WO2020203563A1 - Etching liquid for liquid crystal polymer and method for etching liquid crystal polymer - Google Patents
Etching liquid for liquid crystal polymer and method for etching liquid crystal polymer Download PDFInfo
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- WO2020203563A1 WO2020203563A1 PCT/JP2020/013370 JP2020013370W WO2020203563A1 WO 2020203563 A1 WO2020203563 A1 WO 2020203563A1 JP 2020013370 W JP2020013370 W JP 2020013370W WO 2020203563 A1 WO2020203563 A1 WO 2020203563A1
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- etching
- crystal polymer
- acid
- compound
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 241
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 176
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- OYPCNAORHLIPPO-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-dicarboxylic acid Chemical group C1=CC(C(=O)O)(C(O)=O)CC=C1C1=CC=CC=C1 OYPCNAORHLIPPO-UHFFFAOYSA-N 0.000 description 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
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- 229930185605 Bisphenol Natural products 0.000 description 1
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- 239000004386 Erythritol Substances 0.000 description 1
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- 101000667666 Homo sapiens E3 ubiquitin-protein ligase RNF170 Proteins 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 150000004984 aromatic diamines Chemical class 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 description 1
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- KKZJGLLVHKMTCM-UHFFFAOYSA-N mitoxantrone Chemical compound O=C1C2=C(O)C=CC(O)=C2C(=O)C2=C1C(NCCNCCO)=CC=C2NCCNCCO KKZJGLLVHKMTCM-UHFFFAOYSA-N 0.000 description 1
- 229960001156 mitoxantrone Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
Definitions
- a novel etching solution suitable for a liquid crystal polymer an etching method using the etching solution, and the like.
- an etching solution for a liquid crystal polymer and an etching method for the liquid crystal polymer in which the shape of the liquid crystal polymer after etching is close to the design shape and etching can be performed with high in-plane uniformity.
- a method for etching a liquid crystal polymer in which peeling of the adhesive surface between the metal layer and the liquid crystal polymer does not occur when the liquid crystal polymer adhered to the metal layer is etched.
- the polyvalent carboxylic acid (polyvalent carboxylic acid compound) used in the etching solution of the present invention also includes derivatives (for example, salts) and hydrates of the polyvalent carboxylic acid.
- the polyvalent carboxylic acid may be either an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid, and typically, an aliphatic polyvalent carboxylic acid may be preferably used.
- Such an aliphatic polyvalent carboxylic acid may be either a saturated fatty acid or an unsaturated fatty acid.
- the hydroxy acid may be either an aliphatic hydroxy acid or an aromatic hydroxy acid, and the aliphatic hydroxy acid may be either a saturated or unsaturated fatty acid.
- the number of hydroxyl groups may be 1 or more, and may be, for example, 1 to 10 (for example, 1 to 5).
- the number of carboxyl groups may be 1 or more, and may be, for example, 1 to 10 (for example, 1 to 5).
- aromatic dicarboxylic acid examples include an arenedicarboxylic acid [for example, benzenedicarboxylic acid (for example, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, etc.), naphthalenedicarboxylic acid (for example, 2,6-naphthalene).
- C 6-20 areane dicarboxylic acid such as (dicarboxylic acid)], dicarboxybiphenyl (4,4-dicarboxybiphenyl, etc.), di (carboxyphenyl) ether, mono or polyalkylene glycol di (carboxyphenyl) ether, etc.], etc. Can be mentioned.
- aromatic components include substituents ⁇ for example, halogen atoms, aliphatic groups [for example, aliphatic hydrocarbon groups such as alkyl groups (for example, C 1-4 alkyl groups)], aromatic groups [for example, for example. It may have an aromatic hydrocarbon group such as an aryl group (for example, a phenyl group)] and the like.
- the metal forming the metal layer may be, for example, gold, silver, copper, iron, nickel, aluminum, or an alloy metal thereof.
- the thickness of the metal layer can be appropriately set as needed, and is, for example, preferably 5 to 50 ⁇ m, more preferably 8 to 35 ⁇ m.
- photocrosslinkable resin compositions are "Photopolymer Handbook” (edited by Photopolymer Association, published in 1989, published by Industrial Research Association Co., Ltd.) and "Photopolymer Technology” (edited by Ao Yamamoto and Mototaro Nagamatsu, 1988). It is described in (published by Nikkan Kogyo Shimbun), etc., and a desired photocrosslinkable resin composition can be used.
- the thickness of the photocrosslinkable resin layer is preferably 15 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
- a stripping solution suitable for the photocrosslinkable resin layer to be used is used, and the dry film resist pattern is removed by spraying from the vertical direction of the substrate toward the substrate surface.
- the stripping solution generally 2 to 4% by mass of an aqueous sodium hydroxide solution is used, and more preferably 3% by mass of an aqueous sodium hydroxide solution is used.
- the etching process methods such as immersion treatment, paddle treatment, spray treatment, brushing, and scraping can be used.
- immersion treatment is preferable from the viewpoint of the uniformity of the etching treatment.
- the temperature of the etching solution is preferably 40 to 100 ° C.
- the optimum temperature varies depending on the type of the liquid crystal polymer, the thickness of the film containing the liquid crystal polymer, the shape of the pattern obtained by the etching method of the liquid crystal polymer, etc., but the temperature of the etching solution is more preferably 50 to 95 ° C. Yes, more preferably 60 to 90 ° C, and particularly preferably 70 ° C or higher.
- the pretreatment step methods such as immersion treatment, paddle treatment, spray treatment, brushing, and scraping can be used.
- immersion treatment is preferable from the viewpoint of the uniformity of the pretreatment.
- the pretreatment liquid of the present invention is preferably used at 50 ° C. or higher.
- the temperature of the pretreatment liquid is more preferably 60 ° C. or higher.
- the etching resist is a dry film resist pattern, the swelling of the dry film resist pattern becomes large and an adverse effect on the etching treatment may be observed. Therefore, the temperature of the pretreatment liquid is preferably 90 ° C. or lower.
- the temperature of the etching solution-the temperature of the first washing solution is less than 25 ° C, and the temperature of the first washing solution-the temperature of the second washing solution is less than 25 ° C, so that the liquid crystal polymer adhered to the metal layer is etched.
- the liquid crystal polymer can be etched without causing peeling of the adhesive surface between the metal layer and the liquid crystal polymer.
- peeling of the adhesive surface between the metal layer and the liquid crystal polymer may occur at this point.
- the temperature of the etching solution-the temperature of the first washing liquid is less than 25 ° C
- the temperature of the first washing liquid-the temperature of the second washing liquid is 25 ° C or more, the metal layer and the liquid crystal polymer are adhered. Surface peeling may occur.
- a dry film resist (dry film resist) as a mask under the conditions of a temperature of 100 ° C., a speed of 0.5 m / min, and a pressure of 0.5 MPa using a roll laminator on the surface of the liquid crystal polymer of the liquid crystal polymer substrate with copper foil.
- DFR thickness: 30 ⁇ m, manufactured by Asahi Kasei Corporation, AQ3058) was laminated. Then, it was patterned by exposure and developed with a 1% by mass aqueous sodium carbonate solution to form a dry film resist pattern having an aperture pattern. After forming the aperture pattern, the dry film resist pattern was exposed to 1000 mJ.
- the time required to etch to the bottom surface of the opening was evaluated as the "etching time".
- the etching time is preferably 50 minutes or less, more preferably 40 minutes or less, and further preferably 30 minutes or less.
- the reproducibility of the shape of the opening of the liquid crystal polymer after etching with respect to the shape of the opening of the dry film resist pattern was evaluated as the "opening shape”. The results are shown in Table 7.
- ⁇ The shape does not collapse.
- ⁇ (Good): There is a slight collapse of the shape.
- ⁇ (Average): The shape may be deformed, but this is not a problem.
- ⁇ (Poor): The shape collapses, which causes a problem.
- thermoplastic liquid crystal polymer and the metal foil were heat-bonded so that the copper foil and the liquid crystal polymer were in contact with each other, the release layer and the carrier foil were peeled off, and the liquid crystal polymer base material with the copper foil (the metal layer was adhered). Liquid crystal polymer) was obtained.
- opening diameter and "in-plane uniformity” were evaluated.
- opening diameter the opening diameters of 60 openings in the plane were measured, and an average value was calculated. Then, the amount of change in the opening diameter every 30 days was determined as compared with that before the start of running, and evaluated according to the following evaluation criteria.
- the etching solution for a liquid crystal polymer of the present invention can be used for roughening a liquid crystal polymer film, and is a resin composition layer containing a liquid crystal polymer and having excellent heat resistance, dielectric properties, mechanical strength, chemical resistance, and the like. Can also be etched. For example, it can be applied to fine processing of insulating resin in a multi-layer build-up wiring board, a module board with built-in components, a flip chip package board, a motherboard for mounting a package board, and the like.
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Abstract
Description
本発明の他の課題は、エッチング後の液晶ポリマーの形状が設計形状に近く、高い面内均一性でエッチングできる液晶ポリマー用エッチング液及び液晶ポリマーのエッチング方法を提供することである。
本発明のさらに他の課題は、エッチング後の液晶ポリマーの形状が、設計通りの形状となり、かつ迅速にエッチングできる生産性の高い液晶ポリマーのエッチング方法を提供することである。
本発明の別の課題は、金属層に接着された液晶ポリマーをエッチングした場合に、金属層と液晶ポリマーの接着面の剥がれが発生しない液晶ポリマーのエッチング方法を提供することである。 An object of the present invention is to provide a novel etching solution suitable for a liquid crystal polymer, an etching method using the etching solution, and the like.
Another object of the present invention is to provide an etching solution for a liquid crystal polymer and an etching method for the liquid crystal polymer, in which the shape of the liquid crystal polymer after etching is close to the design shape and etching can be performed with high in-plane uniformity.
Still another object of the present invention is to provide a highly productive etching method for a liquid crystal polymer, in which the shape of the liquid crystal polymer after etching becomes the shape as designed and the etching can be performed quickly.
Another object of the present invention is to provide a method for etching a liquid crystal polymer in which peeling of the adhesive surface between the metal layer and the liquid crystal polymer does not occur when the liquid crystal polymer adhered to the metal layer is etched.
すなわち、本発明は、下記の発明等に関する。 As a result of diligent studies to solve the above problems, the present inventors can obtain a new etching solution by combining specific components (further, combining them at a predetermined ratio), and such etching. The liquid is suitable for etching the liquid crystal polymer, in particular, the liquid crystal polymer can be etched efficiently (for example, the shape of the liquid crystal polymer after etching can be made close to the design shape, and the in-plane uniformity is high. Etching) and the like were found, and further studies were carried out to complete the present invention.
That is, the present invention relates to the following inventions and the like.
液晶ポリマー用エッチング液において、該エッチング液が、第1成分としての5~45質量%のアルカリ金属水酸化物及び第2成分としての5~80質量%の、分子量が70以上であるアルカノールアミン化合物を含有することを特徴とする液晶ポリマー用エッチング液。 <1>
In the etching solution for liquid crystal polymer, the etching solution contains 5 to 45% by mass of an alkali metal hydroxide as a first component and 5 to 80% by mass as a second component, and an alkanolamine compound having a molecular weight of 70 or more. An etching solution for a liquid crystal polymer, which comprises.
さらに、1~60質量%の第3成分を含有し、第3成分が、アルコール化合物及びカルボン酸化合物から選択された少なくとも1種を含有することを特徴とする<1>に記載の液晶ポリマー用エッチング液。 <2>
The liquid crystal polymer according to <1>, further comprising 1 to 60% by mass of a third component, wherein the third component contains at least one selected from an alcohol compound and a carboxylic acid compound. Etching solution.
第3成分が、ポリオール化合物、多価カルボン酸化合物及びヒドロキシ酸化合物から選択された少なくとも1種を含有する<2>に記載の液晶ポリマー用エッチング液。 <3>
The etching solution for a liquid crystal polymer according to <2>, wherein the third component contains at least one selected from a polyol compound, a polyvalent carboxylic acid compound, and a hydroxy acid compound.
第3成分がポリオール化合物を含有する<2>又は<3>に記載のエッチング液。 <4>
The etching solution according to <2> or <3>, wherein the third component contains a polyol compound.
上記ポリオール化合物の分子量が80以上200以下である<3>又は<4>に記載のエッチング液。 <5>
The etching solution according to <3> or <4>, wherein the polyol compound has a molecular weight of 80 or more and 200 or less.
上記ポリオール化合物が3つ以上のヒドロキシル基を有する<3>~<5>のいずれかに記載のエッチング液。 <6>
The etching solution according to any one of <3> to <5>, wherein the polyol compound has three or more hydroxyl groups.
上記ポリオール化合物が、グリセリンを含有する<3>~<6>のいずれかに記載のエッチング液。 <7>
The etching solution according to any one of <3> to <6>, wherein the polyol compound contains glycerin.
第3成分が、多価カルボン酸化合物を含有する<2>~<7>のいずれかに記載のエッチング液。 <8>
The etching solution according to any one of <2> to <7>, wherein the third component contains a polyvalent carboxylic acid compound.
第3成分が、ヒドロキシ酸化合物を含有する<2>~<8>のいずれかに記載のエッチング液。 <9>
The etching solution according to any one of <2> to <8>, wherein the third component contains a hydroxy acid compound.
<1>~<9>のいずれかに記載のエッチング液を用いて、液晶ポリマーをエッチング処理するエッチング工程を有することを特徴とする液晶ポリマーのエッチング方法。 <10>
A method for etching a liquid crystal polymer, which comprises an etching step of etching a liquid crystal polymer using the etching solution according to any one of <1> to <9>.
エッチング工程前に、50~100質量%のアルカノールアミン化合物を含有する前処理液を液晶ポリマーに接触させる前処理工程をさらに有する<10>に記載の液晶ポリマーのエッチング方法。 <11>
The method for etching a liquid crystal polymer according to <10>, further comprising a pretreatment step of bringing a pretreatment liquid containing 50 to 100% by mass of an alkanolamine compound into contact with the liquid crystal polymer before the etching step.
前処理液の温度が50℃以上である<11>記載の液晶ポリマーのエッチング方法。 <12>
The method for etching a liquid crystal polymer according to <11>, wherein the temperature of the pretreatment liquid is 50 ° C. or higher.
エッチング工程後に、水洗液(水洗水等)を用いた水洗工程をさらに有する<10>~<12>のいずれかに記載の液晶ポリマーのエッチング方法。 <13>
The method for etching a liquid crystal polymer according to any one of <10> to <12>, further comprising a water washing step using a water washing liquid (water washing water or the like) after the etching step.
水洗工程が、第一水洗液による第一水洗工程及び第二水洗液による第二水洗工程をこの順に含み、エッチング液の温度-第一水洗液の温度が25℃未満であり、第一水洗液の温度-第二水洗液の温度が25℃未満である<13>に記載の液晶ポリマーのエッチング方法。 <14>
The water washing step includes the first water washing step by the first water washing liquid and the second water washing step by the second water washing liquid in this order, and the temperature of the etching solution-the temperature of the first water washing liquid is less than 25 ° C. -The method for etching a liquid crystal polymer according to <13>, wherein the temperature of the second washing liquid is less than 25 ° C.
水洗液(水洗水等)[水洗工程(例えば、第一水洗工程及び/又は第二水洗工程)で使用した水洗液(水洗水等)]をエッチング液に補充する<13>又は<14>に記載の液晶ポリマーのエッチング方法。 <15>
In <13> or <14>, the etching solution is replenished with a washing solution (washing water, etc.) [water washing solution (washing water, etc.) used in the washing step (for example, the first washing step and / or the second washing step)]. The method for etching a liquid crystal polymer according to the above method.
本発明の他の態様では、エッチング後の液晶ポリマーの形状が設計形状に近く、高い面内均一性でエッチングできる液晶ポリマー用エッチング液及び液晶ポリマーのエッチング方法を提供することができる。
本発明のさらに他の態様では、エッチング後の液晶ポリマーの形状が、設計通りの形状となり、かつ迅速にエッチングできる生産性の高い液晶ポリマーのエッチング方法を提供することができる。
本発明の別の態様では、金属層に接着された液晶ポリマーをエッチングした場合に、金属層と液晶ポリマーの接着面の剥がれが発生しない液晶ポリマーのエッチング方法を提供することができる。 According to the present invention, it is possible to provide a novel etching solution suitable for a liquid crystal polymer, an etching method using the etching solution, and the like.
In another aspect of the present invention, it is possible to provide an etching solution for a liquid crystal polymer and an etching method for the liquid crystal polymer, in which the shape of the liquid crystal polymer after etching is close to the design shape and etching can be performed with high in-plane uniformity.
In still another aspect of the present invention, it is possible to provide a highly productive etching method for a liquid crystal polymer in which the shape of the liquid crystal polymer after etching becomes the shape as designed and the etching can be performed quickly.
In another aspect of the present invention, it is possible to provide a method for etching a liquid crystal polymer in which peeling of the adhesive surface between the metal layer and the liquid crystal polymer does not occur when the liquid crystal polymer adhered to the metal layer is etched.
本発明のエッチング液は、液晶ポリマー用エッチング液(液晶ポリマーのエッチング液、液晶ポリマーをエッチングするための液)である。 <Etching liquid>
The etching solution of the present invention is an etching solution for a liquid crystal polymer (an etching solution for a liquid crystal polymer, a liquid for etching a liquid crystal polymer).
また、第3成分の含有量は、第3成分を構成する成分にもよるが、エッチング液において、例えば、80質量%以下、70質量%以下、60質量%以下、50質量%以下、40質量%以下等であってもよい。
特に、本発明のエッチング液は、第3成分の含有量が1~60質量%であることが好ましい。また、第三成分としては、ポリオール化合物、多価カルボン酸化合物及び/又はヒドロキシ酸化合物を含有してもよい。本発明のエッチング液が、このような第3成分(例えば、ポリオール化合物、多価カルボン酸化合物及び/又はヒドロキシ酸化合物)を含有することによって、液晶ポリマーをより均一に溶解することができる。 The content of the third component (the total content when two or more are combined) depends on the components constituting the third component, but in the etching solution, for example, 0.1% by mass or more and 0.5% by mass. It may be 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 3 mass% or more, 5 mass% or more, 8 mass% or more, 10 mass% or more, and the like.
The content of the third component depends on the components constituting the third component, but in the etching solution, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass. It may be less than or equal to%.
In particular, the etching solution of the present invention preferably contains a third component of 1 to 60% by mass. Further, as the third component, a polyol compound, a polyvalent carboxylic acid compound and / or a hydroxy acid compound may be contained. When the etching solution of the present invention contains such a third component (for example, a polyol compound, a polyvalent carboxylic acid compound and / or a hydroxy acid compound), the liquid crystal polymer can be dissolved more uniformly.
アルコール化合物[アルカノールアミン化合物(エタノールアミン化合物)ではないアルコール化合物]としては、モノアルコール化合物[例えば、アルカノール(例えば、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール等)、脂環式モノオール(例えば、シクロヘキサノール)等の非芳香族モノオール化合物(脂肪族モノオール)等]、ポリオール化合物等が含まれる。
アルコール化合物は、1種類を単独で使用しても良いし、2種類以上を組み合わせて使用しても良い。 [Alcohol compound]
Examples of the alcohol compound [alcohol compound that is not an alkanolamine compound (ethanolamine compound)] include monoalcohol compounds [for example, alkanol (for example, ethanol, propanol, butanol, pentanol, hexanol, etc.), and alicyclic monool (for example,). Non-aromatic monool compounds such as cyclohexanol) (aliphatic monool) and the like], polyol compounds and the like are included.
One type of alcohol compound may be used alone, or two or more types may be used in combination.
なお、非芳香族アルコール化合物は、飽和及び不飽和化合物のいずれであってもよい。 Further, the alcohol compound may be an aromatic alcohol compound [aromatic alcohol compound described later (for example, benzyl alcohol, phenoxyethanol, etc.), etc.], and a non-aromatic alcohol compound (non-aromatic monool compound, non-aromatic). It may be a polyol compound) or may contain both of them.
The non-aromatic alcohol compound may be either a saturated compound or an unsaturated compound.
カルボン酸化合物(単に「カルボン酸」という場合がある)としては、カルボン酸、カルボン酸誘導体(例えば、カルボン酸塩)等が含まれる。なお、カルボン酸化合物(カルボン酸、カルボン酸塩等)は、水和物等であってもよい。 [Carboxylic acid compound]
Carboxylic acid compounds (sometimes simply referred to as "carboxylic acids") include carboxylic acids, carboxylic acid derivatives (eg, carboxylic acid salts) and the like. The carboxylic acid compound (carboxylic acid, carboxylic acid salt, etc.) may be a hydrate or the like.
本発明のエッチング液に使用されるヒドロキシ酸(ヒドロキシ酸化合物)には、上述のように、ヒドロキシ酸の誘導体(例えば、塩等)も含まれる。また、上述のように、ヒドロキシ酸やその塩等は水和物であってもよい。 (Hydroxy acid compound)
As described above, the hydroxy acid (hydroxy acid compound) used in the etching solution of the present invention also includes a derivative of the hydroxy acid (for example, a salt or the like). Further, as described above, the hydroxy acid, its salt and the like may be a hydrate.
ヒドロキシ酸において、カルボキシル基の数は、1以上であればよく、例えば、1~10(例えば、1~5)等であってもよい。 In the hydroxy acid, the number of hydroxyl groups may be 1 or more, and may be, for example, 1 to 10 (for example, 1 to 5).
In the hydroxy acid, the number of carboxyl groups may be 1 or more, and may be, for example, 1 to 10 (for example, 1 to 5).
本発明に使用される液晶ポリマーとしては、サーモトロピック液晶ポリマー等の各種の液晶ポリマーを用いることができる。このような液晶ポリマーとしては、例えば、液晶ポリエステル等が挙げられる。 <Liquid polymer>
As the liquid crystal polymer used in the present invention, various liquid crystal polymers such as a thermotropic liquid crystal polymer can be used. Examples of such a liquid crystal polymer include liquid crystal polyester and the like.
本発明のエッチング方法は、本発明のエッチング液を用いて液晶ポリマーをエッチング処理する工程を有する。 <Etching method>
The etching method of the present invention includes a step of etching a liquid crystal polymer using the etching solution of the present invention.
[エッチング]
p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸の共重合物(モル比:73/27)で、融点が280℃、厚さが20μmである熱可塑性液晶ポリマーフィルム(面積:横500mm×500mm、厚み:20μm)と、厚み3μmの銅箔と剥離層とキャリア箔とがこの順に積層された剥離可能な金属箔を準備し、銅箔と上記液晶ポリマーフィルム(液晶ポリマー)が接触するように両者を熱圧着させた後、剥離層及びキャリア箔を剥離して、銅箔付き液晶ポリマーを得た。銅箔付き液晶ポリマー基材の液晶ポリマーフィルム面を粗面化し、その上にロールラミネーターを用いて、温度100℃、速度0.5m/min、圧力0.5MPaの条件で、マスクとしてドライフィルムレジスト(DFR、厚み:30μm、旭化成社製、AQ3058)をラミネートした。その後、露光によりパターニングし、炭酸ナトリウム水溶液にて現像し、マスクに開口パターンを形成した。開口パターンを形成した後、マスクに対して1000mJの露光処理を行った。 [Examples 1-1 to 3-16]
[etching]
A thermoplastic liquid crystal polymer film (area: width 500 mm ×) which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27), has a melting point of 280 ° C. and a thickness of 20 μm. Prepare a peelable metal foil in which a copper foil having a thickness of 3 μm, a release layer, and a carrier foil are laminated in this order (500 mm, thickness: 20 μm) so that the copper foil and the liquid crystal polymer film (liquid crystal polymer) come into contact with each other. After heat-bonding both of them, the release layer and the carrier foil were peeled off to obtain a liquid crystal polymer with a copper foil. A dry film resist is used as a mask under the conditions of a temperature of 100 ° C., a speed of 0.5 m / min, and a pressure of 0.5 MPa by roughening the liquid crystal polymer film surface of the liquid crystal polymer base material with a copper foil and using a roll laminator on the surface. (DFR, thickness: 30 μm, manufactured by Asahi Kasei Corporation, AQ3058) was laminated. Then, it was patterned by exposure and developed with an aqueous sodium carbonate solution to form an opening pattern on the mask. After forming the aperture pattern, the mask was exposed to 1000 mJ.
開口部において、液晶ポリマー(液晶ポリマーフィルム)の除去が確実にできているかを「樹脂残渣」で評価した。また、液晶ポリマーの開口形状における変形を「アンダーカット」で評価した。さらに、「面内の均一性」の評価として、目標となる開口径(目標開口径)が同一であり、面内にある60か所の開口部を観察し、開口径が最大となる開口の開口径を「最大値」、開口径が最小となる開口の開口径を「最小値」とし、「(最大値-最小値)/開口目標値×100」で変動値(%)を求め、「面内均一性」を評価した。また、エッチング液のランニング性を評価するために、50シート/1日を、延べ30日間(約1.5ヶ月間)使用した後、同様の試験を行った。結果を表1~表6に示す。各評価の基準を下記に示す。 [Examples 1-1 to 3-16]
It was evaluated by "resin residue" whether or not the liquid crystal polymer (liquid crystal polymer film) was surely removed at the opening. In addition, the deformation of the liquid crystal polymer in the opening shape was evaluated by "undercut". Furthermore, as an evaluation of "in-plane uniformity", the target opening diameter (target opening diameter) is the same, 60 openings in the plane are observed, and the opening with the maximum opening diameter is observed. The opening diameter is set to the "maximum value", the opening diameter of the opening that minimizes the opening diameter is set to the "minimum value", and the fluctuation value (%) is obtained by "(maximum value-minimum value) / opening target value x 100". "In-plane uniformity" was evaluated. Further, in order to evaluate the running property of the etching solution, 50 sheets / day were used for a total of 30 days (about 1.5 months), and then the same test was performed. The results are shown in Tables 1 to 6. The criteria for each evaluation are shown below.
○(Excellent):液晶ポリマーが残っていない。
○△(Good):極微量の液晶ポリマーが残っているが、問題とならない。
△(Average):微量の液晶ポリマーが残っているが、プラズマ洗浄処理で容易に除去できる。
×(Poor):多くの液晶ポリマーが残り、プラズマ洗浄処理で容易に除去できない。 "Resin residue"
◯ (Excellent): No liquid crystal polymer remains.
○ Δ (Good): A very small amount of liquid crystal polymer remains, but this is not a problem.
Δ (Average): A small amount of liquid crystal polymer remains, but it can be easily removed by plasma cleaning treatment.
X (Poor): Many liquid crystal polymers remain and cannot be easily removed by plasma cleaning treatment.
○(Excellent):アンダーカットが見られない。
○△(Good):極めて小さいアンダーカットが見られる。
△(Average):小さいアンダーカットが見られるが、問題とならない。
×(Poor):大きいアンダーカットが見られ、問題となる。 "undercut"
○ (Excellent): No undercut is seen.
○ △ (Good): Very small undercut is seen.
Δ (Average): A small undercut is seen, but this is not a problem.
× (Poor): A large undercut is seen, which is a problem.
○(Excellent):非常に均一性が高い。変動値が3%未満。
○△(Good):均一性が高い。変動値が3%以上5%未満。
△(Average):均一。変動値が5%以上6%未満。
×(Poor):不均一。変動値が6%以上。 (In-plane uniformity / running property: evaluated by etching solution before and after running)
◯ (Excellent): Very high uniformity. The fluctuation value is less than 3%.
○ △ (Good): High uniformity. The fluctuation value is 3% or more and less than 5%.
Δ (Average): Uniform. The fluctuation value is 5% or more and less than 6%.
× (Poor): Non-uniform. The fluctuation value is 6% or more.
PHB(p-ヒドロキシ安息香酸)と6-ヒドロキシ-2-ナフトエ酸の共重合物(モル比:73/27)で、融点が280℃、厚さが20μmである熱可塑性液晶ポリマーフィルム(面積:横500mm×500mm、厚み:20μm)と、厚み3μmの銅箔と剥離層とキャリア箔とがこの順に積層された剥離可能な金属箔を準備し、銅箔と上記液晶ポリマーが接触するように両者を熱圧着させた後、剥離層及びキャリア箔を剥離して、銅箔付き液晶ポリマーを得た。銅箔付き液晶ポリマー基材の液晶ポリマー面を粗面化し、その上にロールラミネーターを用いて、温度100℃、速度0.5m/min、圧力0.5MPaの条件で、マスクとしてドライフィルムレジスト(DFR、厚み:30μm、旭化成社製、AQ3058)をラミネートした。その後、露光によりパターニングし、1質量%の炭酸ナトリウム水溶液にて現像し、開口パターンを有するドライフィルムレジストパターンを形成した。開口パターンを形成した後、ドライフィルムレジストパターンに対して1000mJの露光処理を行った。 [Examples 4-1 to 4-19]
A thermoplastic liquid crystal polymer film (area:) which is a copolymer of PHB (p-hydroxybenzoic acid) and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27), has a melting point of 280 ° C. and a thickness of 20 μm. Prepare a peelable metal foil in which a copper foil having a width of 500 mm × 500 mm and a thickness of 3 μm, a peeling layer, and a carrier foil are laminated in this order, and both so that the copper foil and the liquid crystal polymer come into contact with each other. Was heat-bonded, and then the release layer and the carrier foil were peeled off to obtain a liquid crystal polymer with a copper foil. A dry film resist (dry film resist) as a mask under the conditions of a temperature of 100 ° C., a speed of 0.5 m / min, and a pressure of 0.5 MPa using a roll laminator on the surface of the liquid crystal polymer of the liquid crystal polymer substrate with copper foil. DFR, thickness: 30 μm, manufactured by Asahi Kasei Corporation, AQ3058) was laminated. Then, it was patterned by exposure and developed with a 1% by mass aqueous sodium carbonate solution to form a dry film resist pattern having an aperture pattern. After forming the aperture pattern, the dry film resist pattern was exposed to 1000 mJ.
○(Excellent):形状の崩れが無い。
○△(Good):微小な形状の崩れがある。
△(Average):形状の崩れはあるが、問題とならない。
×(Poor):形状が崩れ、問題となる。 The evaluation criteria for the opening shape are shown below.
◯ (Excellent): The shape does not collapse.
○ △ (Good): There is a slight collapse of the shape.
Δ (Average): The shape may be deformed, but this is not a problem.
× (Poor): The shape collapses, which causes a problem.
[エッチング]
PHBと6-ヒドロキシ-2-ナフトエ酸の共重合物(モル比:73/27)で、融点が280℃、厚さが20μmである熱可塑性液晶ポリマーフィルム(面積:横500mm×500mm、厚み:20μm)と、厚み18μmの銅箔を準備し、銅箔と上記液晶ポリマーが接触するように両者を熱圧着させて、銅箔付き液晶ポリマー基材を得た。 [Examples 5-1 to 5-36]
[etching]
A thermoplastic liquid crystal polymer film (area: width 500 mm × 500 mm, thickness: 500 mm × 500 mm, thickness: 280 ° C., thickness 20 μm), which is a copolymer of PHB and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27). 20 μm) and a copper foil having a thickness of 18 μm were prepared, and the copper foil and the liquid crystal polymer were heat-bonded so as to come into contact with each other to obtain a liquid crystal polymer substrate with a copper foil.
各例で得られたテスト材を、アクリル樹脂で包埋後、切断、研磨して断面観察用の試料片を作製した。光学顕微鏡により、金属層に接着された液晶ポリマーの断面を観察し、液晶ポリマーと金属層の接着面に剥がれが発生しているか否かを確認した。結果を表9に示す。 (Presence or absence of peeling on the adhesive surface between the liquid crystal polymer and the metal layer)
The test material obtained in each example was embedded in an acrylic resin, cut and polished to prepare a sample piece for cross-section observation. The cross section of the liquid crystal polymer adhered to the metal layer was observed with an optical microscope, and it was confirmed whether or not the adhesive surface between the liquid crystal polymer and the metal layer had peeled off. The results are shown in Table 9.
[エッチング]
p-ヒドロキシ安息香酸と6-ヒドロキシ-2-ナフトエ酸の共重合物(モル比:73/27)で、融点が280℃、厚さが20μmである熱可塑性液晶ポリマー(面積:横500mm×500mm、厚み:20μm)と、厚み3μmの銅箔と剥離層とキャリア箔とがこの順に積層された金属箔を準備した。銅箔と上記液晶ポリマーが接触するように、熱可塑性液晶ポリマーと金属箔とを熱圧着させた後、剥離層及びキャリア箔を剥離して、銅箔付き液晶ポリマー基材(金属層が接着した液晶ポリマー)を得た。 [Example 6-1 to Example 6-28]
[etching]
A copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27), a thermoplastic liquid crystal polymer having a melting point of 280 ° C. and a thickness of 20 μm (area: width 500 mm × 500 mm). , Thickness: 20 μm), and a metal foil in which a copper foil having a thickness of 3 μm, a release layer, and a carrier foil were laminated in this order was prepared. After the thermoplastic liquid crystal polymer and the metal foil were heat-bonded so that the copper foil and the liquid crystal polymer were in contact with each other, the release layer and the carrier foil were peeled off, and the liquid crystal polymer base material with the copper foil (the metal layer was adhered). Liquid crystal polymer) was obtained.
(I)例6-1、5、9、13、17、21及び25では、処理した面積に比例して、100ml/m2のエッチング液を補充する。液面を一定にするために液を補充する液面補充は行わない。 [Etching solution replenishment method: running conditions]
(I) In Examples 6-1 and 5, 9, 13, 17, 21 and 25, 100 ml / m 2 of the etching solution is replenished in proportion to the treated area. Liquid level is replenished to keep the liquid level constant. Liquid level replenishment is not performed.
○(Good):変化量が4%未満
△(Average):変化量が4%以上7%未満
×(Poor):変化量7%以上 (Running performance evaluation: opening diameter)
○ (Good): Change amount is less than 4% △ (Average): Change amount is 4% or more and less than 7% × (Poor): Change amount is 7% or more
○(Good):非常に均一性が高い。変化量が5%未満。
△(Average):均一。変化量が5%以上6%未満。
×(Poor):均一とは言えない。変化量が6%以上。 (Running performance evaluation: In-plane uniformity)
◯ (Good): Very high uniformity. The amount of change is less than 5%.
Δ (Average): Uniform. The amount of change is 5% or more and less than 6%.
× (Poor): Not uniform. The amount of change is 6% or more.
Claims (15)
- 液晶ポリマー用エッチング液において、該エッチング液が、第1成分としての5~45質量%のアルカリ金属水酸化物及び第2成分としての5~80質量%の、分子量が70以上であるアルカノールアミン化合物を含有することを特徴とする液晶ポリマー用エッチング液。 In the etching solution for liquid crystal polymer, the etching solution contains 5 to 45% by mass of an alkali metal hydroxide as a first component and 5 to 80% by mass as a second component, and an alkanolamine compound having a molecular weight of 70 or more. An etching solution for a liquid crystal polymer, which comprises.
- さらに、1~60質量%の第3成分を含有し、第3成分が、アルコール化合物及びカルボン酸化合物から選択された少なくとも1種を含有することを特徴とする請求項1に記載の液晶ポリマー用エッチング液。 The liquid crystal polymer according to claim 1, further comprising a third component of 1 to 60% by mass, and the third component contains at least one selected from an alcohol compound and a carboxylic acid compound. Etching solution.
- 第3成分が、ポリオール化合物、多価カルボン酸化合物及びヒドロキシ酸化合物から選択された少なくとも1種を含有する請求項2に記載の液晶ポリマー用エッチング液。 The etching solution for a liquid crystal polymer according to claim 2, wherein the third component contains at least one selected from a polyol compound, a polyvalent carboxylic acid compound, and a hydroxy acid compound.
- 第3成分がポリオール化合物を含有する請求項2又は請求項3に記載のエッチング液。 The etching solution according to claim 2 or 3, wherein the third component contains a polyol compound.
- 上記ポリオール化合物の分子量が80以上200以下である請求項3又は請求項4に記載のエッチング液。 The etching solution according to claim 3 or 4, wherein the molecular weight of the polyol compound is 80 or more and 200 or less.
- 上記ポリオール化合物が3つ以上のヒドロキシル基を有する請求項3~5のいずれかに記載のエッチング液。 The etching solution according to any one of claims 3 to 5, wherein the polyol compound has three or more hydroxyl groups.
- 上記ポリオール化合物が、グリセリンを含有する請求項3~6のいずれかに記載のエッチング液。 The etching solution according to any one of claims 3 to 6, wherein the polyol compound contains glycerin.
- 第3成分が、多価カルボン酸化合物を含有する請求項2~7のいずれかに記載のエッチング液。 The etching solution according to any one of claims 2 to 7, wherein the third component contains a polyvalent carboxylic acid compound.
- 第3成分が、ヒドロキシ酸化合物を含有する請求項2~8のいずれかに記載のエッチング液。 The etching solution according to any one of claims 2 to 8, wherein the third component contains a hydroxy acid compound.
- 請求項1~9のいずれかに記載のエッチング液を用いて、液晶ポリマーをエッチング処理するエッチング工程を有することを特徴とする液晶ポリマーのエッチング方法。 A method for etching a liquid crystal polymer, which comprises an etching step of etching a liquid crystal polymer using the etching solution according to any one of claims 1 to 9.
- エッチング工程前に、50~100質量%のアルカノールアミン化合物を含有する前処理液を液晶ポリマーに接触させる前処理工程をさらに有する請求項10に記載の液晶ポリマーのエッチング方法。 The method for etching a liquid crystal polymer according to claim 10, further comprising a pretreatment step of bringing a pretreatment liquid containing 50 to 100% by mass of an alkanolamine compound into contact with the liquid crystal polymer before the etching step.
- 前処理液の温度が50℃以上である請求項11記載の液晶ポリマーのエッチング方法。 The method for etching a liquid crystal polymer according to claim 11, wherein the temperature of the pretreatment liquid is 50 ° C. or higher.
- エッチング工程後に、水洗液を用いた水洗工程をさらに有する請求項10~12のいずれかに記載の液晶ポリマーのエッチング方法。 The method for etching a liquid crystal polymer according to any one of claims 10 to 12, further comprising a washing step using a washing liquid after the etching step.
- 水洗工程が、第一水洗液による第一水洗工程及び第二水洗液による第二水洗工程をこの順に含み、エッチング液の温度-第一水洗液の温度が25℃未満であり、第一水洗液の温度-第二水洗液の温度が25℃未満である請求項13に記載の液晶ポリマーのエッチング方法。 The water washing step includes the first water washing step by the first water washing liquid and the second water washing step by the second water washing liquid in this order, and the temperature of the etching solution-the temperature of the first water washing liquid is less than 25 ° C. -The method for etching a liquid crystal polymer according to claim 13, wherein the temperature of the second washing liquid is less than 25 ° C.
- 水洗液をエッチング液に補充する請求項13又は14に記載の液晶ポリマーのエッチング方法。 The method for etching a liquid crystal polymer according to claim 13 or 14, wherein the washing liquid is replenished with the etching liquid.
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