JP3585289B2 - New tricarbonyl group-containing silicon compounds and metal surface treatment agents - Google Patents
New tricarbonyl group-containing silicon compounds and metal surface treatment agents Download PDFInfo
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- JP3585289B2 JP3585289B2 JP15077395A JP15077395A JP3585289B2 JP 3585289 B2 JP3585289 B2 JP 3585289B2 JP 15077395 A JP15077395 A JP 15077395A JP 15077395 A JP15077395 A JP 15077395A JP 3585289 B2 JP3585289 B2 JP 3585289B2
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- carbon atoms
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- tricarbonyl
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Links
- 229910052751 metal Inorganic materials 0.000 title claims description 21
- 239000002184 metal Substances 0.000 title claims description 21
- 150000003377 silicon compounds Chemical class 0.000 title claims description 10
- 239000012756 surface treatment agent Substances 0.000 title description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000002587 enol group Chemical group 0.000 claims 2
- 150000002085 enols Chemical group 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 229910000077 silane Inorganic materials 0.000 description 24
- -1 silane compound Chemical class 0.000 description 22
- 125000000468 ketone group Chemical group 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- 229930194542 Keto Natural products 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000003449 preventive effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
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- 239000002253 acid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
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- 238000002845 discoloration Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
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- 239000010962 carbon steel Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
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- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MZFGYVZYLMNXGL-UHFFFAOYSA-N undec-10-enoyl chloride Chemical compound ClC(=O)CCCCCCCCC=C MZFGYVZYLMNXGL-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- SMUKODJVMQOSAB-UHFFFAOYSA-N 2-ethylbutanoyl chloride Chemical compound CCC(CC)C(Cl)=O SMUKODJVMQOSAB-UHFFFAOYSA-N 0.000 description 1
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 description 1
- MFIQXAVMTLKUJR-UHFFFAOYSA-N 2-methylpentanoyl chloride Chemical compound CCCC(C)C(Cl)=O MFIQXAVMTLKUJR-UHFFFAOYSA-N 0.000 description 1
- BUTKIHRNYUEGKB-UHFFFAOYSA-N 3,3-dimethylbutanoyl chloride Chemical compound CC(C)(C)CC(Cl)=O BUTKIHRNYUEGKB-UHFFFAOYSA-N 0.000 description 1
- ISULZYQDGYXDFW-UHFFFAOYSA-N 3-methylbutanoyl chloride Chemical compound CC(C)CC(Cl)=O ISULZYQDGYXDFW-UHFFFAOYSA-N 0.000 description 1
- PRRBQHNMYJRHFW-UHFFFAOYSA-M 3-oxoheptanoate Chemical compound CCCCC(=O)CC([O-])=O PRRBQHNMYJRHFW-UHFFFAOYSA-M 0.000 description 1
- KRIUXIBKTKZYHV-UHFFFAOYSA-N 3-oxohex-5-enoic acid Chemical compound OC(=O)CC(=O)CC=C KRIUXIBKTKZYHV-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- KQWWVLVLVYYYDT-UHFFFAOYSA-N ethyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OCC KQWWVLVLVYYYDT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- UCVODTZQZHMTPN-UHFFFAOYSA-N heptanoyl chloride Chemical compound CCCCCCC(Cl)=O UCVODTZQZHMTPN-UHFFFAOYSA-N 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Description
【０００１】
【産業上の利用分野】
本発明は銅、鉄鋼およびアルミニウム製品を主とする金属の防錆および金属と樹脂との接着性の改善等を行うための表面処理剤および該表面処理剤に好適な新規シラン化合物に関する。
【０００２】
【従来の技術】
各種金属に関する要求は様々である。例えばプリント回路用の銅箔は紙−フェノール樹脂含浸基材やガラス−エポキシ樹脂含浸基材等に加熱、加圧して積層して、銅張積層板が形成され、これをエッチングして回路網を形成し、これに半導体装置等の素子を搭載することにより電子機器用のボードが作られる。
これらの過程では基材との接着、加熱、酸やアルカリ液への浸漬、レジストインクの塗布、ハンダ付け等が行われるため、銅箔には各種の性能が要求される。また保管時に銅箔表面の酸化変色がないことも要求されている。これらの要求を満たすために、黄銅層形成処理（特公昭５１−３５７１１号公報、同５４−６７０１号公報）やクロメート処理、亜鉛または酸化亜鉛とクロム酸化物とからなる亜鉛−クロム基混合物被覆処理等（特公昭５８−７０７７号公報）が行われている。しかしながら、最近、プリント回路が緻密化しているので、使用されるプリント回路用銅箔に要求される特性はますます厳しくなっている。
【０００３】
又、鉄鋼製品は建築物、自動車、船舶、缶など様々なところで使用されているが、錆びるという重大な欠点がある。鉄製品の防錆剤には従来水溶性防錆剤、気化性防錆剤、油性防錆剤等の各種防錆剤が使用されている。一般的に水溶性防錆剤は一時的短時間の防錆を目的とし、長期の防錆には用いられていない。また気化性防錆剤は密閉状態で本来の防錆力を発揮するものである。油性防錆剤は比較的防錆力が強く長期の防錆に耐えるものであり、液状の防錆油、防錆添加剤や皮膜形成剤等を揮発性有機溶剤に溶解したもの、粘着性の防錆グリース等がある。このように様々な防錆剤が多数開発され、それぞれの環境によって使い分けられているが、今もなお、防錆剤の一層の充実が望まれているのが現状である。
又、アルミニウムまたはアルミニウム合金は軽量であるため自動車分野において、燃費向上の観点から注目され始めている。アルミニウム合金がパネル材として使用される場合は、プレス成形等の加工が施された後に塗装が行われるのが通常であり、特に自動車の外板材では耐食性に対する要求特性からカチオン型の電着塗装が施されている。しかしながら、アルミニウム合金に対する塗装の密着性が十分に得られず、また塗装後の耐食性も十分でないという欠点がある。
【０００４】
【発明が解決しようとする課題】
本発明はこうした要請に対応できる、すなわち金属、特には銅、鉄鋼およびアルミニウム製品に対して、金属表面に強く吸着し、薄膜においても防錆作用を有し、かつ樹脂との接着性に優れる新規なシラン化合物およびそれに用いた新規な金属表面処理剤を提供することを目的とするものである。
【０００５】
【課題を解決するための手段】
本発明者は鋭意研究を進めた結果、下記一般式（１）および（２）に示すトリカルボニル基を含有するケイ素化合物が金属表面に対して優れた防錆作用を有し、かつ金属と樹脂との接着性に優れることを見出した。
本発明はかかる知見に基づきなされたものであり、その要旨は、
（１）下記一般式（１）で表わされる新規トリカルボニル基含有ケイ素化合物。
【０００６】
【化３】
〔ただし、該トリカルボニル基含有ケイ素化合物は、上記一般式（１）の互変異性体であるエノール形も含む。また、一般式（１）においてＲ１は炭素数２〜１０のアルキレン基、Ｒ２は炭素数１〜５のアルキル基、Ｒ３，Ｒ４は炭素数１〜１０のアルキル基であって、かつＲ３，Ｒ４の少なくともいずれかが炭素数１〜５のとき、Ｒ１は炭素数６〜１０であり、またＲ１の炭素数が１〜５のとき、Ｒ３，Ｒ４の少なくともいずれかが炭素数６〜１０であり、ｘ，ｙ，ｚはそれぞれ０または１を示す。〕
（２）下記一般式（２）で表わされるトリカルボニル基含有ケイ素化合物を有効成分とする金属表面処理剤にある。
【０００８】
【化４】
〔ただし、該トリカルボニル基含有ケイ素化合物は、上記一般式（２）の互変異性体であるエノール型も含む。また、一般式（２）においてＲ１は炭素数２〜１０のアルキレン基、Ｒ２は炭素数１〜５のアルキル基、Ｒ３、Ｒ４はそれぞれ炭素数１〜１０のアルキル基であって、かつＲ３、Ｒ４の少なくともいずれかが炭素数１〜５のとき、Ｒ １ は炭素数６〜１０であり、またＲ １ の炭素数が１〜５のとき、Ｒ ３ ，Ｒ ４ の少なくともいずれかが炭素数６〜１０であり、ｘ、ｙ、ｚはそれぞれ０または１を示す〕
以下に本発明をさらに詳細に説明する。上記一般式（２）におけるＲ１は炭素数が２〜１０のアルキル基である。Ｒ２は炭素数が１〜５のアルキル基であるが、特には合成の容易性やシランの加水分解のし易さの点からメチル基、エチル基が好適である。Ｒ３およびＲ４は炭素数１〜１０のアルキル基である。アルキル基が長いと金属に表面処理したときにそのアルキル基が外側に配向するため撥水性を示す。同様にＲ１もアルキレン基が長いと撥水性が向上する。また、アルキル基が短いと立体障害が減少するためトリカルボニル基の金属に対する吸着性が増加する。
【００１０】
すなわち、Ｒ３およびＲ４は一方のアルキル基が長く、もう一方が短いことが撥水性およびトリカルボニル基の金属に対する吸着性の点から好適である。また、Ｒ１のアルキレン基が炭素数６〜１０と長く、Ｒ３および／またはＲ４のアルキル基が炭素数１〜５と短い場合も同様に撥水性および吸着性の点から好適である。さらにこの逆の関係すなわちＲ１のアルキレン基が炭素数１〜５と短く、Ｒ３および／またはＲ４のアルキル基が炭素数６〜１０と長い場合も同様に撥水性および吸着性の点から好ましい。
このような観点から、一般式（２）においてＲ１，Ｒ３，Ｒ４は、一般式（１）におけるＲ１，Ｒ３，Ｒ４と同義である場合、すなわち、Ｒ１が炭素数２〜１０のアルキレン基、Ｒ３，Ｒ４は炭素数１〜１０のアルキル基であって、かつＲ３，Ｒ４の少なくともいずれかが炭素数１〜５のとき、Ｒ１は炭素数６〜１０であり、またＲ１の炭素数が１〜５のとき、Ｒ３，Ｒ４の少なくともいずれかが炭素数６〜１０である場合が好ましい。
本発明の上記一般式（１），（２）で表わされるトリカルボニル基含有シラン化合物として、特に好ましいものを挙げると、例えば
【００１１】
【化５】
【化６】
などがある。ただし、上記化合物はケト形のみ記載しているが、下記に示すようにケト形とエノール形の互変異性体で存在しており、エノール形についても本特許の請求範囲に含まれる（以下、ケト形のみを記載するが、エノール形も含まれているものとする）。
【００１４】
【化７】
本発明の上記一般式（１）で表わされるトリカルボニル基含有シラン化合物は、反応式（３）および（４）または反応式（５）および（６）で表わされる反応により合成される。すなわち、前者はジカルボニル化合物と二重結合を有する化合物ｉを塩化マグネシウムおよびアミンの存在下で反応させた後〔反応式（３）参照〕、白金存在下でトリアルコキシシランと反応させる〔ヒドロシリル化反応、反応式（４）参照〕ことにより製造する方法、また、後者は二重結合を有するジカルボニル化合物と化合物ｉｉを塩化マグネシウムおよびアミンの存在下で反応させた後〔反応式（５）参照〕、白金存在下でトリアルコキシシランと反応させる〔ヒドロシリル化反応、反応式（６）参照〕ことにより製造する方法である。
【００１６】
【化８】
〔上記式中、Ｒ３，Ｒ４およびｘ，ｙ，ｚは前記一般式（１）におけるそれぞれの記号と同義であり、Ｒ５は結合手、または炭素数１〜８のアルキル基を示す〕
【００１８】
【化９】
（なお、上記式中、Ｒ５−ＣＨ２ＣＨ２−、Ｒ２はそれぞれ前記一般式（１）におけるＲ１，Ｒ２と同義である。）
【００２０】
【化１０】
（上記式中、Ｒ３，Ｒ４およびｘ，ｙ，ｚは前記一般式（１）におけるそれぞれの記号と同義であり、Ｒ５は結合手または炭素数１〜８のアルキル基を示す。）
【００２２】
【化１１】
（なお、上記式中、Ｒ５−ＣＨ２ＣＨ２−、Ｒ２はそれぞれ前記一般式（１）におけるＲ１，Ｒ２と同義である。）
また、上記反応式（３）〜（６）により同様にして上記一般式（２）で表わされるトリカルボニル基含有シラン化合物も製造することができる。
上記反応式（３）に表わされている二重結合を有する化合物ｉとして好ましいのは、アクリル酸クロリド、１０−ウンデセノイルクロリドである。また、二重結合を有するカルボン酸、例えばビニルアセトアセティックアシッドや４−ペンタノイックアシッド等を塩化チオニル、三塩化リン、五塩化リン等により酸クロリド化してもよい。
上記反応式（３）に表わされているジカルボニル化合物は２，４−ペンタンジオン、２，２，６，６−テトラメチル−３，５−ヘプタンジオン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸ｎ−ブチル、アセト酢酸ｔ−ブチル、プロピオニル酢酸エチル、ブチリル酢酸エチル、ジメチルマロネート、ジエチルマロネート等が挙げられる。
上記反応式（４）に表わされているトリアルコキシシランとして好ましいのは、トリメトキシシラン、トリエトキシシラン等である。
【００２４】
上記反応式（５）に表わされている化合物ｉｉはアセチルクロリド、プロピオニルクロリド、ブチリルクロリド、ｔ−ブチルアセチルクロリド、２−エチルブチリルクロリド、バレリルクロリド、イソバレリルクロリド、２−メチルバレリルクロリド、ヘキサノイルクロリド、２−エチルヘキサノイルクロリド、ヘプタノイルクロリド、オクタノイルクロリド、ノナノイルクロリド、デカノイルクロリド等が挙げられる。
上記反応式（５）に表わされている二重結合を有するジカルボニル化合物はアセト酢酸アリル等が挙げられる。
【００２５】
上記反応式（３）および（５）の反応は文献〔Ｍ．Ｗ．Ｒａｔｈｋｅ，Ｐ．Ｊ．，Ｃｏｗａｎ，Ｊ．Ｏｒｇ．Ｃｈｅｍ．，５０，２６２２（１９８８）またはＪ．Ｓｋａｒｚｅｗｓｋｉ，Ｔｅｔｒａｈｅｄｒｏｎ，４５，４５９３〕に基づいて合成できる。すなわち、反応溶媒にジカルボニル化合物と塩化マグネシウムを混合して混合溶液を得、この混合溶液中にアミンおよび化合物ｉまたはｉｉを順次滴下する。そしてこれらを滴下後、反応を十分行わせるために、還流することが好ましい。反応時間は５分〜２４時間程度で十分である。反応溶媒としては塩化メチレンまたはアセトニトリル等が好適である。また、この反応は水分を嫌うので気相から水分が混入しないように、乾燥した窒素、アルゴン等の水分を含まない気体の雰囲気下で行うことが好ましい。
反応混合物はカラムクロマトグラフィー、抽出、蒸留等の既知の手段により精製され、単離されうるが、抽出し蒸留する方法が簡便で好ましい。
また、反応式（４）および（６）のヒドロシリル化反応は、二重結合を有するトリカルボニル化合物と１〜２０倍モル量のトリアルコキシシランを、トリカルボニル化合物に対して１０−５〜１０−７倍モル量の塩化白金酸の存在下、室温〜１５０℃で数時間反応させることにより合成される。この反応は特には反応溶媒を必要としないが、トルエン等の溶媒を用いてもよい。
【００２６】
反応混合物はカラムクロマトグラフィー、蒸留等の既知の手段により精製され、単離されうるが、過剰のトリアルコキシシランを濃縮により除去するのみでも純度よくトリカルボニル基含有シラン化合物が得られる。
上記トリカルボニル基含有シラン化合物を金属表面処理剤として用いる場合、その対象金属には特に制限はないが、銅、鉄鋼、アルミニウムおよびそれらの合金等の表面処理剤として用いることが好適である。また、その膜厚は金属の種類および用途によってそれぞれ異なるが、数分子層〜数百μｍが好ましい。
上記トリカルボニル基含有シラン化合物は、そのまま金属に塗布してもよいが、メタノール、エタノール等のアルコール類、アセトン、酢酸エチル等の溶剤で０．００１〜２０重量％になるように希釈し、この液に金属を浸漬させる方法またはこの液を金属にシャワーする方法で塗布することが簡便で好ましい。また、それらの希釈液に水、酢酸水溶液または塩酸等を少量添加し、１時間〜２４時間程度撹拌するとシランの加水分解が十分に進行し、シロキサン皮膜がより厚く形成されるため、本発明の効果を十分に発揮することができる。
【００２７】
【実施例】
Ｉ．トリカルボニル基含有シラン化合物の合成例１
１．アセト酢酸メチルと１０−ウンデセノイルクロリドとの反応
【００２８】
【化１２】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、アセト酢酸メチル０．１５ｍｏｌ（１７．２ｇ）、塩化メチレン２００ｍｌ、塩化マグネシウム０．１５ｍｏｌ（１４．１ｇ）を入れた。０℃に冷却した後、ピリジン０．３ｍｏｌ（２３．４ｇ）を加え、１５分間撹拌した。混合液中に１０−ウンデセノイルクロリド０．１５ｍｏｌ（３０ｇ）を滴下し、０℃で１時間撹拌後、２時間、５０℃で撹拌した。反応混合物を０℃に冷却し、６ｍｏｌ／Ｌの塩酸を１１０ｍｌ滴下した。十分に撹拌後、有機層を水洗し、硫酸マグネシウムで乾燥した。溶媒を除去後、減圧蒸留により二重結合を有するトリカルボニル化合物を得た〔沸点：１２３．５〜１３０．０℃／０．４ｍｍＨｇ、収率：８１％（収量：３３．８ｇ）〕。得られた化合物はＧＣにより単成分であることを確認し、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図１〜３に示す。
図１〜３に示すように、下記の各シグナルが認められた。また、本化合物は１Ｈ−ＮＭＲの積分比より、ほとんどエノール形で存在することが確認された。
【００３０】
【化１３】
〔図１．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．３（ｓ，３Ｈ）
ｂ：１７．９（ｓ，エノール形），３．４（ｓ，ケト形）
ｃ：３．８（ｓ，３Ｈ）
ｄ：２．６〜２．７（ｔ，２Ｈ）
ｅ：１．６（ｍ，２Ｈ）
ｆ：１．３（ｍ，１０Ｈ）
ｇ：１．９〜２．０（ｍ，２Ｈ）
ｈ：５．７〜５．９（ｍ，１Ｈ）
ｉ：４．８〜５．０（ｍ，２Ｈ）
〔図２．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２５．７
ｂ：１０８．１（エノール形），４８．０（ケト形）
ｃ：５１．４
ｄ：３７．８
ｅ：２５．７
ｆ：２８．９〜２９．８
ｇ：３３．７
ｈ：１３８．９
ｉ：１１４．０
ｊまたはｌ：１９５．６または１９９．０
ｋ：１６７．４
〔図３．ＩＲ（ｃｍ−１）〕
νＣＨ：２８２０〜３０３０、νＣ＝Ｏ：１５５０〜１７２０
２．ヒドロシリル化反応
【００３２】
【化１４】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、トリメトキシシラン０．０２７ｍｏｌ（３．２５ｇ）と０．２％のエタノール溶液として塩化白金酸９．０×１０−７ｍｏｌ（０．２３ｍｌ）を入れた。混合液中に室温下で上記合成した二重結合を有するトリカルボニル化合物０．０１８ｍｏｌ（５．１ｇ）を滴下した。滴下後、７０℃、１時間加熱し、真空ポンプで１時間濃縮することによりトリカルボニル基含有シラン化合物Ａを得た〔収率：９６．６％（収量：６．９ｇ）〕。得られた化合物は１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図４〜６に示す。
図４〜６に示すように、下記の各シグナルが認められた。本化合物Ａはケト形とエノール形で存在し、その存在比は１Ｈ−ＮＭＲより、約２９：７１（ケト形：エノール形）であることが確認された。
【００３４】
【化１５】
〔図４．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．４（ｓ，３Ｈ）
ｂ：１８．１（ｓ，エノール形），３．７，５．４（ｓ，ケト形）
ｃ：３．８（ｓ，３Ｈ）
ｄ：２．７（ｔ，２Ｈ）
ｅ：１．７（ｍ，２Ｈ）
ｆ：１．２〜１．４（ｍ，１０Ｈ）
ｇ：１．２〜１．４（ｍ，２Ｈ）
ｈ：１．２〜１．４（ｍ，２Ｈ）
ｉ：０．６〜０．７（ｍ，２Ｈ）
ｊ：３．６（ｓ，９Ｈ）
〔図５．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２６．２
ｂ：１０９．１（エノール形），５９．１（ケト形）
ｃ：５２．０
ｄ：３８．９
ｅ：２６．７
ｆ：３０．２〜３０．７
ｇ：３４．２
ｈ：２３．８
ｉ：１０．３
ｊ：５０．９
ｋまたはｍ：１９６．９または２００．４
ｌ：１６７．９
〔図６．ＩＲ（ｃｍ−１）〕
νＣＨ：２８２０〜３０３０、νＣ＝Ｏ：１５５０〜１７２０
νＳｉＯＣＨ３：１０８０，８２０
ＩＩ．トリカルボニル基含有シラン化合物の合成例２
【００３６】
【化１６】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、アセト酢酸アリル０．０６ｍｏｌ（８．５ｇ）、塩化メチレン７０ｍｌ、塩化マグネシウム０．０６ｍｏｌ（５．７ｇ）を入れた。０℃に冷却した後、ピリジン０．１２ｍｏｌ（９．５ｇ）を加え、１５分間撹拌した。混合液中にオクタノイルクロリド０．０６ｍｏｌ（９．８ｇ）を滴下し、０℃で１時間撹拌後、２時間、５０℃で撹拌した。反応混合物を０℃に冷却し、６ｍｏｌ／Ｌの塩酸を４０ｍｌ滴下した。十分に撹拌後、有機層を水洗し、硫酸マグネシウムで乾燥した。溶媒を除去後、減圧蒸留により二重結合を有するトリカルボニル化合物を得た〔沸点：１０２．２〜１０４．１℃／０．５５ｍｍＨｇ、収率：６７％（収量：１０．８ｇ）〕。得られた化合物はＧＣにより単成分であることを確認し、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図７〜９に示す。
図７〜９に示すように、下記の各シグナルが認められた。本化合物Ａはケト形とエノール形で存在し、その存在比は１Ｈ−ＮＭＲの積分比より約１０：９０（ケト形：エノール形）であることが確認された。
【００３８】
【化１７】
〔図７．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．３（ｓ，３Ｈ）
ｂ：１７．９（ｓ，エノール形），３．４（ｓ，ケト形）
ｃ：４．７（ｍ，２Ｈ）
ｄ：５．９〜６．０（ｍ，１Ｈ）
ｅ：５．２〜５．４（ｍ，２Ｈ）
ｆ：２．６〜２．７（ｍ，２Ｈ）
ｇ：１．５〜１．７（ｍ，２Ｈ）
ｈ：１．３（ｍ，８Ｈ）
ｉ：０．９（ｍ，３Ｈ）
〔図８．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２５．６
ｂ：１０８．１（エノール形），４８．０（ケト形）
ｃ：６５．５
ｄ：１３１．８
ｅ：１１８．９
ｆ：３７．８
ｇ：２５．８
ｈ：２９．０〜３７．８
ｉ：１４．０
ｊまたはｌ：１９８．９または１９５．７
ｋ：１６６．７
〔図９．ＩＲ（ｃｍ−１）〕
νＣＨ：２８２０〜３０３０、νＣ＝Ｏ：１５５０〜１７２０
２．ヒドロシリル化反応
【００４０】
【化１８】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、トリメトキシシラン０．０１７ｍｏｌ（２．０ｇ）と０．２％のエタノール溶液として塩化白金酸５．５×１０−７ｍｏｌ（０．１４ｍｌ）を入れた。混合液中に室温下で上記合成した二重結合を有するトリカルボニル化合物０．０１１ｍｏｌ（２．９５ｇ）を滴下した。滴下後、７０℃、１時間加熱し、真空ポンプで１時間濃縮することによりトリカルボニル基含有シラン化合物Ｂを得た（収率：８９．９％（収量：３．８６ｇ）〕。得られた化合物は１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図１０〜１２に示す。
図１０〜１２に示すように、下記の各シグナルが認められた。本化合物Ｂはケト形とエノール形で存在し、その存在比は１Ｈ−ＮＭＲの積分比より約１８：８２（ケト形：エノール形）であることが確認された。
【００４２】
【化１９】
〔図１０．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．１（ｓ，３Ｈ）
ｂ：１７．９（ｓ，エノール形）、５．４，３．４（ｓ，ケト形）
ｃ：４．０〜４．１（ｍ，２Ｈ）
ｄ：１．６〜１．７（ｍ，２Ｈ）
ｅ：０．５〜０．６（ｍ，２Ｈ）
ｆ：３．４（ｓ，９Ｈ）
ｇ：２．５〜２．６（ｍ，２Ｈ）
ｈ：１．１〜１．５（ｍ，１０Ｈ）
ｉ：０．８〜０．９（ｍ，３Ｈ）
〔図１１．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２６．３
ｂ：１０９．４（エノール形）、１００．３，５９．３（ケト形）
ｃ：６７．６
ｄ：２３．２
ｅ：６．８
ｆ：５１．０
ｇ：３８．９
ｈ：２３．４〜３２．９
ｉ：１４．８
ｊまたはｌ：１９６．８または２００．１
ｋ：１６７．５
〔図１２．ＩＲ（ｃｍ−１）〕
νＣＨ：２８２０〜３０３０、νＣ＝Ｏ：１５５０〜１７２０
νＳｉＯＣＨ３：１０８０〜８２０
ＩＩＩ．トリカルボニル基含有シラン化合物の合成例３
１．アセト酢酸アリルとアセチルクロリドとの反応
【００４４】
【化２０】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、アセト酢酸アリル０．１５ｍｏｌ（２１．３ｇ）、塩化メチレン１６０ｍｌ、塩化マグネシウム０．１５ｍｏｌ（１４．３ｇ）を入れた。０℃に冷却した後、ピリジン０．３ｍｏｌ（２３．７ｇ）を加え、１５分間撹拌した。混合液中にアセチルクロリド０．１５ｍｏｌ（１１．８ｇ）を滴下し、０℃で１時間撹拌後、２時間、５０℃で撹拌した。反応混合物を０℃に冷却し、６ｍｏｌ／Ｌの塩酸を１００ｍｌ滴下した。十分に撹拌後、有機層を水洗し、硫酸マグネシウムで乾燥した。溶媒を除去後、減圧蒸留により二重結合を有するトリカルボニル化合物を得た〔沸点：５５．３〜５７．５℃／１．１ｍｍＨｇ、収率：５６％（収量：１５．５ｇ）〕。得られた化合物はＧＣにより単成分であることを確認し、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図１３〜１５に示す。
図１３〜１５に示すように、下記の各シグナルが認められた。本化合物は１Ｈ−ＮＭＲの積分比より、ほとんどエノール形で存在することが確認された。
【００４６】
【化２１】
〔図１３．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．４（ｓ，３Ｈ）
ｂ：１８．０（ｓ，エノール形），３．４（ｓ，ケト形）
ｃ：４．７（ｍ，２Ｈ）
ｄ：５．９〜６．０（ｍ，１Ｈ）
ｅ：５．３〜５．４（ｍ，２Ｈ）
ｆ：２．４（ｓ，３Ｈ）
〔図１４．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２６．０
ｂ：１０８．４（エノール形），４９．０（ケト形）
ｃ：６５．３
ｄ：１３１．８
ｅ：１１８．８
ｆ：２６．０
ｇ：１９６．５
ｈ：１６６．５
ｉ：１９６．５
〔図１５．ＩＲ（ｃｍ−１）〕
νＣＨ：２８９０〜３１００、νＣ＝Ｏ：１５５０〜１７２０
２．ヒドロシリル化反応
【００４８】
【化２２】
温度計、還流冷却器、滴下ロートを取り付けた５００ｍｌの四つ口フラスコを十分アルゴンで置換した後、トリメトキシシラン０．０１７ｍｏｌ（２．０ｇ）と０．２％のエタノール溶液として塩化白金酸５．５×１０−７ｍｏｌ（０．１４ｍｌ）を入れた。混合液中に室温下で上記合成した二重結合を有するトリカルボニル化合物０．０１１ｍｏｌ（２．０ｇ）を滴下した。滴下後、７０℃、１時間加熱し、真空ポンプで１時間濃縮することによりトリカルボニル基含有シラン化合物Ｃを得た（収率：８５．５％（収量：２．８９ｇ）〕。得られた化合物は１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲにより同定した。これらの結果を図１６〜１８に示す。
図１６〜１８に示すように、下記の各シグナルが認められた。本化合物は１Ｈ−ＮＭＲの積分比より、ほとんどエノール形で存在することが確認された。
【００５０】
【化２３】
〔図１６．１Ｈ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２．３（ｓ，３Ｈ）
ｂ：１７．９（ｓ，１Ｈ，エノール形），３．４，５．４（ｓ，ケト形）
ｃ：４．０〜４．１（ｍ，２Ｈ）
ｄ：１．６〜１．７（ｍ，２Ｈ）
ｅ：０．６（ｍ，２Ｈ）
ｆ：３．５（ｓ，９Ｈ）
ｇ：２．３（ｍ，３Ｈ）
〔図１７．１３Ｃ−ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）〕
ａ：２６．５
ｂ：１０９．４（エノール形），５９．４，１０１．０（ケト形）
ｃ：６７．６
ｄ：２３．３
ｅ：６．７
ｆ：５１．０
ｇ：２６．５
ｈ：１９７．９
ｉ：１６７．５
ｊ：１９７．９
〔図１８．ＩＲ（ｃｍ−１）〕
νＣＨ：２８２０〜３０３０、νＣ＝Ｏ：１５５０〜１７２０
νＳｉＯＣＨ３：１０８０〜８２０
ＩＶ．銅に対する防錆試験
電解銅箔（日鉱グールド・フォイル製；ＪＴＣ箔：厚さ７５μｍ、４．５×４．５ｃｍ）の光沢面をアセトンで脱脂し、３％の硫酸水溶液で洗浄した。この銅箔に上記のトリカルボニル基含有シラン化合物Ａ〜Ｃの６％メタノール溶液をスピンコーターで塗布後、１５０℃、３０分間乾燥させ、０．３μｍのトリカルボニル基含有シラン化合物Ａ〜Ｃの薄膜を作成し、これを試験片とした。この試験片を温度８０℃、湿度９５％の恒温恒湿槽に２４時間入れ、変色の程度で耐湿性を評価した。また、１８０℃、３０分間熱処理し、変色の程度で耐熱性を評価した。この結果を表１に示した。また比較としてなにも塗布していない銅箔についても同様に評価した。その結果を表１に併せて示した。
【００５２】
【表１】
Ｖ．炭素鋼に対する防錆試験
炭素鋼（Ｓ．４５Ｃ、日本テストパネル製、厚さ２．０ｍｍ、５．５×５．５ｃｍ）を１０００番のサンドペーパーで研磨後、アセトンで５分間超音波洗浄した。この炭素鋼表面に上記のトリカルボニル基含有シラン化合物Ａの所定濃度メタノール溶液（濃度および添加剤は表２参照）をスピンコーター（５００回転、６０秒）で塗布後、１５０℃、３０分間乾燥させ、トリカルボニル基含有シラン化合物Ａの薄膜を作成し、これを試験片とした。
この試験片を温度８０℃、湿度９５％の恒温恒湿槽に２４時間入れ、変色の程度で耐湿性を評価した。結果を表２に示した。また３％塩化ナトリウム水溶液中に２４時間浸漬し、変色の程度で耐塩水性を評価した。この結果を表２に示した。また比較としてなにも塗布していない炭素鋼についても同様に評価した。その結果を表２に併せて示した。
【００５４】
【表２】
ＶＩ．アルミニウムに対する防錆試験
アルミ板（Ａ５０５２Ｐ、日本テストパネル製、厚さ２．０ｍｍ、５．５×５．５ｃｍ）をアセトンで５分間超音波洗浄し、５％Ｎａ２ＣＯ３水溶液に３０分間浸漬後水洗した。このアルミ板表面に上記のトリカルボニル基含有シラン化合物Ａ〜Ｃの２％メタノール溶液をスピンコーター（５００回転、６０秒）で塗布後、１５０℃、３０分間乾燥させ、トリカルボニル基含有シラン化合物の薄膜を作成し、これを試験片とした。
この試験片を沸騰水に１時間浸漬し、変色の程度で耐湿性を評価した。この結果を表３に示した。また比較としてなにも塗布していないアルミニウムについても同様に評価した。その結果を表３に併せて示した。
【００５６】
【表３】
また、トリカルボニル基含有シラン化合物Ａ〜Ｃの０．１％メタノール溶液を上記と同様の方法でアルミ板に表面処理した後、エポキシ樹脂（エピコート８２８：１００部、ＬＸ２Ｓ：６０部、メタノール：１００部）をスピンコーターにより塗布し、７０℃、３時間熱処理し、厚さ２０μｍのエポキシ樹脂被膜を作成した。この試験片を５％食塩水に２日間浸漬後、碁盤目試験を行い樹脂との接着性を評価した。その結果を表４に示した。また、比較としてなにも塗布していないアルミニウムについても同様に評価した。その結果を表４に併せて示した。
【００５８】
【表４】
【発明の効果】
以上説明したように、本発明のトリカルボニル基含有シラン化合物は金属表面処理剤、特に銅、鉄鋼、アルミニウムの表面処理剤として有用なもので、耐熱性、防錆および樹脂との接着性に優れるという効果を有するものである。
【図面の簡単な説明】
【図１】トリカルボニル基含有シラン化合物の合成例１で得られた中間体の１Ｈ−ＮＭＲ、
【図２】同１３Ｃ−ＮＭＲ、
【図３】同ＦＴ−ＩＲ、
【図４】トリカルボニル基含有シラン化合物の合成例１で得られた同化合物の１Ｈ−ＮＭＲ、
【図５】同１３Ｃ−ＮＭＲ、
【図６】同ＦＴ−ＩＲ、
【図７】トリカルボニル基含有シラン化合物の合成例２で得られた中間体の１Ｈ−ＮＭＲ、
【図８】同１３Ｃ−ＮＭＲ、
【図９】同ＦＴ−ＩＲ、
【図１０】トリカルボニル基含有シラン化合物の合成例２で得られた同化合物の１Ｈ−ＮＭＲ、
【図１１】同１３Ｃ−ＮＭＲ、
【図１２】同ＦＴ−ＩＲ、
【図１３】トリカルボニル基含有シラン化合物の合成例３で得られた中間体の１Ｈ−ＮＭＲ、
【図１４】同１３Ｃ−ＮＭＲ、
【図１５】同ＦＴ−ＩＲ、
【図１６】トリカルボニル基含有シラン化合物の合成例３で得られた同化合物の１Ｈ−ＮＭＲ、
【図１７】同１３Ｃ−ＮＭＲ、
【図１８】同ＦＴ−ＩＲ。[0001]
[Industrial applications]
The present invention relates to a surface treatment agent for preventing rust of metals, mainly copper, steel and aluminum products, and improving the adhesion between a metal and a resin, and a novel silane compound suitable for the surface treatment agent.
[0002]
[Prior art]
The requirements for various metals vary. For example, copper foil for printed circuits is laminated by heating, pressing, and the like on a paper-phenol resin-impregnated base material or a glass-epoxy resin-impregnated base material to form a copper-clad laminate, which is etched to form a circuit network. A board for an electronic device is manufactured by forming and mounting elements such as a semiconductor device on the board.
In these processes, the copper foil is required to have various performances because bonding to the base material, heating, immersion in an acid or alkaline solution, application of a resist ink, soldering, and the like are performed. It is also required that the copper foil surface does not undergo oxidative discoloration during storage. In order to satisfy these requirements, a brass layer forming treatment (JP-B-51-35711 and JP-B-54-6701), a chromate treatment, and a coating treatment with a zinc-chromium group mixture composed of zinc or zinc oxide and chromium oxide. (Japanese Patent Publication No. 58-7077). However, recently, as printed circuits are becoming finer, characteristics required for copper foils for printed circuits used are becoming more and more severe.
[0003]
In addition, steel products are used in various places such as buildings, automobiles, ships, cans and the like, but have a serious drawback of rusting. Conventionally, various rust preventive agents such as a water-soluble rust preventive, a vaporizable rust preventive, and an oil-based rust preventive have been used as rust preventives for iron products. Generally, a water-soluble rust inhibitor is intended for temporary short-time rust prevention and is not used for long-term rust prevention. Further, the vaporizable rust preventive exerts its original rust preventive power in a closed state. Oil-based rust preventives have relatively strong rust-proofing ability and withstand long-term rust-proofing, and are prepared by dissolving liquid rust-preventive oil, rust-preventive additives and film-forming agents in volatile organic solvents, Rust prevention grease and the like are available. As described above, a large number of various rust preventive agents have been developed and used depending on the respective environments. However, even now, there is a demand for further enhancement of rust preventive agents.
Also, aluminum or aluminum alloys are starting to attract attention in the automotive field from the viewpoint of improving fuel efficiency because of their light weight. When an aluminum alloy is used as a panel material, coating is usually performed after processing such as press forming, and in particular, cationic electrodeposition coating is required for the outer panel material of automobiles due to the required properties for corrosion resistance. It has been subjected. However, there are drawbacks in that the adhesion of the coating to the aluminum alloy cannot be sufficiently obtained, and that the corrosion resistance after coating is not sufficient.
[0004]
[Problems to be solved by the invention]
The present invention can respond to such a demand, that is, a novel metal, particularly a copper, steel and aluminum product, which strongly adheres to the metal surface, has a rust-preventing action even in a thin film, and has excellent adhesion to a resin. It is an object of the present invention to provide a novel silane compound and a novel metal surface treating agent used therefor.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has found that a silicon compound containing a tricarbonyl group represented by the following general formulas (1) and (2) has an excellent rust-preventing action on the metal surface, It has been found that it has excellent adhesiveness with the adhesive.
The present invention has been made based on such findings, the gist of which is
(1) A novel tricarbonyl group-containing silicon compound represented by the following general formula (1).
[0006]
Embedded image
[However, the tricarbonyl group-containing silicon compound also includes an enol form which is a tautomer of the general formula (1). In the general formula (1), R 1 is an alkylene group having 2 to 10 carbon atoms, R 2 is an alkyl group having 1 to 5 carbon atoms, R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms, and when at least one of R 3, R 4 is from 1 to 5 carbon atoms, R 1 is 6 to 10 carbon atoms, and when the number of carbon atoms of R 1 is from 1 to 5, at least R 3, R 4 Any one has 6 to 10 carbon atoms, and x, y, and z each represent 0 or 1. ]
(2) A metal surface treating agent comprising a tricarbonyl group-containing silicon compound represented by the following general formula (2) as an active ingredient.
[0008]
Embedded image
[However, the tricarbonyl group-containing silicon compound also includes an enol type which is a tautomer of the general formula (2). Further, R 1 in the general formula (2) is an alkylene group, R 2 represents an alkyl group having 1 to 5 carbon atoms, R 3, R 4 are each an alkyl group having 1 to 10 carbon atoms having 2 to 10 carbon atoms and R3, when at least one of R4 is C1-5, R 1 is 6 to 10 carbon atoms, and when the number of carbon atoms of R 1 is from 1 to 5, R 3, at least one of R 4
Hereinafter, the present invention will be described in more detail. R 1 in the general formula (2) is an alkyl group having 2 to 10 carbon atoms. R 2 is an alkyl group having 1 to 5 carbon atoms, and in particular, a methyl group and an ethyl group are preferable in view of easiness of synthesis and hydrolysis of silane. R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms. When the alkyl group is long, when the metal is subjected to surface treatment, the alkyl group is oriented outward, so that the metal exhibits water repellency. Similarly, when R 1 has a long alkylene group, the water repellency is improved. Further, when the alkyl group is short, steric hindrance is reduced, so that the adsorbability of the tricarbonyl group to the metal is increased.
[0010]
That is, it is preferable that one of R 3 and R 4 has a long alkyl group and the other has a short one in terms of water repellency and adsorptivity of a tricarbonyl group to a metal. Also, the case where the alkylene group of R 1 has a long carbon number of 6 to 10 and the alkyl group of R 3 and / or R 4 has a short carbon number of 1 to 5 is similarly preferable from the viewpoint of water repellency and adsorptivity. Further, when the alkylene group of R 1 is as short as 1 to 5 carbon atoms and the alkyl group of R 3 and / or R 4 is as long as 6 to 10 carbon atoms, the water repellency and the adsorptivity are similarly increased. preferable.
From this point of view, R 1, R 3, R 4 in formula (2), R 1 in the general formula (1), R 3, if R 4 as synonymous, i.e., the number R 1 carbon 2 When R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms and at least one of R 3 and R 4 has 1 to 5 carbon atoms, R 1 has 6 to 10 carbon atoms. When R 1 has 1 to 5 carbon atoms, it is preferable that at least one of R 3 and R 4 has 6 to 10 carbon atoms.
Particularly preferred tricarbonyl group-containing silane compounds represented by the above general formulas (1) and (2) of the present invention include, for example,
Embedded image
Embedded image
and so on. However, although only the keto form is described, the compound exists as a tautomer of a keto form and an enol form as shown below, and the enol form is also included in the claims of the present invention (hereinafter, referred to as “enol form”). Only the keto form is described, but the enol form is also included).
[0014]
Embedded image
The tricarbonyl group-containing silane compound represented by the general formula (1) of the present invention is synthesized by the reaction represented by the reaction formulas (3) and (4) or the reaction formulas (5) and (6). That is, in the former, a dicarbonyl compound and a compound i having a double bond are reacted in the presence of magnesium chloride and an amine [see reaction formula (3)], and then reacted with trialkoxysilane in the presence of platinum [hydrosilylation] Reaction, see reaction formula (4)], and the latter is to react a dicarbonyl compound having a double bond with compound ii in the presence of magnesium chloride and an amine [see reaction formula (5)]. And a reaction with a trialkoxysilane in the presence of platinum [hydrosilylation reaction, see reaction formula (6)].
[0016]
Embedded image
[In the above formula, R 3 and R 4 and x, y and z have the same meanings as those in the general formula (1), and R 5 represents a bond or an alkyl group having 1 to 8 carbon atoms.]
[0018]
Embedded image
(In the above formula, R 5 —CH 2 CH 2 — and R 2 have the same meanings as R 1 and R 2 in the general formula (1), respectively.)
[0020]
Embedded image
(In the above formula, R 3 , R 4 and x, y, z have the same meanings as those in the general formula (1), and R 5 represents a bond or an alkyl group having 1 to 8 carbon atoms.)
[0022]
Embedded image
(In the above formula, R 5 —CH 2 CH 2 — and R 2 have the same meanings as R 1 and R 2 in the general formula (1), respectively.)
Further, a tricarbonyl group-containing silane compound represented by the above general formula (2) can be produced in the same manner according to the above reaction formulas (3) to (6).
Preferred as the compound i having a double bond represented by the above reaction formula (3) is acrylic acid chloride and 10-undecenoyl chloride. Further, a carboxylic acid having a double bond, for example, vinyl acetoacetic acid or 4-pentanoic acid, may be acid chlorided with thionyl chloride, phosphorus trichloride, phosphorus pentachloride or the like.
The dicarbonyl compound represented by the above reaction formula (3) is 2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, methyl acetoacetate, ethyl acetoacetate, Examples include n-butyl acetate, t-butyl acetoacetate, ethyl propionyl acetate, ethyl butyryl acetate, dimethyl malonate, and diethyl malonate.
Preferred as the trialkoxysilane represented by the above reaction formula (4) are trimethoxysilane, triethoxysilane and the like.
[0024]
The compound ii represented by the above reaction formula (5) is acetyl chloride, propionyl chloride, butyryl chloride, t-butylacetyl chloride, 2-ethylbutyryl chloride, valeryl chloride, isovaleryl chloride, 2-methyl Valeryl chloride, hexanoyl chloride, 2-ethylhexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride and the like can be mentioned.
The dicarbonyl compound having a double bond represented by the above reaction formula (5) includes, for example, allyl acetoacetate.
[0025]
The reactions of the above reaction formulas (3) and (5) are described in literature [M. W. Ratke, P .; J. Cowan, J .; Org. Chem. , 50, 2622 (1988) or J. Amer. Skarzewski, Tetrahedron, 45 , 4593]. That is, a dicarbonyl compound and magnesium chloride are mixed in a reaction solvent to obtain a mixed solution, and an amine and a compound i or ii are sequentially dropped into the mixed solution. Then, after these are dropped, it is preferable to carry out reflux in order to carry out the reaction sufficiently. A reaction time of about 5 minutes to 24 hours is sufficient. As a reaction solvent, methylene chloride or acetonitrile is suitable. In addition, since this reaction dislikes moisture, it is preferable to perform the reaction in an atmosphere of a moisture-free gas such as nitrogen or argon so that moisture does not enter from the gas phase.
The reaction mixture can be purified and isolated by known means such as column chromatography, extraction and distillation, but the method of extraction and distillation is simple and preferred.
In addition, the hydrosilylation reaction of the reaction formulas (4) and (6) is performed by adding a tricarbonyl compound having a double bond and a 1 to 20-fold molar amount of trialkoxysilane to 10 −5 to 10 − with respect to the tricarbonyl compound. It is synthesized by reacting at room temperature to 150 ° C. for several hours in the presence of a 7- fold molar amount of chloroplatinic acid. This reaction does not particularly require a reaction solvent, but a solvent such as toluene may be used.
[0026]
The reaction mixture can be purified and isolated by known means such as column chromatography and distillation, but a tricarbonyl group-containing silane compound can be obtained with high purity only by removing excess trialkoxysilane by concentration.
When the tricarbonyl group-containing silane compound is used as a metal surface treating agent, the target metal is not particularly limited, but is preferably used as a surface treating agent for copper, steel, aluminum, and alloys thereof. In addition, the film thickness varies depending on the type and use of the metal, but is preferably several molecular layers to several hundred μm.
The tricarbonyl group-containing silane compound may be directly applied to a metal, but diluted with a solvent such as an alcohol such as methanol or ethanol, acetone or ethyl acetate to a concentration of 0.001 to 20% by weight. It is simple and preferable to apply the method by dipping the metal in the liquid or by showering the liquid on the metal. When a small amount of water, an aqueous solution of acetic acid or hydrochloric acid is added to these diluents, and the mixture is stirred for about 1 to 24 hours, hydrolysis of the silane proceeds sufficiently and a siloxane film is formed thicker. The effect can be fully exhibited.
[0027]
【Example】
I. Synthesis Example 1 of Tricarbonyl Group-Containing Silane Compound
1. Reaction of methyl acetoacetate with 10-undecenoyl chloride
Embedded image
After sufficiently replacing the 500-ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.15 mol (17.2 g) of methyl acetoacetate, 200 ml of methylene chloride, and 0.15 mol of magnesium chloride (14. 1g). After cooling to 0 ° C., 0.3 mol (23.4 g) of pyridine was added, and the mixture was stirred for 15 minutes. 0.15 mol (30 g) of 10-undecenoyl chloride was added dropwise to the mixture, and the mixture was stirred at 0 ° C for 1 hour and then at 50 ° C for 2 hours. The reaction mixture was cooled to 0 ° C., and 110 ml of 6 mol / L hydrochloric acid was added dropwise. After sufficient stirring, the organic layer was washed with water and dried over magnesium sulfate. After removing the solvent, a tricarbonyl compound having a double bond was obtained by distillation under reduced pressure [boiling point: 123.5 to 130.0 ° C / 0.4 mmHg, yield: 81% (yield: 33.8 g)]. The obtained compound was confirmed to be a single component by GC, and identified by 1 H-NMR, 13 C-NMR, and FT-IR. These results are shown in FIGS.
As shown in FIGS. 1 to 3, the following signals were observed. Further, it was confirmed from the integration ratio of 1 H-NMR that the present compound was almost present in an enol form.
[0030]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.3 (s, 3H)
b: 17.9 (s, enol form), 3.4 (s, keto form)
c: 3.8 (s, 3H)
d: 2.6 to 2.7 (t, 2H)
e: 1.6 (m, 2H)
f: 1.3 (m, 10H)
g: 1.9 to 2.0 (m, 2H)
h: 5.7 to 5.9 (m, 1H)
i: 4.8 to 5.0 (m, 2H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 25.7
b: 108.1 (enol type), 48.0 (keto type)
c: 51.4
d: 37.8
e: 25.7
f: 28.9 to 29.8
g: 33.7
h: 138.9
i: 114.0
j or l: 195.6 or 199.0
k: 167.4
[FIG. IR (cm -1 )]
ν CH: 2820~3030, ν C = O: 1550~1720
2. Hydrosilylation reaction [0032]
Embedded image
After sufficiently replacing the 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.027 mol (3.25 g) of trimethoxysilane and a 0.2% ethanol solution of chloroplatinic acid 9 were prepared. 0.0 × 10 −7 mol (0.23 ml). At room temperature, 0.018 mol (5.1 g) of the tricarbonyl compound having a double bond synthesized above was dropped into the mixture at room temperature. After the dropwise addition, the mixture was heated at 70 ° C. for 1 hour and concentrated by a vacuum pump for 1 hour to obtain a tricarbonyl group-containing silane compound A [yield: 96.6% (yield: 6.9 g)]. The obtained compound was identified by 1 H-NMR, 13 C-NMR and FT-IR. These results are shown in FIGS.
As shown in FIGS. 4 to 6, the following signals were observed. This compound A exists in a keto form and an enol form, and the abundance ratio was confirmed to be about 29:71 (keto form: enol form) by 1 H-NMR.
[0034]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.4 (s, 3H)
b: 18.1 (s, enol form), 3.7, 5.4 (s, keto form)
c: 3.8 (s, 3H)
d: 2.7 (t, 2H)
e: 1.7 (m, 2H)
f: 1.2 to 1.4 (m, 10H)
g: 1.2 to 1.4 (m, 2H)
h: 1.2 to 1.4 (m, 2H)
i: 0.6 to 0.7 (m, 2H)
j: 3.6 (s, 9H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 26.2
b: 109.1 (enol type), 59.1 (keto type)
c: 52.0
d: 38.9
e: 26.7
f: 30.2-30.7
g: 34.2
h: 23.8
i: 10.3
j: 50.9
k or m: 196.9 or 200.4
l: 167.9
[FIG. IR (cm -1 )]
ν CH: 2820~3030, ν C = O: 1550~1720
ν SiOCH3 : 1080,820
II. Synthesis Example 2 of Tricarbonyl Group-Containing Silane Compound
[0036]
Embedded image
After sufficiently replacing the 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.06 mol (8.5 g) of allyl acetoacetate, 70 ml of methylene chloride, 0.06 mol of magnesium chloride (5. 7g). After cooling to 0 ° C., 0.12 mol (9.5 g) of pyridine was added, and the mixture was stirred for 15 minutes. 0.06 mol (9.8 g) of octanoyl chloride was added dropwise to the mixture, and the mixture was stirred at 0 ° C for 1 hour and then at 50 ° C for 2 hours. The reaction mixture was cooled to 0 ° C., and 40 ml of 6 mol / L hydrochloric acid was added dropwise. After sufficient stirring, the organic layer was washed with water and dried over magnesium sulfate. After removing the solvent, a tricarbonyl compound having a double bond was obtained by distillation under reduced pressure [boiling point: 102.2 to 104.1 ° C / 0.55 mmHg, yield: 67% (yield: 10.8 g)]. The obtained compound was confirmed to be a single component by GC, and identified by 1 H-NMR, 13 C-NMR, and FT-IR. These results are shown in FIGS.
As shown in FIGS. 7 to 9, the following signals were observed. This compound A exists in a keto form and an enol form, and the abundance ratio was confirmed to be about 10:90 (keto form: enol form) from the integration ratio of 1 H-NMR.
[0038]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.3 (s, 3H)
b: 17.9 (s, enol form), 3.4 (s, keto form)
c: 4.7 (m, 2H)
d: 5.9 to 6.0 (m, 1H)
e: 5.2 to 5.4 (m, 2H)
f: 2.6 to 2.7 (m, 2H)
g: 1.5 to 1.7 (m, 2H)
h: 1.3 (m, 8H)
i: 0.9 (m, 3H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 25.6
b: 108.1 (enol type), 48.0 (keto type)
c: 65.5
d: 131.8
e: 118.9
f: 37.8
g: 25.8
h: 29.0-37.8
i: 14.0
j or l: 198.9 or 195.7
k: 166.7
[FIG. IR (cm -1 )]
ν CH: 2820~3030, ν C = O: 1550~1720
2. Hydrosilylation reaction [0040]
Embedded image
After sufficiently replacing the 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.017 mol (2.0 g) of trimethoxysilane and 0.2% ethanol solution of chloroplatinic acid were added. 0.5 × 10 −7 mol (0.14 ml). At room temperature, 0.011 mol (2.95 g) of the tricarbonyl compound having a double bond synthesized above was added dropwise to the mixture at room temperature. After the dropwise addition, the mixture was heated at 70 ° C. for 1 hour and concentrated by a vacuum pump for 1 hour to obtain a tricarbonyl group-containing silane compound B (yield: 89.9% (yield: 3.86 g)). The compound was identified by 1 H-NMR, 13 C-NMR, and FT-IR, and the results are shown in FIGS.
As shown in FIGS. 10 to 12, the following signals were observed. This compound B exists in a keto form and an enol form, and the abundance ratio was confirmed to be about 18:82 (keto form: enol form) based on the integration ratio of 1 H-NMR.
[0042]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.1 (s, 3H)
b: 17.9 (s, enol form), 5.4, 3.4 (s, keto form)
c: 4.0 to 4.1 (m, 2H)
d: 1.6 to 1.7 (m, 2H)
e: 0.5 to 0.6 (m, 2H)
f: 3.4 (s, 9H)
g: 2.5 to 2.6 (m, 2H)
h: 1.1 to 1.5 (m, 10H)
i: 0.8 to 0.9 (m, 3H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 26.3
b: 109.4 (enol form), 100.3, 59.3 (keto form)
c: 67.6
d: 23.2
e: 6.8
f: 51.0
g: 38.9
h: 23.4-32.9
i: 14.8
j or l: 196.8 or 200.1
k: 167.5
[FIG. IR (cm -1 )]
ν CH: 2820~3030, ν C = O: 1550~1720
ν SiOCH3 : 1800-820
III. Synthesis Example 3 of Tricarbonyl Group-Containing Silane Compound
1. Reaction of allyl acetoacetate with acetyl chloride
Embedded image
After sufficiently replacing the 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, allyl acetoacetate 0.15 mol (21.3 g), methylene chloride 160 ml, magnesium chloride 0.15 mol (14. 3g). After cooling to 0 ° C., 0.3 mol (23.7 g) of pyridine was added, and the mixture was stirred for 15 minutes. 0.15 mol (11.8 g) of acetyl chloride was added dropwise to the mixture, and the mixture was stirred at 0 ° C for 1 hour and then at 50 ° C for 2 hours. The reaction mixture was cooled to 0 ° C., and 100 ml of 6 mol / L hydrochloric acid was added dropwise. After sufficient stirring, the organic layer was washed with water and dried over magnesium sulfate. After removing the solvent, a tricarbonyl compound having a double bond was obtained by distillation under reduced pressure [boiling point: 55.3 to 57.5 ° C / 1.1 mmHg, yield: 56% (yield: 15.5 g)]. The obtained compound was confirmed to be a single component by GC, and identified by 1 H-NMR, 13 C-NMR, and FT-IR. These results are shown in FIGS.
As shown in FIGS. 13 to 15, the following signals were observed. From the integration ratio of 1 H-NMR, it was confirmed that the present compound was almost present in an enol form.
[0046]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.4 (s, 3H)
b: 18.0 (s, enol form), 3.4 (s, keto form)
c: 4.7 (m, 2H)
d: 5.9 to 6.0 (m, 1H)
e: 5.3 to 5.4 (m, 2H)
f: 2.4 (s, 3H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 26.0
b: 108.4 (enol type), 49.0 (keto type)
c: 65.3
d: 131.8
e: 118.8
f: 26.0
g: 196.5
h: 166.5
i: 196.5
[FIG. IR (cm -1 )]
ν CH: 2890~3100, ν C = O: 1550~1720
2. Hydrosilylation reaction [0048]
Embedded image
After sufficiently replacing the 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.017 mol (2.0 g) of trimethoxysilane and 0.2% ethanol solution of chloroplatinic acid were added. 0.5 × 10 −7 mol (0.14 ml). At room temperature, 0.011 mol (2.0 g) of the tricarbonyl compound having a double bond synthesized above was dropped into the mixture at room temperature. After the dropwise addition, the mixture was heated at 70 ° C. for 1 hour and concentrated by a vacuum pump for 1 hour to obtain a tricarbonyl group-containing silane compound C (yield: 85.5% (yield: 2.89 g)). The compound was identified by 1 H-NMR, 13 C-NMR, and FT-IR, and the results are shown in FIGS.
As shown in FIGS. 16 to 18, the following signals were observed. From the integration ratio of 1 H-NMR, it was confirmed that the present compound was almost present in an enol form.
[0050]
Embedded image
[FIG. 1 H-NMR (CDCl 3 , δ ppm)]
a: 2.3 (s, 3H)
b: 17.9 (s, 1H, enol form), 3.4, 5.4 (s, keto form)
c: 4.0 to 4.1 (m, 2H)
d: 1.6 to 1.7 (m, 2H)
e: 0.6 (m, 2H)
f: 3.5 (s, 9H)
g: 2.3 (m, 3H)
[FIG. 13 C-NMR (CDCl 3 , δ ppm)]
a: 26.5
b: 109.4 (enol type), 59.4, 101.0 (keto type)
c: 67.6
d: 23.3
e: 6.7
f: 51.0
g: 26.5
h: 197.9
i: 167.5
j: 197.9
[FIG. IR (cm -1 )]
ν CH: 2820~3030, ν C = O: 1550~1720
ν SiOCH3 : 1800-820
IV. Rust prevention test on copper The glossy surface of electrolytic copper foil (manufactured by Nikko Gould Foil; JTC foil: thickness 75 µm, 4.5 x 4.5 cm) is degreased with acetone and washed with a 3% aqueous sulfuric acid solution. did. The copper foil is coated with a 6% methanol solution of the above-mentioned tricarbonyl group-containing silane compounds A to C by a spin coater, dried at 150 ° C. for 30 minutes, and formed into a thin film of 0.3 μm of the tricarbonyl group-containing silane compounds A to C. Was prepared and used as a test piece. The test piece was placed in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 95% for 24 hours, and the moisture resistance was evaluated by the degree of discoloration. Further, heat treatment was performed at 180 ° C. for 30 minutes, and heat resistance was evaluated based on the degree of discoloration. The results are shown in Table 1. For comparison, a copper foil to which no coating was applied was similarly evaluated. The results are shown in Table 1.
[0052]
[Table 1]
V. Rust test <br/> carbon steel to carbon steel (S.45C, manufactured by Nippon Test Panel, thickness 2.0 mm, 5.5 × 5.5cm) after polishing at No. 1000 of the
The test piece was placed in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 95% for 24 hours, and the moisture resistance was evaluated by the degree of discoloration. The results are shown in Table 2. The sample was immersed in a 3% aqueous sodium chloride solution for 24 hours, and the degree of discoloration was evaluated for salt water resistance. The results are shown in Table 2. For comparison, carbon steel not coated with anything was similarly evaluated. The results are also shown in Table 2.
[0054]
[Table 2]
VI. Rust test <br/> aluminum plate to aluminum (A5052P, manufactured by Nippon Test Panel, thickness 2.0 mm, 5.5 × 5.5cm) and washed 5 min ultrasonically acetone, 5% Na 2 CO 3 aqueous solution And then washed with water. A 2% methanol solution of the above-mentioned tricarbonyl group-containing silane compounds A to C is applied to the surface of the aluminum plate with a spin coater (500 rotations, 60 seconds), dried at 150 ° C. for 30 minutes, and dried. A thin film was prepared and used as a test piece.
The test piece was immersed in boiling water for 1 hour, and the moisture resistance was evaluated based on the degree of discoloration. Table 3 shows the results. For comparison, aluminum that was not coated with anything was also evaluated. The results are also shown in Table 3.
[0056]
[Table 3]
Also, a 0.1% methanol solution of tricarbonyl group-containing silane compounds A to C was subjected to surface treatment on an aluminum plate in the same manner as described above, and then epoxy resin (Epicoat 828: 100 parts, LX2S: 60 parts, methanol: 100 parts) Was applied by a spin coater and heat-treated at 70 ° C. for 3 hours to form an epoxy resin film having a thickness of 20 μm. After this test piece was immersed in 5% saline for 2 days, a grid test was performed to evaluate the adhesiveness to the resin. Table 4 shows the results. For comparison, aluminum that was not coated with anything was similarly evaluated. The results are also shown in Table 4.
[0058]
[Table 4]
【The invention's effect】
As described above, the tricarbonyl group-containing silane compound of the present invention is useful as a metal surface treatment agent, particularly a copper, steel, and aluminum surface treatment agent, and has excellent heat resistance, rust prevention, and adhesion to a resin. This has the effect.
[Brief description of the drawings]
[1] 1 H-NMR of the intermediate obtained in Synthesis Example 1 tricarbonyl group-containing silane compound,
FIG. 2 shows the same 13 C-NMR,
FIG. 3 shows the FT-IR,
FIG. 4 shows a 1 H-NMR of the tricarbonyl group-containing silane compound obtained in Synthesis Example 1 of the same,
FIG. 5 shows 13 C-NMR,
FIG. 6 shows the FT-IR,
FIG. 7 shows 1 H-NMR of an intermediate obtained in Synthesis Example 2 of a tricarbonyl group-containing silane compound,
FIG. 8: 13 C-NMR,
FIG. 9 shows the FT-IR,
FIG. 10 shows 1 H-NMR of a tricarbonyl group-containing silane compound obtained in Synthesis Example 2 of the same,
FIG. 11 shows 13 C-NMR,
FIG. 12 shows the FT-IR,
FIG. 13 shows 1 H-NMR of an intermediate obtained in Synthesis Example 3 of a tricarbonyl group-containing silane compound,
FIG. 14 shows 13 C-NMR,
FIG. 15 shows the FT-IR,
FIG. 16 shows 1 H-NMR of a tricarbonyl group-containing silane compound obtained in Synthesis Example 3 of the same,
FIG. 17 shows the same 13 C-NMR,
FIG. 18 is the same FT-IR.
Claims (2)
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