 or less, and further preferably 5000 or less. Thus, the polyorganosiloxane (C) is excellent in compatibility with the amino resin (A), and a release agent layer excellent in surface state can be easily formed. Further, migration of the polyorganosiloxane (C) from the release agent layer to the ceramic green sheet is easily suppressed. On the other hand, the weight average molecular weight of the polyorganosiloxane (C) is preferably 500 or more, particularly preferably 1000 or more, and further preferably 2000 or more. Thus, the polyorganosiloxane (C) can easily lower the surface free energy of the release surface of the release agent layer, and can easily achieve the desired release property.
The content of the polyorganosiloxane (C) in the stripper composition is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, particularly preferably 0.30 parts by mass or more, and further preferably 0.50 parts by mass or more, per 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). Thus, the release film of the present embodiment can easily achieve a desired releasability from the ceramic green sheet. The content of the polyorganosiloxane (C) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, particularly preferably 5 parts by mass or less, and further preferably 4 parts by mass or less, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). This effectively suppresses migration of the polyorganosiloxane (C) from the release agent layer to the ceramic green sheet. In the release film of the present embodiment, even if the content of the polyorganosiloxane (C) is small, the light releasability can be sufficiently exhibited for the above-described reasons.
(4) Acid catalyst (D)
In the release film of the present embodiment, the release agent composition contains an acid catalyst (D). By containing the acid catalyst (D), the reaction between the amino resins (a) and the hydroxyl-containing acrylic resin (B), and the reaction between the polyorganosiloxane (C) and the alkoxysilane hydrolysis polycondensate (E) described later are efficiently performed, whereby a stripper layer exhibiting sufficient elasticity is formed.
The acid catalyst (D) is not particularly limited as long as it has a catalytic action on the reaction, but at least 1 of a sulfonic acid catalyst and a phosphoric acid catalyst is particularly preferably used. These catalysts have high catalytic activity, and thus the curing of the stripper layer is easily performed at a lower temperature. Examples of the sulfonic acid catalyst include p-toluenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, and the like, and among these, p-toluenesulfonic acid is preferably used. In the case where a holo-ether type melamine resin is mainly used as the amino resin (a), a sulfonic acid type catalyst is preferably used in order to efficiently perform the condensation reaction of the melamine resin. Examples of the phosphoric acid catalyst include phosphoric acid and phosphorous acid. In the case where an imino-methylol melamine resin is mainly used as the amino resin (a), a phosphoric acid catalyst is preferably used in order to efficiently perform the condensation reaction of the melamine resin. As examples of the acid catalyst (D) other than the above, hydrochloric acid, sulfuric acid, nitric acid, and the like can also be used.
The content of the acid catalyst (D) in the stripper composition is preferably 0.5 parts by mass or more, particularly preferably 0.7 parts by mass or more, and further preferably 1.0 part by mass or more, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). Thus, in addition to the condensation reaction between the amino resins (a) and the condensation reaction between the hydroxyl-containing acrylic resins (B), the reaction between the amino resins (a), the hydroxyl-containing acrylic resins (B), the polyorganosiloxane (C) and the alkoxysilane hydrolysis polycondensate (E) described later can be effectively performed. The content is preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and further preferably 10 parts by mass or less, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). Thus, the three-dimensional structure formed in the stripper layer is easy to hold a low molecular weight component, and the precipitation of the component from the stripper layer can be effectively suppressed.
(5) Alkoxysilane hydrolysis polycondensates (E)
In the release film of the present embodiment, the release agent composition preferably also contains an alkoxysilane hydrolysis polycondensate (E) having a siloxane bond (si—o—si) as a skeleton. When the release agent composition contains the alkoxysilane hydrolysis polycondensate (E), the alkoxysilane hydrolysis polycondensate (E) is reacted with the hydroxyl group-containing acrylic resin (B) and the hydroxyl group-containing polyorganosiloxane (C) to form a further hard coating film, whereby light releasability to the ceramic green sheet is more easily exhibited. In addition, the migration inhibition effect of the silicone component is more excellent.
The alkoxysilane hydrolysis polycondensate (E) is not particularly limited as long as the peelability of the release film is not greatly impaired. The preferable alkoxysilane hydrolysis polycondensate (E) is preferably obtained by hydrolyzing a mixture of a tetraalkoxysilane and/or an oligomer thereof and a phenylalkoxysilane and/or an oligomer thereof, and then performing a polycondensation reaction.
The tetraalkoxysilane is preferably Si (OR) 4 The formula is, in addition, preferably Si as the oligomer of the tetraalkoxysilane n O n-1 (OR) 2n+2 The formula is shown in the specification. In these formulae, R is preferably an alkyl group having 1 to 6 carbon atoms, and n is preferably an integer of 2 to 10.
Preferred specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and from the viewpoint of availability and reactivity in hydrolysis reaction, at least one of tetramethoxysilane and tetraethoxysilane is preferable.
The tetraalkoxysilane oligomer is preferably obtained by subjecting the alkoxysilane monomer to hydrolysis and condensation reaction. As the commercial products, tetramethyl silicate 51 as an average tetramer oligomer of tetramethoxysilane, tetraethyl silicate 40 as an average pentamer oligomer of tetraethoxysilane, and the like are preferably used.
The phenylalkoxysilane is preferably selected from Ph n Si(OR) 4-n The formula is shown in the specification. In the formula, ph represents phenyl, R independently represents alkyl having 1 to 6 carbon atoms, and n represents an integer of 1 to 2. The phenylalkoxysilane oligomer is preferably a dimer to decamer of phenylalkoxysilane represented by the above formula, and particularly preferably a dimer to trimer.
Preferred specific examples of the phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltri-n-butoxysilane. Among them, at least one of phenyltrimethoxysilane and phenyltriethoxysilane is preferably used in view of excellent reactivity.
Further, diphenyldialkoxysilane in which 2 phenyl groups are bonded to silicon atoms may be used as the phenylalkoxysilane. In this case, the alkoxy group is preferably methoxy or ethoxy.
The hydrolysis and polycondensation reaction of the mixture of the tetraalkoxysilane and/or oligomer thereof and the phenylalkoxysilane and/or oligomer thereof can be carried out by a known method. The ratio of the tetraalkoxysilane and/or oligomer thereof to the phenylalkoxysilane and/or oligomer thereof in the mixture is preferably 1:1 to 1:0.1 in terms of mass ratio.
The content of the alkoxysilane hydrolysis polycondensate (E) in the stripper composition is preferably 2 parts by mass or more, particularly preferably 5 parts by mass or more, further preferably 10 parts by mass or more, per 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). This makes the migration inhibition effect of the silicone component more excellent. The content of the alkoxysilane hydrolysis polycondensate (E) is preferably 50 parts by mass or less, particularly preferably 40 parts by mass or less, and further preferably 30 parts by mass or less, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). Thus, the release agent layer is easily cured, and good release properties and migration inhibition properties of the silicone component are easily achieved.
In addition, in the release film of the present embodiment, by using the alkoxysilane hydrolysis polycondensate (E), the antistatic property is also improved. It has been predicted that antistatic properties cannot be obtained when the alkoxysilane hydrolysis polycondensate (E) as described above is used as a material for the release agent layer. However, contrary to this expectation, the inventors of the present application found that by using the alkoxysilane hydrolysis polycondensate (E), the antistatic properties at a level required for the release film for the ceramic green sheet production process can be achieved. For example, the surface resistivity of the release film of the present embodiment may be the same value as that of the polyethylene terephthalate film as an insulator.
Although not limited to this, it is assumed that the state of the tribostatic sequence of the component contained in the stripper layer is changed by the alkoxysilane hydrolysis polycondensate (E) as one of the reasons for obtaining such antistatic properties. In general, the tribostatic series is a series in which substances that are easily positively charged when 2 substances are rubbed are arranged above and substances that are easily negatively charged are arranged below. The farther apart the positions in the tribostatic sequence are, the easier it is to charge when rubbing 2 substances.
In general, the amino resin (a) and the hydroxyl-containing acrylic resin (B) are located at a position in the triboelectric series farther from the material of the base material (e.g., polyethylene terephthalate film). Therefore, in the case of the release agent layer containing the amino resin (a), the release electrification of the release film is extremely easily generated when the release film is unwound from the roll body or the like.
On the other hand, the alkoxysilane hydrolysis polycondensate (E) is located closer to polyethylene terephthalate, which is often used as a base material of a release film for ceramic green sheet production, in the triboelectric series than the amino resin (a) and the hydroxyl-containing acrylic resin (B). By containing such an alkoxysilane hydrolysis polycondensate (E) in the stripper composition of the present embodiment, the alkoxysilane hydrolysis polycondensate (E) is bonded to the amino resin (a) or the hydroxyl-containing acrylic resin (B) at the time of forming the stripper layer. Further, the resulting bonded product has a triboelectric series very close to that of polyethylene terephthalate, compared with the amino resin (a) and the hydroxyl-containing acrylic resin (B) before bonding.
In addition, the stripper composition of the present embodiment contains a polyorganosiloxane (C) that is also located relatively close to the polyethylene terephthalate in the tribostatic sequence. The polyorganosiloxane (C) can be bonded by reacting with the amino resin (a), the hydroxyl group-containing acrylic resin (B) or the alkoxysilane hydrolysis polycondensate (E) through the functional group of the polyorganosiloxane (C), and therefore the position of the triboelectric series of the crosslinked structure bonded by the polyorganosiloxane (C) is very close to the position of the polyethylene terephthalate.
As described above, in the release agent layer using the alkoxysilane hydrolysis polycondensate (E), the interval between the frictional static electricity sequences between the component contained in the release agent layer and the substrate (polyethylene terephthalate) is significantly reduced compared with the conventional release agent layer, and as a result, the release electrification is less likely to occur.
The above description is not limited to the sole reason why the release film using the alkoxysilane hydrolysis polycondensate (E) is not easily charged, but there are other additional reasons. However, this additional reason does not include the possibility that the alkoxysilane hydrolysis polycondensate (E) functions as a general antistatic agent. Some of the compounds corresponding to the alkoxysilane hydrolysis polycondensates (E) are generally used as antistatic agents. When the alkoxysilane hydrolysis polycondensate (E) is used as the antistatic agent, a large amount of hydroxyl groups of the alkoxysilane hydrolysis polycondensate (E) are present on the surface of the member using the alkoxysilane hydrolysis polycondensate (E), and thus the surface resistance value of the surface is reduced, and the antistatic effect is exhibited. However, in the release agent layer using the alkoxysilane hydrolysis polycondensate (E), almost all of the hydroxyl groups of the alkoxysilane hydrolysis polycondensate (E) are used for reaction with the amino resin (a), the hydroxyl-containing acrylic resin (B), or the polyorganosiloxane (C) and disappear. Therefore, it is presumed that the alkoxysilane hydrolysis polycondensate (E) does not function as a general antistatic agent in the release agent layer using the alkoxysilane hydrolysis polycondensate (E). This is also suggested by the fact that the surface resistance value of the release agent layer using the alkoxysilane hydrolysis polycondensate (E) is hardly changed as compared with the case where the alkoxysilane hydrolysis polycondensate (E) is not used.
(6) Other ingredients
In addition to the above components, the stripping agent composition may contain other components such as a polyol compound (F), a dispersant, a crosslinking agent, a reaction inhibitor, an adhesion improver, and a lubricant.
The polyol compound (F) is not particularly limited, and various known polyol compounds can be used. By containing the polyol compound (F) in the release agent composition, the elastic modulus of the release agent layer can be easily adjusted to a desired range, and the curability when the release agent composition is cured to form the release agent layer can be easily improved. From this viewpoint, the polyol compound (F) is preferably a compound having a molecular weight or weight average molecular weight of 50 or more. In addition, a compound having a weight average molecular weight of 10000 or less is preferably used, a compound having a weight average molecular weight of 5000 or less is particularly preferably used, and a compound having a weight average molecular weight of 3000 or less is more preferably used.
Specific examples of the polyol compound (F) include aliphatic diols such as 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 5-pentanediol, 2-diethyl-1, 3-propanediol, 1, 9-nonanediol, 1, 10-decanediol, butylethylpropanediol and butylethylpentanediol; alicyclic diols such as 1, 4-cyclohexanedimethanol; trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, dimer diol, hydrogenated dimer diol, triol (trimertriol), hydrogenated triol, castor oil type modified polyol, alkylene oxide adducts of bisphenol compounds or derivatives thereof, and the like. Further, polymer polyols such as polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols and polyolefin polyols can be mentioned. Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol (including ethylene glycol), polypropylene glycol (including propylene glycol), and polytetramethylene glycol (poly tetramethylene glycol), and copolymers such as ethylene oxide-propylene oxide copolymers containing a plurality of alkylene oxides as monomer components (alkylene oxide-other alkylene oxides). They may be used alone or in combination of 2 or more.
When the releasing agent composition contains the polyol compound (F), the content of the polyol compound (F) in the releasing agent composition is preferably 0.1 part by mass or more, particularly preferably 0.5 part by mass or more, and further preferably 1 part by mass or more, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl group-containing acrylic resin (B). The content is preferably 100 parts by mass or less, particularly preferably 70 parts by mass or less, and further preferably 40 parts by mass or less, based on 100 parts by mass of the total of the amino resin (a) and the hydroxyl-containing acrylic resin (B). When the content of the polyol compound (F) is within the above range, the peel force can be easily adjusted to a desired range.
(7) Physical Properties of the Release agent layer
In the release film of the present embodiment, the surface free energy of the release face of the release agent layer is preferably 17mJ/m 2 The above is particularly preferably 19mJ/m 2 The above is more preferably 21mJ/m 2 The above. Furthermore, the surface free energy is preferably 40mJ/m 2 Hereinafter, it is particularly preferably 35mJ/m 2 Hereinafter, it is more preferably 30mJ/m 2 The following is given. In the release film of the present embodiment, the release agent layer is formed of the release agent composition containing the above components, so that the surface free energy of the release surface can be easily adjusted to the above range. Further, the release film of the present embodiment can easily exhibit more excellent releasability from the molded ceramic green sheet by setting the surface free energy to the above range. The method for measuring the free energy of the surface is as shown in the test example described below.
In the release film of the present embodiment, the thickness of the release agent layer is preferably 0.02 μm or more, particularly preferably 0.03 μm or more, and further preferably 0.04 μm or more. Thus, the release agent layer is easily cured, and with this, the desired releasability is easily achieved. The thickness is preferably 0.5 μm or less, particularly preferably 0.4 μm or less, and further preferably 0.3 μm or less. This makes it difficult to affect the curing shrinkage of the release agent composition, to suppress the occurrence of curling of the release film, and to highly maintain the accuracy (particularly, the accuracy in the width direction) of the thickness of the molded ceramic green sheet.
3. Physical properties of release film for ceramic green sheet production process
In the release film of the present embodiment, the arithmetic average roughness (Ra) of the release surface is preferably 50nm or less, particularly preferably 40nm or less, and further preferably 30nm or less. Thus, the release surface has excellent smoothness, and the occurrence of defects such as pinholes and thickness unevenness in the molded ceramic green sheet can be effectively suppressed. The lower limit of the arithmetic average roughness (Ra) is not particularly limited, and may be, for example, 1nm or more, particularly 3nm or more, and further 5nm or more.
In the release film of the present embodiment, the maximum protrusion height (Rp) of the release surface is preferably 1000nm or less, particularly preferably 700nm or less, and further preferably 500nm or less. Thus, the release surface has excellent smoothness, and the occurrence of defects such as pinholes and thickness unevenness in the molded ceramic green sheet can be effectively suppressed. The lower limit of the maximum protrusion height (Rp) is not particularly limited, and may be, for example, 10nm or more, particularly 30nm or more, and further 50nm or more.
The details of the method for measuring the arithmetic average roughness (Ra) and the maximum protrusion height (Rp) of the release surface are described in the test examples described below.
In the release film of the present embodiment, the release force required for peeling the release film from the ceramic green sheet molded on the release surface is preferably 20mN/50mm or less, particularly preferably 18mN/50mm or less, and further preferably 15mN/50mm or less. In the release film of the present embodiment, the amino resin (a) and the hydroxyl-containing acrylic resin (B) are contained in the release agent layer as main components, whereby the polyorganosiloxane (C) is likely to segregate on the surface as compared with the case where only the amino resin (a) is the main component, and as a result, light releasability can be expressed with a small amount of the polyorganosiloxane (C), and the low release force as described above can be easily set. The lower limit of the peeling force is not particularly limited, but is preferably 5mN/50mm or more, particularly preferably 8mN/50mm or more, and further preferably 10mN/50mm or more, in order to prevent unexpected peeling of the ceramic green sheet. The details of the method for measuring the peel force are described in the test examples described below.
4. Method for producing release film for ceramic green sheet production process
The method of producing the release film of the present embodiment is not particularly limited as long as the step of forming the release agent layer from the release agent composition described above is included. For example, it is preferable to obtain a release film by applying a coating liquid containing the release agent composition and an organic solvent as required on one surface of a substrate, and then drying and heating the obtained coating film to cure the release agent composition and form a release agent layer.
Specific examples of the coating method include gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, and die coating.
The organic solvent is not particularly limited, and various solvents can be used. For example, hydrocarbon compounds such as toluene, hexane and heptane, isopropanol, isobutanol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof can be used. Particularly, a mixed solution of methyl ethyl ketone and isopropyl alcohol is preferably used.
The stripper composition coated in the above manner is preferably thermally cured. The heating temperature in this case is preferably 100℃or higher, and particularly preferably 110℃or higher. The heating temperature is preferably 150℃or less, and particularly preferably 140℃or less. The heating time for heat curing is preferably 10 seconds or more, and particularly preferably 15 seconds or more. The heating time is preferably 120 seconds or less, and particularly preferably 90 seconds or less.
5. Method for using release film for ceramic green sheet manufacturing process
The release film of the present embodiment is preferably used for manufacturing a ceramic green sheet. At this time, first, a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide is applied to the release surface of the release agent layer.
The coating may be performed by, for example, a slit coating method (slot coating) or a doctor blade method (doctor blade method). Examples of the binder component contained in the ceramic slurry include butyral resin, acrylic resin, and the like. Examples of the solvent contained in the ceramic slurry include an organic solvent and an aqueous solvent.
After the slurry is applied to the release surface, the ceramic slurry thus applied is dried, whereby the ceramic green sheet can be molded. After the ceramic green sheet is molded, the ceramic green sheet is separated from the release film. In this case, in the release film of the present embodiment, the release film is formed of a release agent composition containing any of the amino resin (a), the hydroxyl group-containing acrylic resin (B), the polyorganosiloxane (C), and other materials, and thus has excellent releasability from the ceramic green sheet. Therefore, the ceramic green sheet can be peeled with an appropriate peeling force without generating cracks, breaks, or the like. In addition, in the release film of the present embodiment, since the amount of the polyorganosiloxane (C) used can be made small, the migration amount of the silicone component to the ceramic green sheet can be reduced.
The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiments also includes all design changes and equivalents falling within the technical scope of the present invention.
For example, another layer may be provided on the surface of the substrate opposite to the release agent layer or between the substrate and the release agent layer.
Examples
The present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
75 parts by mass (solid content equivalent, hereinafter the same) of a methylated melamine resin (NIPPON CARBIDE INDUSTRIES co., manufactured by inc., product name "MW-30", weight average molecular weight: 508), 25 parts by mass of a hydroxyl group-containing acrylic resin (B1) (manufactured by DIC CORPORATION, product name "ACRYDIC a-807-BA"), and 2 parts by mass of a both terminal methanol-modified polydimethylsiloxane (C1; shin-Etsu Chemical co., ltd., manufactured by KF-6001", weight average molecular weight: 2400) as an amino resin (a) were diluted with a mixed solvent of isopropyl alcohol and methyl ethyl ketone and cyclohexanone (mixing ratio: isopropyl alcohol: methyl ethyl ketone: cyclohexanone=40:40:20). To this diluted solution, 4 parts by mass of p-toluenesulfonic acid (Shin-Etsu Chemical co., ltd. Product name "PS-80") as an acid catalyst (D) was added by dilution, and the mixture was stirred uniformly, thereby obtaining a coating solution of a stripper composition having a solid content concentration of 1.8% by mass.
On the other hand, biaxially stretched polyethylene terephthalate film (thickness: 31 μm) was prepared as a substrate. The substrate had an arithmetic average roughness (Ra) of 24nm and a maximum protrusion height (Rp) of 451nm on one surface (hereinafter, sometimes referred to as "first surface"). The other surface (hereinafter, sometimes referred to as "second surface") of the substrate had an arithmetic average roughness (Ra) of 25nm and a maximum protrusion height (Rp) of 465nm.
The coating liquid of the stripping agent composition obtained in the above manner was applied to the first surface of the substrate by using a bar coater, and the obtained coating film was heated at 125℃for 30 seconds, dried and cured to form a stripping agent layer. Thus, a release film in which a release agent layer was laminated on one surface of a base material was obtained.
The thickness of the release agent layer of the release film was measured as described in test example 2, which was described later, and found to be 0.07. Mu.m.
Example 2
A release film was obtained in the same manner as in example 1, except that the blending amount of the amino resin (a) was changed to 50 parts by mass and the blending amount of the hydroxyl-containing acrylic resin (B) was changed to 50 parts by mass.
Example 3
A release film was obtained in the same manner as in example 1 except that the hydroxyl-containing acrylic resin (B) was changed to the hydroxyl-containing acrylic resin (B2) (manufactured by DIC CORPORATION, product name "acrycic WMU-504").
Example 4
A release film was obtained in the same manner as in example 1 except that the hydroxyl-containing acrylic resin (B) was changed to the hydroxyl-containing acrylic resin (B3) (product name "ACRYDIC WAU-139", manufactured by DIC CORPORATION).
Example 5
A release film was obtained in the same manner as in example 1 except that the polyorganosiloxane (C) was changed to a both terminal methanol-modified polydimethylsiloxane (C2; shin-Etsu Chemical Co., ltd., product name "KF-6002", weight-average molecular weight: 4600).
Example 6
A release film was obtained in the same manner as in example 1 except that the polyorganosiloxane (C) was changed to a both terminal methanol-modified polydimethylsiloxane (C3; shin-Etsu Chemical Co., ltd., product name "KF-6003", weight-average molecular weight: 8000).
Example 7
A release film was obtained in the same manner as in example 1 except that the polyorganosiloxane (C) was changed to a side chain methanol-modified polydimethylsiloxane (C4; shin-Etsu Chemical Co., ltd., product name "X-22-4039", weight-average molecular weight: 5300).
Example 8
A release film was obtained in the same manner as in example 1, except that the blending amount of the polyorganosiloxane (C) was changed to 4 parts by mass.
Example 9
75 parts by mass of a methylated melamine resin (NIPPON CARBIDE INDUSTRIES Co., inc. Manufactured by the trade name "MW-30", weight average molecular weight: 508) as an amino resin (a), 25 parts by mass of a hydroxyl-containing acrylic resin (B1) (manufactured by DIC CORPORATION, product name "acrycic a-807-BA"), 2.2 parts by mass of a both terminal methanol-modified polydimethylsiloxane (C1; shin-Etsu Chemical Co., manufactured by ltd., product name "KF-6001", weight average molecular weight: 2400) as a hydroxyl-containing acrylic resin (B), as a polyorganosiloxane (C), and 10 parts by mass of an alkoxysilane hydrolysis polycondensate (E1; coloat Co, manufactured by ltd., product name "N-103X") were diluted with a mixed solvent of isopropyl alcohol and methyl ethyl ketone and cyclohexanone (mixing ratio: isopropyl alcohol: methyl ethyl ketone=40:40:20). To this diluted solution, 4.4 parts by mass of p-toluenesulfonic acid (Shin-Etsu Chemical co., ltd. Product name "PS-80") as an acid catalyst (D) was added by dilution, and the mixture was stirred uniformly, thereby obtaining a coating solution of a stripper composition having a solid content concentration of 1.8% by mass. A release film was obtained in the same manner as in example 1 except that the coating liquid was used.
Example 10
A release film was obtained in the same manner as in example 9 except that the alkoxysilane hydrolysis polycondensate (E) was changed to "PS-903" (E2) manufactured by coloat Co,. Ltd.
Example 11
75 parts by mass of a methylated melamine resin (NIPPON CARBIDE INDUSTRIES CO., INC. Manufactured by INC., product name "MW-30", weight average molecular weight: 508) as an amino resin (A), 25 parts by mass of a hydroxyl-containing acrylic resin (B1) (manufactured by DIC CORPORATION, product name "ACRYDIC A-807-BA"), 2.2 parts by mass of a both terminal methanol-modified polydimethylsiloxane (C1; shin-Etsu Chemical Co., manufactured by Ltd., product name "KF-6001", weight average molecular weight: 2400) as a hydroxyl-containing acrylic resin (B), and 10 parts by mass of ethylene glycol (F1; NIPPON SHOKUBIAI CO., LTD. Manufactured by LTD., product name "(mono) ethylene glycol", molecular weight: 62) as a polyorganosiloxane (C) were diluted with a mixed solvent of isopropyl alcohol and methyl ethyl ketone and cyclohexanone (mixing ratio: isopropyl alcohol: methyl ethyl ketone: cyclohexanone=40:40:20). To this diluted solution, 4.4 parts by mass of p-toluenesulfonic acid (Shin-Etsu Chemical co., ltd. Product name "PS-80") as an acid catalyst (D) was added by dilution, and the mixture was stirred uniformly, thereby obtaining a coating solution of a stripper composition having a solid content concentration of 1.8% by mass. A release film was obtained in the same manner as in example 1 except that the coating liquid was used.
Example 12
A release film was obtained in the same manner as in example 11 except that the polyol compound (F) was changed to propylene glycol (F2; manufactured by SANKYO CHEMICALCO., LTD., product name "propylene glycol", molecular weight: 76).
Example 13
A release film was obtained in the same manner as in example 11 except that the blending amount of the polyorganosiloxane (C) was changed to 4.4 parts by mass.
Example 14
75 parts by mass of a methylated melamine resin (NIPPON CARBIDE INDUSTRIES Co., inc. Manufactured as an amino resin (a), product name "MW-30", weight average molecular weight: 508), 25 parts by mass of a hydroxyl-containing acrylic resin (B1) (manufactured by DIC CORPORATION, product name "acryidic a-807-BA"), 2.4 parts by mass of a both terminal methanol-modified polydimethylsiloxane (C1; shin-Etsu Chemical Co., manufactured by ltd., product name "KF-6001", weight average molecular weight: 2400), 10 parts by mass of an alkoxysilane hydrolysis polycondensate (E) (E1; coloat Co., ltd., manufactured by N-103X "), and 10 parts by mass of an ethylene glycol (F1; okubco., ltco., ltd., manufactured by ltco.) as a polyol compound (F) were diluted with a mixed solvent of isopropyl alcohol and methyl ethyl ketone and cyclohexanone (mixing ratio: isopropyl alcohol: methyl ethyl ketone: cyclohexanone=40:40:20). To this diluted solution, 4.8 parts by mass of p-toluenesulfonic acid (Shin-Etsu Chemical co., ltd. Product name "PS-80") as an acid catalyst (D) was added by dilution, and the mixture was stirred uniformly, thereby obtaining a coating solution of a stripper composition having a solid content concentration of 1.8% by mass. A release film was obtained in the same manner as in example 1 except that the coating liquid was used.
Example 15
A release film was obtained in the same manner as in example 1 except that the thickness of the release agent layer was changed to 0.04 μm.
Example 16
A release film was obtained in the same manner as in example 1 except that the substrate was changed to a biaxially stretched polyethylene terephthalate film (thickness: 31 μm) having an arithmetic average roughness (Ra) of 13nm, a maximum protrusion height (Rp) of 210nm, and an arithmetic average roughness (Ra) of 13nm and a maximum protrusion height (Rp) of 224nm on the first surface.
Example 17
A release film was obtained in the same manner as in example 1 except that the base material was changed to a biaxially stretched polyethylene terephthalate film (thickness: 31 μm) having an arithmetic average roughness (Ra) of 7nm, a maximum protrusion height (Rp) of 70nm, and an arithmetic average roughness (Ra) of 28nm and a maximum protrusion height (Rp) of 498nm on the first surface.
Comparative example 1
A release film was obtained in the same manner as in example 1, except that the hydroxyl group-containing acrylic resin (B) was not blended.
Comparative example 2
A release film was obtained in the same manner as in comparative example 1, except that the blending amount of the polyorganosiloxane (C) was changed to 4 parts by mass.
Comparative example 3
A release film was obtained in the same manner as in comparative example 2 except that the polyorganosiloxane (C) was changed to a both terminal methanol-modified polydimethylsiloxane (C3; shin-Etsu Chemical Co., ltd., product name "KF-6003", weight-average molecular weight: 8000).
Comparative example 4
A release film was obtained in the same manner as in comparative example 2 except that the polyorganosiloxane (C) was changed to a side chain methanol-modified polydimethylsiloxane (C4; shin-Etsu Chemical Co., ltd., product name "X-22-4039", weight-average molecular weight: 5300).
Comparative example 5
A release film was obtained in the same manner as in comparative example 3 except that the blending amount of the polyorganosiloxane (C) was changed to 15 parts by mass.
Comparative example 6
After 100 parts by mass of a heat-curable addition reaction type silicone resin (Shin-Etsu Chemical co., ltd. Manufactured by ltd. Product name "KS-847H"), 2 parts by mass of a platinum catalyst (Shin-Etsu Chemical co., ltd. Manufactured by ltd. Product name "CAT-PL-50T") was further added and mixed, to obtain a coating liquid of a stripper composition having a solid content concentration of 1.5 mass%.
The resulting coating liquid was applied to the first surface of the same substrate as in example 1 using a bar coater, and the resulting coating film was heated at 125℃for 30 seconds, dried and cured to form a release agent layer. Thus, a release film was obtained in which a release agent layer was laminated on one surface of the base material.
The thickness of the release agent layer of the release film was measured as described in test example 2, which was described later, and found to be 0.09. Mu.m.
Test example 1 (evaluation of compatibility of stripper composition)
2g of the amino resin (A) and the hydroxyl-containing acrylic resin (B) used in the examples were diluted with ethyl acetate, respectively, to give a liquid having a solid content of 60% by mass, and 0.02g of undiluted polyorganosiloxane (C) was mixed, respectively. The appearance of these mixed solutions was visually confirmed, and the compatibility of the stripper composition was evaluated based on the following criteria. The results are shown in Table 2.
A: the mixture of the amino resin (A) and the polyorganosiloxane (C) is transparent, and the mixture of the hydroxyl-containing acrylic resin (B) and the polyorganosiloxane (C) is white turbid.
B: the mixed solution of the amino resin (A) and the polyorganosiloxane (C) is white turbid, and the mixed solution of the hydroxyl-containing acrylic resin (B) and the polyorganosiloxane (C) is also white turbid.
C: other than A, B described above
Test example 2 (measurement of thickness of Release agent layer)
The thickness (μm) of the release agent layer of the release film obtained in examples and comparative examples was measured using an ellipsometer (manufactured by J.A. Woollam Co., ltd., product name "M-2000"). The results are shown in Table 2.
Test example 3 (evaluation of curability of Release agent layer)
The release films obtained in examples and comparative examples were produced by wiping cloth (manufactured by OZU corporation, product name "becot AP-2") containing methyl ethyl ketone at 200g/cm 2 Is used to polish the surface of the stripper layer back and forth 10 times. The release surface was then visually observed, and the curability of the release agent layer was evaluated according to the following criteria. The results are shown in Table 2.
A: the stripper layer did not dissolve or fall off.
B: partial dissolution of the stripper layer was observed.
C: the stripper layer is completely dissolved and is detached from the substrate.
Test example 4 (measurement of surface free energy of Release surface)
The contact angles of the various droplets on the release surfaces of the release agent layers were measured for the release films obtained in examples and comparative examples, and based on the values, the surface free energy (mJ/m) was determined according to the kitazaki-hata theory 2 ). The contact angle was measured by the horizontal drop method using a contact angle meter (Kyowa Interface Science Co., ltd., product name "DM-701") based on JIS R3257:1999. For the droplets, diiodomethane was used as a "dispersion component", 1-bromonaphthalene was used as a "dipole component", and distilled water was used as a "hydrogen bond component". The results are shown in Table 2.
Test example 5 (measurement of surface roughness of release surface)
The surfaces on the substrate side of the release films obtained in examples and comparative examples were fixed to a glass plate with a double-sided adhesive tape, and then the arithmetic average roughness (Ra; nm) and the maximum protrusion height (Rp; nm) of the release surfaces were measured in PSI mode under a condition of 50 magnification using an optical interference type surface shape observation device (product name "WYKO-1100" manufactured by Vicat Co., ltd.). Further, ra and Rp were measured 10 times, and the average value thereof was used as Ra and Rp of the peeled surface. The results are shown in Table 2.
Test example 6 (evaluation of chargeability at unwinding)
The release films obtained in examples and comparative examples were prepared, and at the same time, films (hereinafter, sometimes referred to as "substrate films") similar to the substrates used in examples and comparative examples were prepared.
In addition, a device having a metallic guide roller was prepared. The device is configured such that a space of 500mm (test piece length) or more is provided between the guide roller and the ground, and the roller shaft is parallel to the ground and is locked without rotating the device. The guide roller is fixed to a side surface of the guide roller by bonding, with a surface of the prepared base film on the side to be coated with the release agent facing the guide roller and a surface opposite to the side to be coated facing the outside.
On the other hand, the release films obtained in examples and comparative examples were cut into a size of 100mm wide and 500mm long, thick paper was attached to one end in the longitudinal direction thereof, and a weight of 300g was attached to the thick paper portion, whereby a test piece for measurement of chargeability was obtained. Then, the test piece was subjected to static elimination using a static elimination brush, and then the test piece was confirmed to be uncharged (-2 kV to +2 kV) using an electrostatic tester (manufactured by KASUGA DENKI, INC., product name "KSD-1000", measurement mode: high).
Next, the test piece, which was confirmed to be uncharged, was set on the guide roller covered with the base material film while holding the end to which the weight was not attached by hand, and the balance was adjusted by hand holding the end of the test piece so that the test piece did not rotate relative to the guide roller.
Then, the end not attached with the weight was pulled by hand toward the floor to be lowered by 300mm, and the side attached with the weight was raised by 300mm. Then, the tension was relaxed to lower the weight-attached side by 300mm and to raise the weight-unattached side by 300mm. The above-described ascent and descent were performed 1 time back and forth with respect to the guide roller, so that the test piece rubbed against the film, and the state of peeling electrification caused by peeling when unreeling the peeled film from the wound product of the peeled film was simulated.
Then, the electrification amount (kV) of the test piece detached from the guide roller was measured using the above-mentioned electrostatic tester. Based on the value of the charge amount, the chargeability at the time of unreeling was evaluated according to the following criteria. The results are shown in Table 2.
A: the absolute value of the charge amount is below 20 kV.
B: the absolute value of the charged amount is more than 20kV and less than 25kV.
C: the absolute value of the charged quantity is larger than 25kV.
Test example 7 (evaluation of slurry coatability)
100 parts by mass of barium titanate powder (BaTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the Sakai Chemical Industry Co., ltd., product name "BT-03", average particle size: 300 nm), 8 parts by mass of a polyvinyl butyral resin (manufactured by Sekisui Chemical co., ltd., product name "S-L") as a binderEC B/K BM-2 ") and 4 parts by mass of dioctyl phthalate (KANTO CHEMICAL co., inc. Manufactured by product name" dioctyl phthalate deer 1 grade ") as a plasticizer were added to 135 parts by mass of a mixed solution of toluene and ethanol (mass ratio 6:4), mixed and dispersed by a ball mill in the presence of zirconium dioxide beads, and then the beads were removed, thereby preparing a ceramic slurry.
The ceramic slurry was applied to the release surfaces of the release films obtained in examples and comparative examples using a die coater to a width of 250mm and a length of 10m, and then dried at 80℃for 1 minute using a dryer.
Thus, a ceramic green sheet having a thickness of 3 μm was formed on the release film.
Next, a fluorescent lamp was irradiated from the release film side onto the laminate of the ceramic green sheet and the release film obtained in the above-described manner, and the shrinkage degree of both end portions of the ceramic green sheet was visually confirmed, and the slurry coatability was evaluated according to the following criteria. The results are shown in Table 2 as slurry coatability when a ceramic green sheet of "thin film (3 μm)" was produced.
A: no shrinkage was confirmed.
B: a slight (less than 0.5 mm) shrinkage was confirmed.
C: shrinkage of 0.5mm or more was confirmed.
The slurry coatability was evaluated in the same manner as described above, except that barium phthalate powder as a material of the ceramic slurry was changed to Sakai Chemical Industry co., ltd. Product name "BT-02" (average particle diameter: 200 nm), and the thickness of the ceramic green sheet to be molded was changed to 1 μm. The results are also shown in Table 2 in terms of slurry coatability when a ceramic green sheet of "extremely thin (1 μm)" is produced.
Test example 8 (measurement of peel force of acrylic adhesive tape)
An acrylic pressure-sensitive adhesive Tape (manufactured by Nitto Denko Corporation, product name "31B Tape") was attached to the release surfaces of the release films obtained in examples and comparative examples, using a roll weighing 2kg back and forth once. In this state, the mixture was left standing at room temperature of 23℃in an atmosphere of 50% humidity for 24 hours. Then, the release film side of the fabricated sample was fixed to the rigid plate using a double-sided adhesive tape. Then, the acrylic adhesive tape was peeled from the release film at a peeling angle of 180℃and a peeling speed of 300 mm/min using a tensile tester, and the force (peeling force; mN/20 mm) required for peeling was measured. The results are shown in Table 2.
Test example 9 (measurement of Release force of ceramic Green sheet)
By the same procedure as in test example 7, a ceramic green sheet was molded "extremely thin (1 μm)" on the release surface of the release film. The obtained laminate of the ceramic green sheet and the release film was allowed to stand at 23℃under 50% RH for 24 hours, and then cut into a 20mm wide laminate, which was used as a measurement sample.
The surface of the ceramic green sheet side of the measurement sample thus prepared was adhered and fixed to a flat plate, and a release film was peeled off from the ceramic green sheet at a peeling angle of 90℃and a peeling rate of 300 mm/min by using a tensile tester (manufactured by Shimadzu Corporation under the product name "AG-IS 500N"), and the force (peeling force; mN/50 mm) required for peeling was measured. The results are shown in Table 2.
Test example 10 (measurement of adhesion between ceramic Green sheets)
The same procedure as in test example 7 was followed to mold a ceramic green sheet "thin film (3 μm)" on the release surface of the release film. The resulting 2 ceramic green sheets were stacked with the green sheet surface once in contact with the release agent layer aligned with the green sheet surface not in contact with the release agent layer, and at 50kg/cm 2 Pressure at 50℃with a pressure (pressure area: 25 cm) 2 ) After that, the state of the interface of 2 ceramic green sheets was visually observed through the release film. Then, the adhesion of the ceramic green sheets to each other was evaluated according to the following criteria.
A: the ceramic green sheets are bonded to each other by 50% or more of the pressing area.
B: the ceramic green sheets are bonded to each other by 30% or more and less than 50% of the pressing area.
C: the ceramic green sheets are adhered to each other at less than 30% of the pressing area.
Test example 11 (evaluation of operability)
The release films obtained in examples and comparative examples were evaluated for operability when they were formed into a roll shape. Specifically, a release film 400mm wide and 2000mm long was wound around an ABS resin core having an outer diameter of 3 inches at a winding tension of 15kg/m and a winding speed of 150 m/min. In this winding step, the slidability of the contacted release films, the degree of air removal at the time of forming into a roll shape, and the difficulty in generating winding deviation of the release films were evaluated according to the following criteria. The results are shown in Table 2.
A: the sliding property of the contacted release films is good, and the air is well discharged when the release films are made into a roll shape, so that the winding deviation of the release films can be prevented.
B: the sliding properties of the contacted release films are slightly poor, and the removal of air is slightly poor when the release films are rolled into a roll shape, and although a slight winding deviation occurs, there is no problem.
C: the sliding properties of the contacted release films are poor, and the removal of air is poor when the release films are rolled up into a roll shape, and a winding deviation is remarkably generated.
[ test example 12] (evaluation of blocking resistance)
The release films obtained in examples and comparative examples were wound into rolls having a width of 400mm and a length of 5000 m. The release film roll was stored at 23.+ -. 5 ℃ and a humidity of 50.+ -. 10% for 30 days. Then, in the case of unreeling the release film from the release film roll, the blocking resistance was evaluated according to the following criteria. The results are shown in Table 2.
A: the adhesion is not generated at all, and the stripping film can be well unreeled.
B: the release film may be unwound, although blocking tends to occur.
C: blocking occurs, resulting in failure to unwind the release film.
Test example 13 (evaluation of Silicone migration Property)
A polyvinyl butyral (PVB) -based binder resin (manufactured by Sekisui Chemical Co., ltd., product name: BL-S) was diluted with a mixed solvent of toluene and ethanol (mixing ratio: 50:50) to obtain a PVB resin solution having a solid content concentration of 20% by mass. The PVB resin solution was uniformly applied to the release surfaces of the release films obtained in examples and comparative examples using a 35 μm coater, and then dried at 60℃for 1 minute using a dryer. Thus, a release film having a layer of PVB resin sheet having a thickness of 4 μm was obtained.
The release film was peeled from the PVB resin sheet, and the silicon atom ratio (atomic%) was calculated from the following formula based on the amounts (XPS count) of silicon atoms (Si), carbon atoms (C), and oxygen atoms (O) measured by X-ray photoelectron spectroscopy (XPS) on the surface of the PVB resin sheet that had been in contact with the release surface of the release film. The results are shown in Table 2.
Silicon atomic ratio (atomic%) = [ (Si element amount)/(C element amount) + (O element amount) + (Si element amount) ] } ] x 100
Further, based on the obtained silicon atomic ratio, the organosilicon migration was evaluated according to the following judgment criteria. The results are shown in Table 2.
A: the silicon atomic ratio is less than 0.5 atomic%.
B: the silicon atomic ratio is 0.5 atomic% or more and less than 1.0 atomic%.
C: the silicon atomic ratio is 1.0 atomic% or more.
When the silicon atomic ratio is 0.5 atomic% or more, pinholes may occur during the application of the slurry or stacking deviation may occur in the step of stacking ceramic green sheets, and the resulting stacked ceramic product may be a product failure.
Details of abbreviations and the like described in the tables are as follows.
[ hydroxyl-containing acrylic resin (B) ]
B1: hydroxyl-containing acrylic resin (DIC CORPORATION, product name "ACRYDIC A-807-BA", hydroxyl value: 22.0-27.0mgKOH/g, tg:65 ℃ C., weight average molecular weight: 65000)
B2: hydroxyl-containing acrylic resin (manufactured by DIC CORPORATION, product name "ACRYDIC WMU-504", hydroxyl value: 53.0-61.0mgKOH/g, tg:60 ℃ C., weight average molecular weight: 9000)
B3: hydroxyl-containing acrylic resin (DIC CORPORATION, product name "ACRYDIC WAU-139", hydroxyl value: 47.0-53.0mgKOH/g, tg:50 ℃ C., weight average molecular weight: 8000)
Polyorganosiloxane (C)
C1: two-terminal methanol modified polydimethylsiloxane
( Shin-Etsu Chemical co., ltd. Product name "KF-6001", weight average molecular weight: 2400 )
C2: two-terminal methanol modified polydimethylsiloxane
( Shin-Etsu Chemical co., ltd. Product name "KF-6002", weight average molecular weight: 4600 )
And C3: two-terminal methanol modified polydimethylsiloxane
( Shin-Etsu Chemical co., ltd. Product name "KF-6003", weight average molecular weight: 8000 )
And C4: side chain methanol modified polydimethylsiloxane
( Shin-Etsu Chemical co., ltd. Product name "X-22-4039", weight average molecular weight: 5300 )
[ alkoxysilane hydrolysis polycondensate (E) ]
E1: colcoat Co,. Ltd. Manufactured under the product name "N-103X"
E2: colcoat Co,. Ltd. Manufactured under the product name "PS-903"
[ polyol Compound (F) ]
F1: ethylene glycol (NIPPON SHOKUBIAI CO., LTD. Manufactured, product name "(Single) ethylene glycol", molecular weight: 62)
F2: propylene glycol (SANKYO CHEMICAL CO., LTD. Manufactured by product name "propylene glycol", molecular weight: 76)
As is clear from table 2, the release film obtained in the examples has low release force to the ceramic green sheet and a small migration amount of the silicone component. The release film obtained in examples also had good properties in terms of slurry coatability, curability of the release agent layer, smoothness of the release surface (surface roughness), handleability, and blocking resistance.
Industrial applicability
The release film for a ceramic green sheet production process of the present invention is suitable for molding a ceramic green sheet.
Claims (12)
1. A release film for a ceramic green sheet production process comprising a base material and a release agent layer provided on one side of the base material, characterized in that,
the release agent layer is formed from a release agent composition containing an amino resin (A), a hydroxyl-containing acrylic resin (B), a polyorganosiloxane (C), and an acid catalyst (D).
2. The release film for a ceramic green sheet production process according to claim 1, wherein the content of the hydroxyl group-containing acrylic resin (B) in the release agent composition is 5 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the amino resin (a).
3. The release film for a ceramic green sheet production process according to claim 1 or 2, wherein the polyorganosiloxane (C) has at least 1 hydroxyl group in 1 molecule.
4. The release film for a ceramic green sheet production process according to any one of claims 1 to 3, wherein the polyorganosiloxane (C) has at least 1 organic group selected from a polyester group, a polyether group and a methanol group.
5. The release film for a ceramic green sheet production process according to any one of claims 1 to 4, wherein the weight average molecular weight of the polyorganosiloxane (C) is 500 to 20000.
6. The release film for a ceramic green sheet production process according to any one of claims 1 to 5, wherein the content of the polyorganosiloxane (C) in the release agent composition is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the total of the amino resin (a) and the hydroxyl group-containing acrylic resin (B).
7. The release film for a ceramic green sheet production process according to any one of claims 1 to 6, wherein the release agent composition contains an alkoxysilane hydrolysis polycondensate (E) having a siloxane bond (Si-O-Si) as a skeleton.
8. The release film for a ceramic green sheet production process according to any one of claims 1 to 7, wherein the acid catalyst (D) comprises at least 1 of a sulfonic acid catalyst and a phosphoric acid catalyst.
9. The release film for a ceramic green sheet production process according to any one of claims 1 to 8, wherein the release agent composition contains a polyol compound (F) having a molecular weight or a weight average molecular weight of 50 to 10000.
10. The release film for a ceramic green sheet production process according to any one of claims 1 to 9, wherein the thickness of the release agent layer is 0.02 μm or more and 0.5 μm or less.
11. The release film for a ceramic green sheet production process according to any one of claims 1 to 10, wherein an arithmetic average roughness (Ra) of a surface of the base material on the release agent layer side is 1nm to 50nm, and a maximum protrusion height (Rp) of the surface is 10nm to 1000 nm.
12. The release film for a ceramic green sheet production process according to any one of claims 1 to 11, wherein an arithmetic average roughness (Ra) of a surface of the base material opposite to the release agent layer is 10nm to 50nm, and a maximum protrusion height (Rp) of the surface is 100nm to 1000 nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021058566 | 2021-03-30 | ||
| JP2021-058566 | 2021-03-30 | ||
| PCT/JP2022/008846 WO2022209547A1 (en) | 2021-03-30 | 2022-03-02 | Release film for use in ceramic green sheet production process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116963887A true CN116963887A (en) | 2023-10-27 |
Family
ID=83458507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280019947.XA Pending CN116963887A (en) | 2021-03-30 | 2022-03-02 | Release film for ceramic green sheet production process |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2022209547A1 (en) |
| CN (1) | CN116963887A (en) |
| TW (1) | TW202304710A (en) |
| WO (1) | WO2022209547A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024185776A1 (en) * | 2023-03-07 | 2024-09-12 | リンテック株式会社 | Release sheet |
| WO2024190267A1 (en) * | 2023-03-10 | 2024-09-19 | 信越化学工業株式会社 | Light-release additive for release sheet, resin composition for release sheet, and release sheet |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3459722B2 (en) * | 1996-03-28 | 2003-10-27 | 帝人株式会社 | Release film |
| JP6395011B2 (en) * | 2016-03-07 | 2018-09-26 | 荒川化学工業株式会社 | Thermosetting release coating composition and release film |
| JP7082890B2 (en) * | 2018-03-23 | 2022-06-09 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| JP6977748B2 (en) * | 2018-08-10 | 2021-12-08 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| KR20210145132A (en) * | 2019-03-26 | 2021-12-01 | 린텍 가부시키가이샤 | release sheet |
| WO2020203654A1 (en) * | 2019-03-29 | 2020-10-08 | リンテック株式会社 | Release film for ceramic green sheet production process |
| JP7205379B2 (en) * | 2019-05-23 | 2023-01-17 | 信越化学工業株式会社 | Release paper or resin composition for release film, release paper and release film |
-
2022
- 2022-03-02 JP JP2023510707A patent/JPWO2022209547A1/ja active Pending
- 2022-03-02 WO PCT/JP2022/008846 patent/WO2022209547A1/en active Application Filing
- 2022-03-02 CN CN202280019947.XA patent/CN116963887A/en active Pending
- 2022-03-10 TW TW111108718A patent/TW202304710A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022209547A1 (en) | 2022-10-06 |
| WO2022209547A1 (en) | 2022-10-06 |
| TW202304710A (en) | 2023-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI701138B (en) | Release film for ceramic green sheet manufacturing process | |
| KR102491714B1 (en) | Releasing film for ceramic green sheet production step | |
| CN110294856B (en) | Release film for ceramic green sheet production process | |
| JP6474327B2 (en) | Release film for ceramic green sheet manufacturing process | |
| CN116963887A (en) | Release film for ceramic green sheet production process | |
| CN113557111B (en) | Release film for ceramic green sheet production process | |
| JP7283810B2 (en) | release film | |
| WO2020050081A1 (en) | Mold release film for ceramic green sheet production | |
| KR20170096963A (en) | Release film for ceramic green sheet manufacturing process and method for manufacturing the same | |
| JP6699814B1 (en) | Release film for manufacturing ceramic green sheets | |
| KR20150132229A (en) | Release film for green sheet manufacturing, and method for manufacturing release film for green sheet manufacturing | |
| JP7385817B2 (en) | Release film for ceramic green sheet production | |
| TWI468290B (en) | Release film | |
| KR20170096966A (en) | Release film for ceramic green sheet manufacturing process and method for manufacturing the same | |
| JP2020026135A (en) | Release film for ceramic green sheet manufacturing | |
| JP3962161B2 (en) | Carrier sheet for manufacturing ceramic capacitors | |
| TW202248366A (en) | Release film for use in ceramic green sheet production process | |
| JP2023142931A (en) | release film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |