JPH01168865A - Production of article coated with copper film - Google Patents
Production of article coated with copper filmInfo
- Publication number
- JPH01168865A JPH01168865A JP62325567A JP32556787A JPH01168865A JP H01168865 A JPH01168865 A JP H01168865A JP 62325567 A JP62325567 A JP 62325567A JP 32556787 A JP32556787 A JP 32556787A JP H01168865 A JPH01168865 A JP H01168865A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- article
- acid
- film
- copper film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 239000010949 copper Substances 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 12
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 12
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 229920001721 polyimide Polymers 0.000 abstract description 10
- 150000001879 copper Chemical class 0.000 abstract description 9
- 235000011187 glycerol Nutrition 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical group OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- ZTBHEZIOGARBOD-UHFFFAOYSA-N 2,3,4-trimethylpentane-2,3,4-triol Chemical compound CC(C)(O)C(C)(O)C(C)(C)O ZTBHEZIOGARBOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- -1 bentanediol Chemical compound 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリイミド、全芳香族ポリアミド、ポリアミ
ドイミド、ＰＰＳ （ポリフェニレンサルファイド）、
ポリベンツイミダゾール等の超耐熱性の樹脂のフィルム
、シート、成形体、繊維、布、ペーパー、粉などの物品
に銅被膜を形成する新規な方法に関するものであり、本
製造法による銅膜形成物品は、特別の前処理をすること
なく銅が強固に付着したものであり、しかもハロゲンな
どの腐食性を有する元素を全く含まないものであるので
、そのままで或いは更に銅その他の金属をメツキなどの
下地として電気、接着、その他の各種用途に好適に使用
されるものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polyimide, wholly aromatic polyamide, polyamideimide, PPS (polyphenylene sulfide),
This article relates to a new method for forming a copper coating on articles such as films, sheets, molded articles, fibers, cloth, paper, powder, etc. made of ultra-heat-resistant resin such as polybenzimidazole, and includes articles on which a copper coating is formed using this manufacturing method. Copper is firmly attached without any special pre-treatment, and it does not contain any corrosive elements such as halogens, so it can be used as is or with copper or other metals plated. It is suitably used as a base for electrical, adhesive, and various other uses.
超耐熱性樹脂物品に、銅被膜を形成する方法としては、
無電解メツキ法、蒸着法、圧接法、接着剤による接着な
どがある。The method for forming a copper coating on super heat-resistant resin articles is as follows:
Examples include electroless plating, vapor deposition, pressure welding, and bonding with adhesives.
無電解メツキ法は、最も一般的であり優れた方法である
が、通常は用いる樹脂に応じた特別の前処理を必須とす
るものであり、その工程が煩雑であるという欠点を有し
ている。The electroless plating method is the most common and excellent method, but it usually requires special pretreatment depending on the resin used, and has the disadvantage that the process is complicated. .
蒸着法は、蒸着のための特別の設備を必須とし、大型品
の製造が困難であり、またセラミックスの種類によって
は接着性を向上させるための前処理が必要であった。更
に、圧接法、接着剤による接着など適宜使用されるもの
であるが、圧着不可能であったり、成形品の形状が限定
されたり、接着剤を使用する場合、接着層が厚くなり、
接着層の物性が得られた物品の物性を劣化させるなどの
欠点があるものであった。The vapor deposition method requires special equipment for vapor deposition, making it difficult to manufacture large products, and depending on the type of ceramic, pretreatment is required to improve adhesiveness. Furthermore, although pressure bonding methods and bonding with adhesives are used as appropriate, there are cases where pressure bonding is not possible, the shape of the molded product is limited, and when adhesives are used, the adhesive layer becomes thicker.
This method has the disadvantage that the physical properties of the adhesive layer deteriorate the physical properties of the resulting product.
本発明は、上記の事情に鑑み、簡便な方法により、経済
的で高品質の銅膜の形成された材料を提供する方法につ
いて検討した結果、完成したものである。In view of the above circumstances, the present invention was completed as a result of studies on a method of providing an economical and high-quality material with a copper film formed thereon by a simple method.
すなわち、本発明は、超耐熱性の樹脂物品の所望部に、
水酸化銅又は有機酸銅から選択された銅化合物と多価ア
ルコールとを必須成分とする混合液を塗布した後、非酸
化性雰囲気中で１６５℃以上で該超耐熱性樹脂物品の変
形劣化温度以下の温度に加熱することを特徴とする銅膜
形成物品の製造法である。That is, in the present invention, a desired part of an ultra-heat-resistant resin article,
After applying a mixed solution containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components, the deformation deterioration temperature of the super heat-resistant resin article is at 165°C or higher in a non-oxidizing atmosphere. This is a method for producing a copper film-forming article, which is characterized by heating to the following temperature.
以下、本発明について説明する。The present invention will be explained below.
本発明の超耐熱性樹脂物品とは、フィルム、シート、成
形体、繊維、布、ペーパー、粉等の各梯形の物品である
。具体的な超耐熱性樹脂としては、ポリイミド、全芳香
族ポリアミド、ポリアミドイミド、ＰＰＳ （ポリフェ
ニレンサルファイド）、ポリベンツイミダゾールが挙げ
られる。The super heat-resistant resin articles of the present invention are trapezoidal articles such as films, sheets, molded bodies, fibers, cloth, paper, and powder. Specific examples of super heat-resistant resins include polyimide, wholly aromatic polyamide, polyamideimide, PPS (polyphenylene sulfide), and polybenzimidazole.
上記の樹脂に銅膜を形成するために使用する本発明の水
酸化銅又は有機酸銅から選択された銅化合物と多価アル
コールとを必須成分とする混合液（以下、処理液と記す
）に使用する銅化合物とは、水酸化銅又は有機酸の銅塩
であり、これらは特に限定されないものであるが、銅膜
形成に使用する温度において炭化することなく表面から
離脱し易い化合物が好ましく、価格や入手のし易さを考
慮して適宜選択する。具体的には、蟻酸、酢酸、プロピ
オン酸、酪酸、ピバリン酸、カプロン酸、カプリン酸、
ラウリン酸、ステアリン酸、ナフテン酸、安息香酸、オ
レイン酸、アクリル酸、メタクリル酸、クロトン酸、ペ
ンテン酸などのモノカルボン酸の銅塩；蓚酸、マロン酸
、コハク酸、グルタル酸、アジピン酸、ピメリン酸、コ
ハク酸、アゼライン酸、ブラシリン酸、マレイン酸、フ
マル酸、フタル酸、トリメリット酸、マレイン酸などの
ポリカルボン酸のの銅塩；更に、モノ−或いはポリカル
ボン酸のエステル、アミドなど、グリコール酸などの水
酸基、グルタミン酸などのアミノ酸などの銅塩も挙げら
れる。A mixed solution (hereinafter referred to as treatment solution) containing as essential components a copper compound selected from copper hydroxide or organic acid copper of the present invention and a polyhydric alcohol, which is used to form a copper film on the above resin. The copper compound to be used is copper hydroxide or a copper salt of an organic acid, and these are not particularly limited, but preferably a compound that easily separates from the surface without carbonizing at the temperature used for forming the copper film. Select as appropriate, taking into consideration price and availability. Specifically, formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, capric acid,
Copper salts of monocarboxylic acids such as lauric acid, stearic acid, naphthenic acid, benzoic acid, oleic acid, acrylic acid, methacrylic acid, crotonic acid, pentenoic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline acids, copper salts of polycarboxylic acids such as succinic acid, azelaic acid, brassic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, maleic acid; furthermore, esters and amides of mono- or polycarboxylic acids, etc. Also included are copper salts of hydroxyl groups such as glycolic acid and amino acids such as glutamic acid.
また、多価アルコールとは、水酸基を２個以上含有する
化合物であり、これらも特に限定されないものであるが
、用いる成形体の表面との濡れ特性が良好で、銅膜形成
に使用する温度において表面から炭化することなく離脱
し易い化合物が好ましい。具体的には、エチレングリコ
ール、プロピレングリコール、ブタンジオール、ベンタ
ンジオール、ヘキサンジオール、１．５−ヘキサジエン
−３゜４−ジオール、２．６−オクタジエン−４，５−
ジオール、グリセリン、１．２．３−ブタントリオール
、１．２．３−ペンタントリオール、ペンタメチルグリ
セリン、エリトリット、ペンタエリトリット、アトニッ
ト、アラビット、ジエチレングリコール、トリエチレン
グリコール、ジプロピレングリコール、その他のポリア
ルキレングリコール類、さらにはジェタノールアミン、
トリエタノールアミンなどが挙げられる。Polyhydric alcohol is a compound containing two or more hydroxyl groups, and although it is not particularly limited, it has good wettability with the surface of the molded product and is suitable for use at the temperature used for copper film formation. A compound that can be easily released from the surface without carbonization is preferred. Specifically, ethylene glycol, propylene glycol, butanediol, bentanediol, hexanediol, 1.5-hexadiene-3°4-diol, 2.6-octadiene-4,5-
Diol, glycerin, 1.2.3-butanetriol, 1.2.3-pentanetriol, pentamethylglycerin, erythritol, pentaerythritol, atonite, arabite, diethylene glycol, triethylene glycol, dipropylene glycol, other polyalkylenes Glycols, even jetanolamine,
Examples include triethanolamine.
本発明の処理液は、上記した水酸化銅又は有機酸銅と多
価アルコールとを混合して調整する。処理液中の水酸化
銅又は有機酸銅と多価アルコールとの組成比は、均一に
混合された混合溶液が調整出来る範囲であれば特に限定
されないが、水酸化銅又は有機酸銅をより多く使用する
ことが好ましく、通常、水酸化銅又は有機酸銅を １０
〜７０重量％の範囲、好ましくは２０〜６０重量％の範
囲で用い、常温乃至加熱下に混練して均一とする。The treatment liquid of the present invention is prepared by mixing the above-described copper hydroxide or organic acid copper with a polyhydric alcohol. The composition ratio of copper hydroxide or organic acid copper and polyhydric alcohol in the treatment liquid is not particularly limited as long as a uniformly mixed solution can be prepared, but if more copper hydroxide or organic acid copper is used, It is preferable to use copper hydroxide or organic acid copper.
It is used in a range of 70% by weight, preferably 20 to 60% by weight, and is kneaded uniformly at room temperature or under heating.
なお、本発明の処理液の調整にあたっては、適宜、上記
以外の添加剤類を併用してもよいものであり、これらと
しては有機酸、アミン、有機溶剤、界面活性剤、銅その
他金属の塩類、ポリビニルアルコールなどが例示される
。In addition, when preparing the treatment liquid of the present invention, additives other than those mentioned above may be used in combination as appropriate, and these include organic acids, amines, organic solvents, surfactants, and salts of copper and other metals. , polyvinyl alcohol, etc.
上記の処理液を超耐熱性樹脂物品の所望部に、印刷、刷
毛塗、ディビイング、スプレーコート、バーコード、ロ
ールコートなどその他の塗布手段を使用し、不活性雰囲
気中？で熱処理することにより本発明の銅膜形成物品を
製造する。The above treatment liquid is applied to the desired part of the ultra-heat-resistant resin article by printing, brush coating, dibbing, spray coating, barcoding, roll coating, or other application methods in an inert atmosphere. The copper film-formed article of the present invention is manufactured by heat treatment.
非酸化性雰囲気としては、Ｎ２． Ａｒ、 ＣＯ２，Ｃ
Ｄ、 Ｎ２などのガス雰囲気下とする方法や、単に、塗
布面を耐熱性のテフロン等のフィルム類で被う等して、
加熱し、塗布層よりの分解発生ガス雰囲気に維持するこ
とによる。又、加熱は、赤外線、電子線、マイクロ波な
どの放射線加熱、電気炉、オーブン、オイル加熱、加圧
蒸気その他の手段を適宜使用する温度により選択してバ
ッチ或いは連続的に行うものであり、通常、昇温速度
５０〜ｂＨｒ、好ましくは１００〜ｂ
所定の温度、すなわち１６５℃から超耐熱性樹脂物品の
変形劣化温度以下の温度の範囲、好ましくは１７０℃〜
３００℃の温度の範囲に、単に加熱昇温するか、又は同
温度の範囲で３時間以下、好ましくは数分〜２時間程度
保持することによる。The non-oxidizing atmosphere is N2. Ar, CO2, C
D, under a gas atmosphere such as N2, or simply covering the coated surface with a heat-resistant film such as Teflon.
By heating and maintaining an atmosphere of gas decomposed from the coating layer. In addition, the heating is carried out batchwise or continuously by selecting radiation heating such as infrared rays, electron beams, microwaves, electric furnaces, ovens, oil heating, pressurized steam, and other means depending on the temperature used, Usually heating rate
50-bHr, preferably 100-b A predetermined temperature, i.e., a temperature range from 165°C to below the deformation deterioration temperature of the ultra-heat-resistant resin article, preferably 170°C-
The temperature may be simply heated to a temperature range of 300°C, or the temperature may be maintained at the same temperature range for 3 hours or less, preferably from several minutes to 2 hours.
以下、実施例、比較例によって本発明をさらに具体的に
説明する。尚、実施例、比較例中の部は特に断らない限
り重量基準である。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are based on weight unless otherwise specified.
実施例１
蟻酸銅１００部とグリセリン２００部とを撹拌混合して
粘性のある青色の処理液（以下、処理液１と記す）を得
た。Example 1 100 parts of copper formate and 200 parts of glycerin were stirred and mixed to obtain a viscous blue treatment liquid (hereinafter referred to as treatment liquid 1).
この処理液１を両面光沢面であるポリイミドフィルム（
商品名；カプトン、東し・デュポン■製、厚み ３０ｐ
）の片面に厚み２０１で塗布した後、ボンベよりの窒素
ガス雰囲気下において、３０分間で２００℃まで昇温し
、この温度で６０分間保持した後、取り出した。This treatment solution 1 was applied to a polyimide film (with glossy surfaces on both sides).
Product name: Kapton, made by Azuma DuPont ■, thickness 30p
) to a thickness of 201 cm, the temperature was raised to 200° C. in 30 minutes in a nitrogen gas atmosphere from a cylinder, held at this temperature for 60 minutes, and then taken out.
得られたポリイミドフィルムの表面には、光沢ある銅膜
が均一密着していた。A shiny copper film was uniformly adhered to the surface of the obtained polyimide film.
この銅膜の厚みは０．３／ａ、体積抵抗１． ＯＸ １
０−’Ω・１１セロテープ基盤目テスト（クロスカット
テスト）による剥離試験結果は１００／１００、煮沸２
時間後も膨れ剥離などは全く無かった。The thickness of this copper film is 0.3/a, and the volume resistance is 1. OX1
Peeling test result by 0-'Ω・11 Cellotape base test (cross cut test) is 100/100, boiling 2
Even after hours, there was no swelling or peeling.
また、処理液１の塗布厚みを１２０１とする他は上記と
同様にして均一に密着した光沢ある銅膜を得た。Further, a glossy copper film with uniform adhesion was obtained in the same manner as above except that the coating thickness of treatment liquid 1 was 120 mm.
この銅膜の厚みは３ＪＡ、体積抵抗７． ＯＸ １０−
’Ω・印、セロテープ基盤目テスト（クロスカットテス
ト）による剥離試験結果は１００／１００、煮沸２時間
後も膨れ剥離などは全く無かった。The thickness of this copper film is 3JA, and the volume resistance is 7. OX 10-
'Ω' mark: Peeling test result by Cellotape base cross-cut test (cross-cut test) was 100/100, and there was no swelling or peeling even after 2 hours of boiling.
実施例２
水酸化銅１００部とグリセリン２００部とを撹拌混合し
て粘性のある青色の処理液（以下、処理液２と記す）を
得た。Example 2 100 parts of copper hydroxide and 200 parts of glycerin were stirred and mixed to obtain a viscous blue treatment liquid (hereinafter referred to as treatment liquid 2).
この処理液２を使用し厚み１２０−の厚みに塗布する他
は実施例１と同様にして光沢ある銅膜が均一密着したポ
リイミドフィルムを得た。A polyimide film having a glossy copper film uniformly adhered thereto was obtained in the same manner as in Example 1, except that this treatment solution 2 was applied to a thickness of 120 mm.
この銅膜の厚みは６−１体積抵抗５． ＯＸ １０−’
Ω・印、セロテープ基盤目テスト（クロスカットテスト
）による剥離試験結果は１００／１００、煮沸２時間後
も膨れ剥離などは全く無かった。The thickness of this copper film is 6-1 volume resistance 5. OX 10-'
Ω mark, peel test result by Cellotape base test (cross cut test) was 100/100, and there was no swelling or peeling even after 2 hours of boiling.
実施例３
実施例１において、蟻酸銅１００部に代えて酢酸銅１０
０部を使用する他は同様にして処理液（以下、溶液３と
記す）を得、この処理液３を用いる他は同様にして光沢
ある銅膜が均一密着したポリイミドフィルムを得た。Example 3 In Example 1, 10 parts of copper acetate was substituted for 100 parts of copper formate.
A processing solution (hereinafter referred to as solution 3) was obtained in the same manner except that 0 part was used, and a polyimide film with a glossy copper film uniformly adhered was obtained in the same manner except that this processing solution 3 was used.
実施例４
実施例１において、グリセリン２００部に代えてトリエ
タノールアミン２００部を使用する他は同様にして処理
液（以下、処理液４と記す）を得、この処理液４を用い
る他は同様にして光沢ある銅膜が均一密着したポリイミ
ドフィルムを得た。Example 4 A treatment liquid (hereinafter referred to as treatment liquid 4) was obtained in the same manner as in Example 1, except that 200 parts of triethanolamine was used instead of 200 parts of glycerin; A polyimide film with a glossy copper film uniformly adhered was obtained.
実施例５
実施例１において、グリセリン２００部に代えてエチレ
ングリコール２００部を使用する他は同様にして処理液
（以下、処理液５と記す）を得、この処理液５を用いる
他は同様にして光沢ある銅膜が均一密着したポリイミド
フィルムを得た。Example 5 A treatment liquid (hereinafter referred to as treatment liquid 5) was obtained in the same manner as in Example 1, except that 200 parts of ethylene glycol was used instead of 200 parts of glycerin. A polyimide film with a glossy copper film uniformly adhered was obtained.
実施例６
実施例１において、ポリイミドフィルムに代えて、ＰＰ
Ｓの厚み３ｍｍの成形品を用い、処理液１を厚み１２０
−で塗布する他は同様として銅膜が密着した成形品を得
た。Example 6 In Example 1, instead of polyimide film, PP
Using a molded product S with a thickness of 3 mm, process liquid 1 was applied to a thickness of 120 mm.
A molded product with a copper film in close contact was obtained in the same manner except that it was coated with -.
この銅膜の厚みは３Ａ３、クロスカットテストによる剥
離試験結果は１００／１００、煮沸２時間後も膨れ剥離
などは全く無かった。The thickness of this copper film was 3A3, the peel test result by cross-cut test was 100/100, and there was no swelling or peeling even after 2 hours of boiling.
実施例７
実施例６において、水酸化銅１００部、グリセリン２０
０部及び蟻酸 １０部を撹拌混合して処理液（以下、処
理液６と記す）を得、この処理液６を使用する他は同様
として銅膜が密着した成形品を得た。Example 7 In Example 6, 100 parts of copper hydroxide, 20 parts of glycerin
A treatment liquid (hereinafter referred to as treatment liquid 6) was obtained by stirring and mixing 0 parts of formic acid and 10 parts of formic acid, and a molded article with a copper film in close contact was obtained in the same manner except that this treatment liquid 6 was used.
実施例８
実施例６において、処理液３を使用する他は同様として
銅膜が密着した成形品を得た。Example 8 A molded article with a copper film adhered to it was obtained in the same manner as in Example 6 except that treatment liquid 3 was used.
〔発明の作用および効果］
以上の如くである本発明の製造法によれば、従来は特別
の前処理を施した後でなければ、無電解メツキなどで密
着製に優れた銅膜を形成することが困難であった超耐熱
性の物品に極めて簡単な手段により容易に密着性に優れ
た銅膜が形成された物品が得られるので、この銅膜を電
気メツキ、無電解メツキ、真空蒸着、銅箔接着の代替、
溶接用下地などの下地処理として、銅張フィルム、銅張
板その他の用途に、或いは、そのまま或いは耐酸化塗膜
を形成して、導電性、熱伝導性膜として好適に使用され
るものである。[Operations and Effects of the Invention] According to the manufacturing method of the present invention as described above, conventionally, a copper film with excellent adhesion could be formed by electroless plating or the like only after special pretreatment. By using extremely simple methods, it is possible to easily obtain products with a copper film with excellent adhesion on ultra-heat-resistant products that have previously been difficult to produce. Alternative to copper foil adhesion,
It is suitable for use as a base treatment for welding, etc., for copper-clad films, copper-clad plates, and other uses, or as an electrically conductive and thermally conductive film, either as is or by forming an oxidation-resistant coating. .
Claims (1)
から選択された銅化合物と多価アルコールとを必須成分
とする混合液を塗布した後、非酸化性雰囲気中で１６５
℃以上で該超耐熱性樹脂物品の変形劣化温度以下の温度
に加熱することを特徴とする銅膜形成物品の製造法。After applying a mixed solution containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components to a desired part of an ultra-heat-resistant resin article, the mixture is heated to 165% in a non-oxidizing atmosphere.
A method for producing a copper film-forming article, which comprises heating at a temperature above .degree. C. and below the deformation deterioration temperature of the ultra-heat-resistant resin article.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325567A JPH01168865A (en) | 1987-12-24 | 1987-12-24 | Production of article coated with copper film |
| KR1019880017274A KR960010822B1 (en) | 1987-12-24 | 1988-12-22 | Method for porducing copper film-formed articles |
| EP88121504A EP0322764B1 (en) | 1987-12-24 | 1988-12-22 | Method for producing copper film-formed articles |
| DE8888121504T DE3879441T2 (en) | 1987-12-24 | 1988-12-22 | METHOD FOR PRODUCING BODIES WITH A COPPER COVER. |
| US07/288,928 US4913938A (en) | 1987-12-24 | 1988-12-23 | Method for producing copper film-formed articles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325567A JPH01168865A (en) | 1987-12-24 | 1987-12-24 | Production of article coated with copper film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01168865A true JPH01168865A (en) | 1989-07-04 |
Family
ID=18178329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62325567A Pending JPH01168865A (en) | 1987-12-24 | 1987-12-24 | Production of article coated with copper film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01168865A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257514A (en) * | 2005-03-17 | 2006-09-28 | Bando Chem Ind Ltd | Nanoscale metallic film and method for producing the film |
| WO2013136937A1 (en) | 2012-03-16 | 2013-09-19 | 株式会社Adeka | Copper film-forming composition, and method for producing copper film by using the composition |
| JP2015129318A (en) * | 2014-01-06 | 2015-07-16 | 四国化成工業株式会社 | Copper coating forming agent and formation method of copper coating |
| KR20160027174A (en) | 2013-07-25 | 2016-03-09 | 가부시키가이샤 아데카 | Composition for copper film formation and copper film production method using same |
| KR20160114175A (en) | 2014-03-12 | 2016-10-04 | 가부시키가이샤 아데카 | Copper film forming composition and process for manufacturing copper film using same |
-
1987
- 1987-12-24 JP JP62325567A patent/JPH01168865A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257514A (en) * | 2005-03-17 | 2006-09-28 | Bando Chem Ind Ltd | Nanoscale metallic film and method for producing the film |
| WO2013136937A1 (en) | 2012-03-16 | 2013-09-19 | 株式会社Adeka | Copper film-forming composition, and method for producing copper film by using the composition |
| US9028599B2 (en) | 2012-03-16 | 2015-05-12 | Adeka Corporation | Copper film-forming composition, and method for producing copper film by using the composition |
| KR20160027174A (en) | 2013-07-25 | 2016-03-09 | 가부시키가이샤 아데카 | Composition for copper film formation and copper film production method using same |
| JP2015129318A (en) * | 2014-01-06 | 2015-07-16 | 四国化成工業株式会社 | Copper coating forming agent and formation method of copper coating |
| KR20160114175A (en) | 2014-03-12 | 2016-10-04 | 가부시키가이샤 아데카 | Copper film forming composition and process for manufacturing copper film using same |
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