JP4104154B2 - Liquid crystal polymer etching solution and liquid crystal polymer etching method. - Google Patents
Liquid crystal polymer etching solution and liquid crystal polymer etching method. Download PDFInfo
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- JP4104154B2 JP4104154B2 JP2005102888A JP2005102888A JP4104154B2 JP 4104154 B2 JP4104154 B2 JP 4104154B2 JP 2005102888 A JP2005102888 A JP 2005102888A JP 2005102888 A JP2005102888 A JP 2005102888A JP 4104154 B2 JP4104154 B2 JP 4104154B2
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- 238000005530 etching Methods 0.000 title claims description 138
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 89
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims description 89
- 238000000034 method Methods 0.000 title claims description 21
- 239000000243 solution Substances 0.000 claims description 74
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 239000003513 alkali Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 150000001414 amino alcohols Chemical class 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- -1 aliphatic amino alcohol Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 33
- 229910052802 copper Inorganic materials 0.000 description 33
- 239000004973 liquid crystal related substance Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 238000012545 processing Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 229920000544 Gore-Tex Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- BSIUFWMDOOFBSP-UHFFFAOYSA-N 2-azanylethanol Chemical compound NCCO.NCCO BSIUFWMDOOFBSP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000010329 laser etching Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- QZXIXSZVEYUCGM-UHFFFAOYSA-N 2-aminopropan-2-ol Chemical compound CC(C)(N)O QZXIXSZVEYUCGM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BESJRHHIPGWPTC-UHFFFAOYSA-N azane;copper Chemical compound N.[Cu] BESJRHHIPGWPTC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Classifications
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- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/30604—Chemical etching
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- C11D2111/22—
Description
本発明は微細金属回路をもった電子部品やカラーフィルタの検査用プローブなどの高い寸法精度の要求される電子部品などの製造に関する。 The present invention relates to the manufacture of electronic components having high dimensional accuracy, such as electronic components having fine metal circuits and inspection probes for color filters.
フレキシブルプリント基板、ＴＡＢ、ＣＳＰやハードディスクドライブ用の基材として、また、最近では、カラーフィルタの検査用プローブ用材料としても銅張りポリイミドフィルム基材が使用されている。しかし、ポリイミドは耐熱性は非常に高いが、吸水性が大きく、高い湿度の条件によって寸法精度が低下するという問題がある。そこで、最近では、電子機器の小型化、高精度化、信号の高周波化などに伴い、銅張りポリイミドフィルムに替わって半田接合時に要求される耐熱性を有し、吸水性や誘電率が小さく、さらに寸法精度のすぐれた熱可塑性液晶ポリエステルが注目されるようになってきた。 As a base material for flexible printed circuit boards, TAB, CSP, and hard disk drives, and recently, a copper-clad polyimide film base material is also used as a probe material for color filter inspection. However, although polyimide has very high heat resistance, there is a problem in that the water absorption is large and the dimensional accuracy is deteriorated due to high humidity conditions. Therefore, recently, with the downsizing, high accuracy, and high frequency of electronic devices, it has heat resistance required at the time of soldering instead of copper-clad polyimide film, and has low water absorption and dielectric constant. Further, thermoplastic liquid crystal polyesters having excellent dimensional accuracy have been attracting attention.
一般に、銅張り樹脂基材から電子部品を製造する場合には、金属配線回路のほかに、樹脂基材にスルーホールやブラインドホールのようなビアホール、デバイスホールなどが形成される。特に、フライングリードのような配線をもつデバイスホールや複雑で微細なビアホールの形成では、金属張り樹脂基材に対するパンチング加工やレーザーエッチングの適用が難しいため、それらに替わってプラズマエッチングやエッチング液を使用したケミカルエッチングを使用することが望ましい。 In general, when an electronic component is manufactured from a copper-clad resin base material, via holes, device holes, etc. such as through holes and blind holes are formed in the resin base material in addition to the metal wiring circuit. In particular, in the formation of device holes with wiring like flying leads and complicated and fine via holes, it is difficult to apply punching and laser etching to metal-clad resin substrates, so plasma etching and etching solutions are used instead. It is desirable to use chemical etching.
しかしながら、液晶ポリエステルに代表される液晶ポリマーは、分子構造が剛直な液晶構造をしており、耐薬品が高く、かつ、吸水性や親水性がないため、汎用のポリエステル樹脂であるポリエチレンテレフタレートにおいて、従来から表面加工などのエッチング処理に使われている苛性アルカリ水溶液によるエッチングではエッチング速度が遅すぎて実用的に満足なエッチング加工ができない。 However, liquid crystal polymers represented by liquid crystal polyester have a liquid crystal structure with a rigid molecular structure, high chemical resistance, and no water absorption or hydrophilicity. Therefore, in polyethylene terephthalate, which is a general-purpose polyester resin, Etching with a caustic aqueous solution that has been conventionally used for etching processing such as surface processing cannot achieve practically satisfactory etching processing because the etching rate is too slow.
そこで、最近、ポリイミドエッチング液として開発された無機アルカリ水溶液とアミノアルコールの混合物からなるポリイミドエッチング液を液晶ポリエステルのエッチング液として使用するエッチング方法が提案されている。 Therefore, recently, an etching method has been proposed in which a polyimide etching solution made of a mixture of an inorganic alkaline aqueous solution and amino alcohol, which has been developed as a polyimide etching solution, is used as an etching solution for liquid crystal polyester.
例えば、特許文献１には液晶ポリマーを、３５重量％〜５５重量％の高濃度の無機アルカリ塩と１０〜３５重量％の水溶性可溶化剤（アルカノールアミン）を含む水溶液を用いて、５０°C〜１２０°Cでエッチングする方法が開示されており、エッチング速度が大きく、エッチング加工後に優れた穴形状が得られる旨記載されている。
For example,
しかしながら、このエッチング方法では、液晶ポリエステルのエッチングが良好に進むけれども、液の安定性が極めて悪く、使用中に空気中の炭酸ガスを吸収してエッチング液中に白色の浮遊物や沈殿がすぐに発生し、さらに、この白色物質が時間の経過とともに、反応液中で結晶化し、反応槽壁に付着したり、エッチング処理物に付着しやすい。 However, with this etching method, the liquid crystal polyester proceeds well, but the stability of the solution is extremely poor, and during use, carbon dioxide in the air is absorbed, and white suspended matters and precipitates immediately appear in the etching solution. Furthermore, the white substance is crystallized in the reaction solution over time, and is likely to adhere to the reaction vessel wall or to the etched product.
したがって、この方法を工業的に利用する場合には、通常のエッチング工程でエッチング処理物に付着した付着物を除去することが難しく、安定したエッチング加工操作がやりにくいという問題がある。 Therefore, when this method is used industrially, there is a problem that it is difficult to remove deposits attached to the etched product in a normal etching process, and it is difficult to perform a stable etching process.
また、ポリイミドエッチング液として市販されている約３０重量％の無機アルカリ化合物と約３０重量％（４０重量％以下）のエタノールアミンを含む水溶液を液晶ポリエステルのエッチングに使用する場合は、上記のような不溶解物は生成しないものの、エッチング速度が遅く、エッチング用マスク周辺において液晶ポリエステルのサイドエッチングが起こるため、例えば、図２に示すように孔の開口部の形状が扁平になり、微細な孔加工ができないという問題があった。 In addition, when an aqueous solution containing about 30% by weight inorganic alkali compound and about 30% by weight (40% by weight or less), which is commercially available as a polyimide etching solution, is used for etching liquid crystal polyester, Although insoluble matter is not generated, the etching rate is slow, and side etching of the liquid crystalline polyester occurs around the etching mask. For example, the shape of the opening of the hole becomes flat as shown in FIG. There was a problem that could not.
一方、レーザーエッチングによる方法では、装置的に大掛りなものになり、また、液晶ポリマーが熱可塑性であるため、レーザ光の熱により樹脂が変形することによって、その上に形成された配線やビアホールなどのパターンが変形し、設計どおりのパターン加工ができないという問題がある。 On the other hand, the method using laser etching is large in terms of apparatus, and since the liquid crystal polymer is thermoplastic, the resin is deformed by the heat of the laser beam, so that wiring and via holes formed thereon are formed. There is a problem that the pattern cannot be processed as designed.
液晶ポリエステルに代表される液晶ポリマー基材、特に液晶ポリマーフィルムと金属箔との熱溶着または液晶ポリマー表面へのメッキ処理によって形成された金属張り液晶ポリマーフィルム基材に、エッチング加工によってデバイスホールやビアホールなどを形成する際に用いる液晶ポリマーのエッチング液、及び、そのエッチング液を用いて液晶ポリマーフィルム基材に、設計どおりのパターン形状やビア形状を容易に、かつ、安定したエッチング加工操作によって、しかも安価に加工できる液晶ポリマーのエッチング方法を提供することである。 Device holes and via holes are etched into metal-coated liquid crystal polymer film substrates formed by thermal welding of liquid crystal polymer film and metal foil or plating treatment on the surface of the liquid crystal polymer, represented by liquid crystal polyester. Etching solution of liquid crystal polymer used when forming etc., and liquid crystal polymer film substrate using the etching solution, pattern shape and via shape as designed easily and by stable etching processing operation, An object of the present invention is to provide a method for etching a liquid crystal polymer that can be processed at low cost.
液晶ポリマーフィルムと金属箔との熱溶着または液晶ポリマーへのメッキ処理で形成された金属張り液晶ポリマーフィルム基材において、デバイスホールやブラインドビアなどのビアホールをケミカルエッチング加工で行う場合、パターン形状やビア形状が設計どおりに加工できる工業的に利用価値の高いエッチング液組成やその効果的なエッチング方法について鋭意検討した結果、金属張り液晶ポリマーフィルム基材やその基材を用いて形成された金属配線などを有する液晶ポリマー基板を、無機アルカリ化合物と２−アミノエタノ−ルのような分子中に少なくとも１個以上のアミノ基と水酸基を有する脂肪族アミノアルコール類の水溶液からなり、かつ、これらの構成物質が極めて限定された組成であるアルカリエッチング液でエッチングすることにより、金属や樹脂マスク等に実質的な損傷を与えることなく、そして液晶ポリマーだけを選択的に加水分解して樹脂のサイドエッチングが少ない形状の優れた孔加工が可能な工業的に実用性の高い効果的なエッチング方法を見出した。 When metal vias such as device holes and blind vias are formed by chemical etching on metal-coated liquid crystal polymer film substrates formed by thermal welding of liquid crystal polymer film and metal foil or plating treatment on liquid crystal polymer, pattern shapes and vias As a result of intensive studies on industrially useful etchant compositions whose shapes can be processed as designed and their effective etching methods, metal-coated liquid crystal polymer film substrates and metal wiring formed using these substrates, etc. A liquid crystal polymer substrate comprising an aqueous solution of an aliphatic aminoalcohol having at least one amino group and a hydroxyl group in a molecule such as an inorganic alkali compound and 2-aminoethanol, and these constituents are Etch with alkaline etchant with very limited composition By doing so, it can be used practically industrially without causing substantial damage to metals, resin masks, etc., and by selectively hydrolyzing only the liquid crystal polymer to form holes with less side etching of the resin. We found a highly effective etching method.
すなわち、３０重量％以上３５重量％未満のアルカリ金属水酸化物などの無機アルカリ化合物と、４５〜５０重量％の分子中に少なくとも１個以上のアミノ基と水酸基を有する脂肪族アミノアルコール及び水から構成され、かつ、全アルカリ成分濃度（無機アルカリ化合物とアミノアルコールの合計）が７５重量％〜８０重量％である水溶液を用いて液晶ポリマーをエッチングすることにより、液晶ポリマーが比較的容易にエッチングされ、樹脂マスクや金属配線パターンなどにも実質的な損傷をあたえることなく、図３に示すような、サイドエッチングが少なく、かつ、テーパー角の大きいデバイスホールやビアホールを所望どおりに安定して形成できることを見出した。 That is, from 30% by weight to less than 35% by weight of an inorganic alkali compound such as an alkali metal hydroxide, 45 to 50% by weight of an aliphatic amino alcohol having at least one amino group and a hydroxyl group in the molecule, and water. The liquid crystal polymer is etched relatively easily by etching the liquid crystal polymer using an aqueous solution that is composed and has a total alkali component concentration (total of inorganic alkali compound and amino alcohol) of 75 wt% to 80 wt%. 3) Device holes and via holes having a small taper angle and a large taper angle can be stably formed as desired without giving substantial damage to resin masks, metal wiring patterns, and the like. I found.
本発明によれば、芳香族液晶ポリマーのエッチングにおいて、テーパー角の大きい優れた形状のビアホールを比較的容易に得ることができる上に、従来のポリイミドエッチング用アルカリエッチング液で加工処理を行った場合に比べて、エッチング速度が非常に速いので、サイドエッチングが少ない所望する形状の製品も容易に得ることができる。 According to the present invention, in etching of an aromatic liquid crystal polymer, a via hole having an excellent shape with a large taper angle can be obtained relatively easily, and when processing is performed with a conventional alkali etching solution for polyimide etching Compared to the above, since the etching rate is very high, a product having a desired shape with little side etching can be easily obtained.
また、無機アルカリが３５重量%以上の高濃度アルカリ液に比べて、液の安定性が極めてよくビアホールだけでなく、フライングリードのあるオープンホール（デバイスホール）等も容易に形成することが可能である。さらに、エッチング面の平滑性によりスルーホールやブライドビアホールの導通メッキ処理において非常に良い効果が得られる。 In addition, compared to high-concentration alkaline solutions containing 35% by weight or more of inorganic alkali, the stability of the solution is extremely good, and it is possible to easily form not only via holes but also open holes (device holes) with flying leads. is there. Furthermore, the smoothness of the etched surface can provide a very good effect in the conductive plating treatment of through holes and bride via holes.
本発明で使用される液晶ポリマー基材としては、分子中に水酸基やカルボキシル基を有する芳香族モノマーの共重合で得られるポリエステル樹脂基材がある。これの分子構造を図１に示す。 The liquid crystal polymer substrate used in the present invention includes a polyester resin substrate obtained by copolymerization of an aromatic monomer having a hydroxyl group or a carboxyl group in the molecule. The molecular structure of this is shown in FIG.
具体的には表１に示すような市販されている芳香族液晶ポリエステルであり、住友化学株式会社のエコノール（商品名）、クラレ株式会社のVECSTARなどが挙げられる。 Specifically, it is a commercially available aromatic liquid crystal polyester as shown in Table 1, and includes Econol (trade name) of Sumitomo Chemical Co., Ltd. and VECSTAR of Kuraray Co., Ltd.
また、本発明で使用される液晶ポリマー基材用のエッチング液は、３０重量％以上３５重量％未満、好ましくは３２重量％以上３５重量％未満のアルカリ金属水酸化物などの無機アルカリ化合物と、４５〜５０重量％の分子中に少なくとも１個以上のアミノ基と水酸基を有する脂肪族アミノアルコール及び水から構成され、かつ、全アルカリ成分濃度（無機アルカリ化合物とアミノアルコールの合計）が７５重量％以上８０重量％未満である水溶液である。 The etching liquid for the liquid crystal polymer substrate used in the present invention is 30 wt% or more and less than 35 wt%, preferably 32 wt% or more and less than 35 wt% of an inorganic alkali compound such as an alkali metal hydroxide, It is composed of an aliphatic amino alcohol having at least one amino group and a hydroxyl group in the molecule of 45 to 50% by weight and water, and the total alkali component concentration (total of inorganic alkali compound and amino alcohol) is 75% by weight. The aqueous solution is less than 80% by weight.
前記無機アルカリ化合物としては、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物などが好適に用いられる。これらの無機アルカリ化合物は固形または水溶液のいずれの形態でも使用することができるが、工業的に使用する場合は、水溶液が好適に使用される。 As the inorganic alkali compound, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferably used. These inorganic alkali compounds can be used either in the form of a solid or an aqueous solution, but in the case of industrial use, an aqueous solution is preferably used.
そして、前記の分子中に少なくとも１個以上の水酸基を有する脂肪族アミノアルコールとしては、モノエタノールアミン（２−アミノエタノール）、ジエタノールアミン、α−アミノイソプロパノ−ル、２−アミノブタノール等のような炭素数が２〜４程度のアルキル基を有する水溶性脂肪族アミノアルコールが挙げられる。 The aliphatic amino alcohol having at least one hydroxyl group in the molecule includes monoethanolamine (2-aminoethanol), diethanolamine, α-aminoisopropanol, 2-aminobutanol and the like. Examples thereof include water-soluble aliphatic amino alcohols having an alkyl group having about 2 to 4 carbon atoms.
これらのアミノアルコールは、無機アルカリ水溶液との相溶性がよく、無機アルカリが極端に高濃度でない限り、任意の割合で均一な混合ができるという特徴がある。これらの脂肪族アミノアルコールは１種類だけのアミノアルコールを使用するのではなく二つ以上を混合して使用してもよい。これらの脂肪族アミノアルコール類は水溶性なのでエッチング後の湯洗浄や水洗でアルカリ成分といっしょに簡単に除去することができる。 These amino alcohols are characterized by good compatibility with an aqueous inorganic alkali solution and uniform mixing at an arbitrary ratio as long as the inorganic alkali is not extremely high in concentration. These aliphatic amino alcohols may be used in a mixture of two or more instead of using only one type of amino alcohol. Since these aliphatic amino alcohols are water-soluble, they can be easily removed together with the alkaline component by hot water washing or water washing after etching.
特に、モノエタノールアミン（２−アミノエタノール）は水溶性が高く沸点も１５０°Ｃ以上と高く、１００°Ｃ以下の加熱温度で使用する場合、蒸発による液組成の変化を起こすことなく使用できる。また、液晶ポリエステルへの浸透性や加水分解生成物の溶解性も高い上に、工業的にも容易に入手できるので特に好ましい。 In particular, monoethanolamine (2-aminoethanol) has high water solubility and a boiling point as high as 150 ° C. or higher, and when used at a heating temperature of 100 ° C. or lower, it can be used without causing a change in liquid composition due to evaporation. Further, it is particularly preferable since it has high permeability to liquid crystal polyester and solubility of hydrolysis products, and is easily available industrially.
ところで、従来から無機アルカリ水溶液は液晶ポリエステル樹脂を加水分解する作用があり、表面処理などのエッチングに利用されてきたが、液晶ポリエステルの耐水性が高いため、低濃度水溶液においてはエッチング速度は極めて小さく、工業的に利用する場合においては、特許文献１に記載されているように、３５重量％以上好ましくは４０重量％の極めて高い濃度が必要であるといわれていた。
By the way, conventionally, an inorganic alkaline aqueous solution has an action of hydrolyzing a liquid crystal polyester resin and has been used for etching such as surface treatment. However, since the liquid polyester has high water resistance, the etching rate is extremely low in a low concentration aqueous solution. In industrial use, as described in
しかしながら、このような高濃度の無機アルカリ化合物水溶液を用いた場合には、使用中に空気中の炭酸ガスを吸収してエッチング液中に不溶性の炭酸塩や樹脂の加水分解反応物が固形物として析出または沈殿しやすい。そのため、エッチング液中のこれらの不溶解物を除去したり、エッチング液の組成濃度の調整や液の交換を頻繁に行う必要があるという問題があった。 However, when such a high concentration inorganic alkali compound aqueous solution is used, carbon dioxide gas in the air is absorbed during use, and the insoluble carbonate or resin hydrolysis reaction product in the etching solution becomes a solid. Easy to precipitate or precipitate. For this reason, there is a problem that it is necessary to remove these insoluble substances in the etching solution, and to frequently adjust the composition concentration of the etching solution and replace the solution.
そのような状況の中、本発明において、前述したようなエッチング液組成を最適化することによって、従来法ではエッチング速度が遅く効果がないといわれていた無機アルカリ化合物濃度が３５重量％未満でも、工業的に利用可能な優れたエッチング性能（加工速度と加工形状）を得ることができた。 Under such circumstances, in the present invention, by optimizing the etching solution composition as described above, even if the concentration of the inorganic alkali compound, which has been said to be ineffective due to the slow etching rate in the conventional method, is less than 35% by weight, Excellent etching performance (processing speed and processing shape) that can be used industrially was obtained.
その理由として、前記のアミノアルコールが液晶ポリエステル表面における無機アルカリ成分の濡れ性や浸透性を促進して加水分解反応を速め、さらに、最適濃度のアミノアルコールが液晶ポリエステルの加水分解生成物を樹脂表面からすばやく溶出・除去するためと考えられるが、エッチング速度を高く保持し、かつ、反応液中の不溶物析出を避けるためには、エッチング液中の無機アルカリ化合物、脂肪族アミノアルコールおよび水との混合割合が極めて重要であり、本発明の効果を得るためには、脂肪族アミノアルコールは無機アルカリ化合物に対して少なくとも等量以上を必要とする。 The reason is that the amino alcohol accelerates the hydrolysis reaction by promoting the wettability and permeability of the inorganic alkali component on the liquid crystal polyester surface, and the amino alcohol of the optimum concentration converts the hydrolysis product of the liquid crystal polyester to the resin surface. It is thought to be a quick elution / removal method from the above, but in order to keep the etching rate high and avoid insoluble precipitation in the reaction solution, it is necessary to remove the inorganic alkali compound, aliphatic amino alcohol and water in the reaction solution. The mixing ratio is extremely important. In order to obtain the effects of the present invention, the aliphatic amino alcohol needs to be at least equal to the inorganic alkali compound.
と言っても、例えば、無機アルカリ化合物を３５重量％以上にしてアミノアルコール濃度を４０重量％以上とすると、無機アルカリ化合物の濃度が高いほどエッチング速度が高くなる傾向にあるとはいえ、前述しているように液中に無機アルカリが溶けにくくなって析出してしまうし、また逆に、無機アルカリ濃度やアミノアルコール濃度が本発明でいう最適濃度より薄い場合、例えば、無機アルカリ化合物２８重量％、アミノアルコール３４重量％、水３８重量％程度の場合は、無機アルカリ化合物などの析出はないが、エッチング速度が遅くサイドエッチングが起こりやすいため、図２に示したような扁平な孔の形状のものしか得られない。 However, for example, when the inorganic alkali compound is 35% by weight or more and the amino alcohol concentration is 40% by weight or more, the etching rate tends to increase as the concentration of the inorganic alkali compound increases. If the inorganic alkali concentration or aminoalcohol concentration is less than the optimum concentration in the present invention, the inorganic alkali compound is, for example, 28% by weight. In the case of 34% by weight of amino alcohol and 38% by weight of water, there is no precipitation of inorganic alkali compounds or the like, but the etching rate is slow and side etching is likely to occur, so the shape of the flat hole as shown in FIG. You can only get things.
また、無機アルカリ化合物が３０重量％以上であっても、アミノアルコールが４０重量％未満で、水の割合が30重量%以上とすると、加水分解速度が遅くなることや表面の加水分解生成物の適度な剥離が阻害されるため、液晶ポリエステルの加水分解が不均一となり、さらに、加水分解反応物の溶解除去が不十分となって液中に浮遊し、加工表面もざらざらした状態になったり、エッチング残渣が残ったりしてエッチング部分の形状が不安定になりやすくなる。 Further, even if the inorganic alkali compound is 30% by weight or more, if the amino alcohol is less than 40% by weight and the ratio of water is 30% by weight or more, the hydrolysis rate becomes slow and the hydrolysis product on the surface Since moderate peeling is hindered, the hydrolysis of the liquid crystalline polyester becomes non-uniform, and further, the hydrolysis reaction product is insufficiently dissolved and removed and floats in the liquid, and the processed surface becomes rough, Etching residue remains, and the shape of the etched portion tends to become unstable.
そこで、エッチング速度を低下することなく、液中に不溶解物が生成しないような工業的に利用可能なエッチング液としては、無機アルカリ化合物の濃度を３０重量％以上３５重量％未満とし、さらに、アミノアルコールの濃度を４０重量％以上にして、かつ、水以外の全アルカリ成分（無機アルカリ化合物とアミノアルコールの合計）が７５重量％以上８０重量％未満になるようにすることが重要である。 Therefore, as an industrially usable etching solution that does not generate insoluble matter in the solution without decreasing the etching rate, the concentration of the inorganic alkali compound is 30 wt% or more and less than 35 wt%, It is important that the concentration of amino alcohol is 40% by weight or more, and that all alkali components other than water (total of inorganic alkali compound and amino alcohol) are 75% by weight or more and less than 80% by weight.
したがって、エッチング液中の各成分の適正濃度は、無機アルカリの濃度が３０重量％以上３５重量％未満、アミノアルコールの濃度が４５重量％〜５０重量％、水分濃度が２０〜２５重量％とするのが好ましいのである。 Therefore, the appropriate concentration of each component in the etching solution is such that the concentration of inorganic alkali is 30 wt% or more and less than 35 wt%, the concentration of amino alcohol is 45 wt% to 50 wt%, and the moisture concentration is 20 to 25 wt%. It is preferable.
このような本発明によるエッチング液の各成分の組成比率であるエッチング液であれば、図６に示すように、液を長時間（１０日間）使用した場合においては、エッチング操作中の液晶ポリマーの溶解によってエッチング液は黄色に着色してくるが、液は透明であり白色沈殿物や結晶の析出などは見られないため、安定したエッチング操作ができる。 As shown in FIG. 6, if the etching solution is a composition ratio of each component of the etching solution according to the present invention, the liquid crystal polymer during the etching operation is used when the solution is used for a long time (10 days). Although the etching solution is colored yellow by dissolution, the solution is transparent and no white precipitates or crystals are observed, so that a stable etching operation can be performed.
一方、従来の各成分の組成比率であるエッチング液では、図７に示すように、使用中に空気中の炭酸ガスを吸収してエッチング液中に白色の浮遊物や沈殿が短時間（１日後）に発生し、さらに、この白色物質が時間の経過とともに反応液中で結晶化して反応槽壁に付着したり、エッチング処理物に付着しやすくなるため、安定したエッチング操作ができない。 On the other hand, in the conventional etching solution having the composition ratio of each component, as shown in FIG. 7, the carbon dioxide gas in the air is absorbed during use, and white suspended matters and precipitates appear in the etching solution for a short time (after 1 day). In addition, the white substance crystallizes in the reaction solution over time and adheres to the reaction vessel wall or adheres to the etched product, so that a stable etching operation cannot be performed.
また、表２には、本発明のエッチング液と従来のエッチング液とで液晶ポリマー基材をエッチングした場合のエッチング速度を比較した結果を示す。この表からも明らかなように、本発明のエッチング液によるエッチング速度は非常に速く、従来の市販のエッチング液（例えば、比較例１、４）に比べると、実施例１及び５などでは約１０倍も速いことがわかる。 Table 2 shows the results of comparing the etching rates when the liquid crystal polymer substrate is etched with the etching solution of the present invention and the conventional etching solution. As is apparent from this table, the etching rate with the etching solution of the present invention is very high, and about 10 in Examples 1 and 5 compared with conventional commercially available etching solutions (for example, Comparative Examples 1 and 4). You can see that it is twice as fast.
なお、エッチング液中の無機または有機アルカリ成分の量やモノエタノールアミン等の量は規定濃度の塩酸で電位差滴定することによって管理することができる。 The amount of the inorganic or organic alkali component or monoethanolamine in the etching solution can be controlled by potentiometric titration with a specified concentration of hydrochloric acid.
また、本発明のエッチング液を用いてエッチング処理を行う場合は、液温度条件を６０°C以上９０°C以下、処理時間を１〜２０分間程度とするのが好ましく、より好ましい温度は８０°Cである。温度が低いと反応に時間がかかり、あまり高温になると、水分の蒸発が激しくなり、エッチング液の濃度が変化しやすくなる。 Moreover, when performing an etching process using the etching liquid of this invention, it is preferable that liquid temperature conditions shall be 60 degreeC or more and 90 degrees C or less, and processing time shall be about 1 to 20 minutes, and more preferable temperature is 80 degrees. C. If the temperature is low, the reaction takes time, and if the temperature is too high, the evaporation of moisture becomes intense and the concentration of the etching solution tends to change.
本発明によるエッチング操作において、基材とエッチング液を接触させる方法としては、攪拌状態の液中に基材を浸漬させる方法、基材に液を気中でスプレーする方法、液中でジェット噴流をあてる方法、液中で超音波をあてる方法などが挙げられる。液中で接触させる場合は基板を揺動することが有効である。基材に液を気中でスプレーする方法では炭酸ガスの混入や作業者の安全のためにも密閉系が好ましい。 In the etching operation according to the present invention, as a method of bringing the substrate into contact with the etching solution, a method of immersing the substrate in a stirred solution, a method of spraying the solution in the air, and a jet jet in the solution. Examples thereof include a method of hitting and a method of applying ultrasonic waves in a liquid. When contacting in a liquid, it is effective to swing the substrate. In the method of spraying the liquid on the substrate in the air, a closed system is preferable for the mixing of carbon dioxide gas and the safety of workers.
なお、本発明のエッチング液を用いたエッチング処理によって得られたスルービアホールのSEM（Scanning Electron Microscope）写真を図３に、ブラインドビアホールのSEM写真を図４に示す。いずれもホール側壁部の液晶ポリマーがきれいに除去され、しかも、テーパー角が大きく、エッチング表面には割れや凹凸もなく、比較的平滑な表面となっているのが分かる。 FIG. 3 shows a SEM (Scanning Electron Microscope) photograph of a through via hole obtained by etching using the etching solution of the present invention, and FIG. 4 shows a SEM photograph of a blind via hole. In either case, it can be seen that the liquid crystal polymer on the side wall of the hole is neatly removed, the taper angle is large, and the etching surface is free of cracks and irregularities and has a relatively smooth surface.
［実施例１］ジャパンゴアテックス株式会社製の片面銅張り液晶ポリマーフィルム基材（銅厚み１８μm、液晶ポリエステルフィルム基材「BIAC」厚み１２５μm）のサンプル片（５ｃｍ×５ｃｍ、厚み１４３μm）を、水酸化カリウム（KOH）３４．５重量％、モノエタノールアミン（MEA）４５重量％、水２０．５重量％からなるエッチング液に液温度８０°Cで浸漬し、全体膜厚みの変化を測定し、エッチングされた液晶ポリマー層の厚みの変化を測定した。エッチング液はビーカー中で攪拌しながら行った。時間の経過と共に液晶ポリマー層の膜厚は減少し、６．５分で液晶ポリマー層は完全にエッチングされて、銅表面が露出した。反応時間と液晶ポリマー層の膜厚の減少量はほぼ比例関係にあり、液晶ポリマー層平均のエッチング速度は１９．５μm／分であった。（膜厚はMITUTOYO CORP．製model１D−C１１２で測定）。 Example 1 A sample piece (5 cm × 5 cm, thickness 143 μm) of a single-sided copper-clad liquid crystal polymer film substrate (copper thickness 18 μm, liquid crystal polyester film substrate “BIAC” thickness 125 μm) manufactured by Japan Gore-Tex Co., Ltd. Immerse it in an etching solution consisting of 34.5% by weight of potassium oxide (KOH), 45% by weight of monoethanolamine (MEA) and 20.5% by weight of water at a liquid temperature of 80 ° C., and measure the change in the total film thickness. The change in thickness of the etched liquid crystal polymer layer was measured. The etchant was stirred in a beaker. The film thickness of the liquid crystal polymer layer decreased with the passage of time, and the liquid crystal polymer layer was completely etched in 6.5 minutes to expose the copper surface. The reaction time and the amount of decrease in the film thickness of the liquid crystal polymer layer were in a proportional relationship, and the average etching rate of the liquid crystal polymer layer was 19.5 μm / min. (The film thickness is measured with model 1D-C112 manufactured by MITUTOYO CORP.).
［実施例２］ジャパンゴアテックス株式会社製の片面銅張り液晶ポリマーフィルム基材（銅厚み１８μm、液晶ポリエステルフィルム基材「BIAC」厚み１２５μm）のサンプル片（５ｃｍ×５ｃｍ、厚み１４３μm）を、水酸化カリウム３４重量％、モノエタノールアミン４５重量％、水２１重量％からなるエッチング液に液温度８０°Cで浸漬し、全体膜厚みの変化を測定し、エッチングされた液晶ポリマー層の厚みの変化を測定した。エッチング液はビーカー中で攪拌しながら行った。時間の経過と共に液晶ポリマー層の膜厚は減少し、６．９分で液晶ポリマー層は完全にエッチングされて、銅表面が露出した。反応時間と液晶ポリマー層の膜厚の減少量はほぼ比例関係にあり、液晶ポリマー層平均のエッチング速度は１８μm／分であった。 Example 2 A sample piece (5 cm × 5 cm, thickness 143 μm) of a single-sided copper-clad liquid crystal polymer film base material (copper thickness 18 μm, liquid crystal polyester film base material “BIAC” thickness 125 μm) manufactured by Japan Gore-Tex Co., Ltd.) Immersion in an etching solution consisting of 34% by weight of potassium oxide, 45% by weight of monoethanolamine, and 21% by weight of water at a liquid temperature of 80 ° C., measuring the change in the total film thickness, and changing the thickness of the etched liquid crystal polymer layer Was measured. The etchant was stirred in a beaker. The film thickness of the liquid crystal polymer layer decreased with the passage of time, and the liquid crystal polymer layer was completely etched in 6.9 minutes to expose the copper surface. The reaction time and the amount of decrease in the thickness of the liquid crystal polymer layer were in a proportional relationship, and the average etching rate of the liquid crystal polymer layer was 18 μm / min.
［実施例３］ジャパンゴアテックス株式会社製の片面銅張り液晶ポリマーフィルム基材（銅厚み１８μm、液晶ポリエステルフィルム基材「BIAC」厚み１２５μm）のサンプル片（５ｃｍ×５ｃｍ、厚み１４３μm）を、水酸化カリウム３４．５重量％、モノエタノールアミン４２重量％、水２３．５重量％からなるエッチング液に液温度８０°Cで浸漬し、全体膜厚みの変化を測定し、エッチングされた液晶ポリマー膜の厚みの変化を測定した。エッチング液はビーカー中で攪拌しながら行った。時間の経過と共に液晶ポリマーの膜厚は減少し、８．３分で液晶ポリマー層は完全にエッチングされて、銅表面が露出した。反応時間と液晶ポリマー層の膜厚の減少量はほぼ比例関係にあり、液晶ポリマー層平均のエッチング速度は１５μm／分であった。 Example 3 A sample piece (5 cm × 5 cm, thickness 143 μm) of a single-sided copper-clad liquid crystal polymer film substrate (copper thickness 18 μm, liquid crystal polyester film substrate “BIAC” thickness 125 μm) manufactured by Japan Gore-Tex Co., Ltd. A liquid crystal polymer film etched by immersing it in an etching solution comprising 34.5% by weight of potassium oxide, 42% by weight of monoethanolamine, and 23.5% by weight of water at a liquid temperature of 80 ° C., and measuring the change in the total film thickness. The change in the thickness was measured. The etchant was stirred in a beaker. The film thickness of the liquid crystal polymer decreased with time, and the liquid crystal polymer layer was completely etched in 8.3 minutes, exposing the copper surface. The reaction time and the amount of decrease in the thickness of the liquid crystal polymer layer were in a proportional relationship, and the average etching rate of the liquid crystal polymer layer was 15 μm / min.
［実施例４］新日本製鉄化学株式会社製の「エスパネックス」LCP（液晶ポリマーフィルム基材「VECSTAR」：５０μm／Cu：１８μm）の試験片を、水酸化カリウム３０重量％、モノエタノールアミン４９重量％、水２１重量％からなるエッチング液に液温度８０°Cで浸漬し、全体膜厚みの変化を測定し、エッチングされた液晶ポリマー層の厚みの変化を測定した。時間の経過と共に液晶ポリマー層の膜厚は減少し、３．５分で液晶ポリマー層は完全にエッチングされて、銅表面が露出した。液晶ポリマー層平均のエッチング速度は１４．４μm／分であった。 [Example 4] A test piece of “Espanex” LCP (liquid crystal polymer film substrate “VECSTAR”: 50 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd., 30 wt% potassium hydroxide, monoethanolamine 49 The film was immersed in an etching solution composed of 15% by weight and 21% by weight of water at a liquid temperature of 80 ° C., the change in the total film thickness was measured, and the change in the thickness of the etched liquid crystal polymer layer was measured. The film thickness of the liquid crystal polymer layer decreased with the passage of time, and the liquid crystal polymer layer was completely etched in 3.5 minutes to expose the copper surface. The average etching rate of the liquid crystal polymer layer was 14.4 μm / min.
［実施例５］新日本製鉄化学株式会社製の「エスパネックス」LCP（液晶ポリマーフィルム基材「VECSTAR」：５０μm／Cu：１８μm）の試験片を、水酸化カリウム３４．９重量％、モノエタノールアミン４５重量％、水２０．１重量％からなるエッチング液に液温度８０°Cで浸漬し、全体膜厚みの変化を測定し、エッチングされた液晶ポリマー層の厚みの変化を測定した。時間の経過と共に液晶ポリマーの層の膜厚は減少し、２．３分で液晶ポリマー層は完全にエッチングされて、銅表面が露出した。液晶ポリマー層平均のエッチング速度は２２μm／分であった。 [Example 5] A test piece of “Espanex” LCP (liquid crystal polymer film substrate “VECSTAR”: 50 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd., 34.9% by weight of potassium hydroxide, monoethanol The film was immersed in an etching solution composed of 45% by weight of amine and 20.1% by weight of water at a liquid temperature of 80 ° C., the change in the total film thickness was measured, and the change in the thickness of the etched liquid crystal polymer layer was measured. The film thickness of the liquid crystal polymer layer decreased with the passage of time, and in 2.3 minutes, the liquid crystal polymer layer was completely etched to expose the copper surface. The average etching rate of the liquid crystal polymer layer was 22 μm / min.
［比較例１〜５］実施例１と同じ基材を用いて、エッチング液のKOH／MEA／水の割合を表２のような組成に調整し、実施例１〜５と同じ温度条件でエッチング速度を測定した。結果は表２に示す通りである。 [Comparative Examples 1-5] Using the same base material as in Example 1, the ratio of KOH / MEA / water in the etching solution was adjusted to the composition shown in Table 2, and etching was performed under the same temperature conditions as in Examples 1-5. The speed was measured. The results are as shown in Table 2.
いずれのエッチング速度も比較例５を除いては、実施例１〜５の結果に比べると、１／１０〜１／２と大幅に低いものであった。 Except for Comparative Example 5, all the etching rates were significantly lower, 1/10 to 1/2, compared with the results of Examples 1-5.
エッチング条件：反応温度はすべて80℃、ビーカー中で液を攪拌しながら試料を浸漬した。
材料：「BIAC」はジャパンゴアテックス株式会社の銅張り液晶ポリマーフィルム基材、「VECSTAR」は新日本製鉄化学株式会社の銅張り液晶ポリマーフィルム基材である。
Etching conditions: All reaction temperatures were 80 ° C., and the sample was immersed while stirring the solution in a beaker.
Materials: “BIAC” is a copper-clad liquid crystal polymer film substrate of Japan Gore-Tex Corporation, and “VECSTAR” is a copper-clad liquid crystal polymer film substrate of Nippon Steel Corporation.
比較例５では反応終了後、液温低下とともに液中に結晶が析出し、加温後も簡単には消失しなかった。 In Comparative Example 5, after the completion of the reaction, crystals were precipitated in the liquid as the liquid temperature decreased and did not disappear easily after heating.
［実施例６］新日本製鉄化学株式会社製「エスパネックス」LCP（液晶ポリマーフィルム基材「VECSTAR」：１００μm／Cu：１８μm）の両面にニチゴーモートン社製アルカリ現像タイプのドライフィルムNIT−２１５をラミネートし、銅側のドライフィルムに図５に示すエッチング評価試験用マスク（孔径１００〜８００μm）を使って露光・現像し、パターンマスク加工を行った。つぎに、この試験片を塩化第二鉄エッチング液でマスク開口部の銅膜をエッチングしたあと、アルカリ剥離液で銅側だけのドライフィルムを剥離して、１００〜８００μmの孔径をもつ銅マスクを作った。つぎに、この銅マスク形成液晶ポリマーフィルム試験片を、水酸化カリウム３４．９重量％、エタノールアミン４５重量％、水２０．１重量％からなるエッチング液に液温度８０°Cで５分間浸漬し、液晶ポリマーフィルム基材のエッチング孔加工を行った。結果は図３に示すように、７３度のテーパー角を有するエッチング壁の表面も平滑なきれいな孔を得ることができた。 [Embodiment 6] Nichigo Morton's alkali development type dry film NIT-215 on both sides of “Espanex” LCP (liquid crystal polymer film substrate “VECSTAR”: 100 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd. The laminate was exposed to light and developed using a mask for etching evaluation test (pore diameter: 100 to 800 μm) shown in FIG. 5 on the dry film on the copper side to perform pattern mask processing. Next, after etching the copper film at the mask opening with ferric chloride etching solution on this test piece, the dry film only on the copper side is peeled off with an alkali stripping solution to form a copper mask having a pore diameter of 100 to 800 μm. Had made. Next, this copper mask-forming liquid crystal polymer film test piece was immersed in an etching solution comprising 34.9% by weight of potassium hydroxide, 45% by weight of ethanolamine and 20.1% by weight of water at a liquid temperature of 80 ° C. for 5 minutes. Etching hole processing of the liquid crystal polymer film substrate was performed. As a result, as shown in FIG. 3, the surface of the etching wall having a taper angle of 73 degrees was able to obtain a smooth and smooth hole.
［実施例７］ジャパンゴアテックス株式会社製片面銅張り液晶ポリマーフィルム基材（銅厚み１８μm、液晶ポリエステルフィルム基材「BIAC」厚み１２５μm）のサンプル片［５ｃｍｘ５ｃｍ，厚み１４３μｍ］の両面にドライフィルムをラミネートし、銅側に図５に示す丸孔の評価用パターンマスクを用いて露光・現像を行い、樹脂パターンマスクを作製したあと、塩化第二鉄で銅エッチングを行い、丸孔のある銅マスクパターンを形成した。つぎに、このサンプルを、水酸化カリウム３４．５重量％、モノエタノールアミン４５重量％、水２０．５重量％からなる液温８０°Cのエッチング液で７分間エッチングした。裏面のドライフィルムと銅マスクを剥離したところ、スルーホールをもった液晶フィルム基板が得られた。ビアのテーパー角は７３度であった。この組成のエッチング液では、液中への沈殿物の生成はなく、何度も繰り返しエッチングを行っても処理効果は変わらず安定していた。 [Example 7] A dry film on both sides of a sample piece [5 cm × 5 cm, thickness 143 μm] of a single-sided copper-clad liquid crystal polymer film substrate (copper thickness 18 μm, liquid crystal polyester film substrate “BIAC” thickness 125 μm) manufactured by Japan Gore-Tex Co., Ltd. After laminating and exposing and developing using a pattern mask for evaluation of round holes as shown in FIG. 5 on the copper side, a resin pattern mask is prepared, and then copper etching is performed with ferric chloride to provide a copper mask with round holes. A pattern was formed. Next, this sample was etched for 7 minutes with an etching solution of 34.5% by weight of potassium hydroxide, 45% by weight of monoethanolamine, and 20.5% by weight of water at a liquid temperature of 80 ° C. When the dry film and the copper mask on the back surface were peeled off, a liquid crystal film substrate having through holes was obtained. The taper angle of the via was 73 degrees. In the etching solution having this composition, no precipitate was generated in the solution, and the treatment effect was stable even after repeated etching.
［実施例８］新日本製鉄化学株式会社製「エスパネックス」LCP（液晶ポリマーフィルム基材「VECSTAR」：１００μm／Cu：１８μm）の試験片１００mm×１００mmの両面にドライフィルムをラミネートし、銅側に丸孔のパターンマスクを用いて露光・現像を行い、樹脂パターンマスクを作製したあと、塩化第二鉄で銅エッチングを行い、丸孔のある銅マスクパターンを形成した。つぎに、水酸化カリウム３４．５重量％、エタノールアミン４５重量％、水２０．１重量％からなるエッチング液に液温度８５°Cで５分間浸漬エッチングした。裏面のドライフィルムと銅マスクを剥離したところ、７２度のテーパー角のスルーホールをもった液晶フィルム基板が得られた。この組成のエッチング液では、液中への沈殿物の生成はなく、何度も繰り返しエッチングを行っても処理効果は変わらず安定していた。 [Example 8] A test piece of "Espanex" LCP (liquid crystal polymer film base material "VECSTAR": 100 μm / Cu: 18 μm) made by Nippon Steel Chemical Co., Ltd. was laminated on both sides of a 100 mm × 100 mm test piece, and the copper side Then, exposure and development were carried out using a round hole pattern mask to produce a resin pattern mask, and then copper etching was performed with ferric chloride to form a copper mask pattern with round holes. Next, immersion etching was performed for 5 minutes at a liquid temperature of 85 ° C. in an etching solution composed of 34.5% by weight of potassium hydroxide, 45% by weight of ethanolamine and 20.1% by weight of water. When the dry film and the copper mask on the back surface were peeled off, a liquid crystal film substrate having a through hole with a taper angle of 72 degrees was obtained. In the etching solution having this composition, no precipitate was generated in the solution, and the treatment effect was stable even after repeated etching.
［実施例９］新日本製鉄化学株式会社製「エスパネックス」LCP（液晶ポリマーフィルム基材「VECSTAR」：１００μm／Cu：１８μm）の試験片１００mm×１００mmの両面にドライフィルムをラミネートし、片面に丸孔のパターンマスクを用いて露光・現像を行い、樹脂パターンマスクを作製したあと、塩化第二鉄で銅エッチングを行い、丸孔のある銅マスクパターンを形成した。つぎに、水酸化カリウム３４．５重量％、エタノールアミン４５重量％、水２０．１重量％からなるエッチング液に液温度８５°Cで６分間浸漬エッチングした。裏面のドライフィルムをラミネートしたままで銅マスクを剥離し、ついで、裏面のドライフィルムを剥離したところ、ブラインドビアホールをもった液晶フィルム基板が得られた。この組成のエッチング液では、液中への沈殿物の生成はなく、何度も繰り返しエッチングを行っても処理効果は変わらず安定していた。 [Example 9] A test piece of “Espanex” LCP (liquid crystal polymer film substrate “VECSTAR”: 100 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd. was laminated on both sides of a dry film on one side. Exposure / development was performed using a round hole pattern mask to produce a resin pattern mask, and then copper etching was performed with ferric chloride to form a copper mask pattern with round holes. Next, immersion etching was carried out for 6 minutes at a liquid temperature of 85 ° C. in an etching solution comprising 34.5% by weight of potassium hydroxide, 45% by weight of ethanolamine and 20.1% by weight of water. The copper mask was peeled while the dry film on the back surface was laminated, and then the dry film on the back surface was peeled off to obtain a liquid crystal film substrate having blind via holes. In the etching solution having this composition, no precipitate was generated in the solution, and the treatment effect was stable even after repeated etching.
［比較例６］新日本製鉄化学株式会社製「エスパネックス」LCP（液晶ポリマーフィルム基材べクスタ：１００μm／Cu：１８μm）の両面にニチゴーモートン社製アルカリ現像タイプのドライフィルムNIT−２１５をラミネートし、銅側のドライフィルムに図５のエッチング評価試験用マスク（孔径１００〜８００μm）を使って露光・現像し、パターンマスク加工を行った。つぎに、この試験片を塩化第二鉄エッチング液でマスク開口部の銅膜をエッチングしたあと、アルカリ剥離液で銅側だけのドライフィルムを剥離して、１００〜８００μmの孔径をもつ銅マスクを作った。つぎに、この銅マスクが形成された液晶ポリマーフィルム試験片を、水酸化カリウム２８重量％、エタノールアミン３３重量％、水３９重量％からなるエッチング液に液温度８５°Cで浸漬し、液晶ポリマーフィルム基材にエッチング孔加工を行った。エッチング速度が遅いため、フィルムに孔が開くまでには約４５分間を要した。結果は図２に示すように、樹脂のサイドエッチングが大きく、テーパー角の小さな樹脂壁の表面も平滑でない孔しか得ることができなかった。 [Comparative Example 6] Nichigo Morton's alkali development type dry film NIT-215 is laminated on both sides of “Espanex” LCP (liquid crystal polymer film substrate vector: 100 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd. Then, the copper-side dry film was exposed and developed using the etching evaluation test mask (pore diameter 100 to 800 μm) of FIG. 5 to perform pattern mask processing. Next, after etching the copper film at the mask opening with ferric chloride etching solution on this test piece, the dry film only on the copper side is peeled off with an alkali stripping solution to form a copper mask having a pore diameter of 100 to 800 μm. Had made. Next, the liquid crystal polymer film test piece on which the copper mask was formed was immersed in an etching solution consisting of 28% by weight of potassium hydroxide, 33% by weight of ethanolamine and 39% by weight of water at a liquid temperature of 85 ° C. Etching holes were processed on the film substrate. Since the etching rate was slow, it took about 45 minutes for the holes to open in the film. As a result, as shown in FIG. 2, only side holes of the resin were large, and the surface of the resin wall having a small taper angle was able to obtain only holes that were not smooth.
［比較例７］新日本製鉄化学株式会社製「エスパネックス」LCP（液晶ポリマーフィルム基材べクスタ：１００μm／Cu：１８μm）の両面にニチゴーモートン社製アルカリ現像タイプのドライフィルムNIT−２１５をラミネートし、銅側のドライフィルムに図５のエッチング評価試験用マスク（孔径１００〜８００μm）を使って露光・現像し、パターンマスク加工を行った。つぎに、この試験片をアンモニア銅エッチング液でマスク開口部の銅膜をエッチングしたあと、アルカリ剥離液で銅側だけのドライフィルムを剥離して、１００〜８００μmの孔径をもつ銅マスクを作った。つぎに、この銅マスクが形成された液晶ポリマーフィルム試験片を、水酸化カリウム４０重量％、エタノールアミン３３重量％、水２７重量％からなるエッチング液に液温度８５°Cで７分間浸漬し、液晶ポリマーフィルム基材にエッチング孔加工を行った。樹脂のサイドエッチングが少なく、７１度のテーパー角を有する樹脂壁の表面も平滑な孔が得られた。しかし、エッチング処理後のエッチング液の表面には白い膜状の物質が生成し、室温に一日放置したところ、液中の底部に結晶状の沈殿物が多量に生成していた。 [Comparative Example 7] Nichigo Morton's alkali development type dry film NIT-215 is laminated on both sides of “Espanex” LCP (liquid crystal polymer film substrate vector: 100 μm / Cu: 18 μm) manufactured by Nippon Steel Chemical Co., Ltd. Then, the copper-side dry film was exposed and developed using the etching evaluation test mask (pore diameter 100 to 800 μm) of FIG. 5 to perform pattern mask processing. Next, after etching the copper film of the mask opening with the ammonia copper etching solution on this test piece, the dry film only on the copper side was peeled off with an alkali stripping solution to make a copper mask having a hole diameter of 100 to 800 μm. . Next, the liquid crystal polymer film test piece on which the copper mask was formed was immersed in an etching solution consisting of 40% by weight of potassium hydroxide, 33% by weight of ethanolamine and 27% by weight of water at a liquid temperature of 85 ° C. for 7 minutes. Etching holes were processed in the liquid crystal polymer film substrate. There was little resin side etching, and a smooth hole was also obtained on the surface of the resin wall having a taper angle of 71 degrees. However, a white film-like substance was formed on the surface of the etching solution after the etching treatment, and when left at room temperature for one day, a large amount of crystalline precipitate was formed at the bottom of the solution.
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