JPH06279463A - Novel benzotriazole silanes, their production and surface treatment agent containing the same - Google Patents
Novel benzotriazole silanes, their production and surface treatment agent containing the sameInfo
- Publication number
- JPH06279463A JPH06279463A JP5070046A JP7004693A JPH06279463A JP H06279463 A JPH06279463 A JP H06279463A JP 5070046 A JP5070046 A JP 5070046A JP 7004693 A JP7004693 A JP 7004693A JP H06279463 A JPH06279463 A JP H06279463A
- Authority
- JP
- Japan
- Prior art keywords
- benzotriazole
- compound
- general formula
- formula
- compound represented
- 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
- 239000012756 surface treatment agent Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- XCMSVSBUVANQIE-UHFFFAOYSA-N [SiH4].N1N=NC2=C1C=CC=C2 Chemical class [SiH4].N1N=NC2=C1C=CC=C2 XCMSVSBUVANQIE-UHFFFAOYSA-N 0.000 title description 5
- -1 triazole compound Chemical class 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011889 copper foil Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000012964 benzotriazole Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- LXWLHXNRALVRSL-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propylsilane Chemical compound [SiH3]CCCOCC1CO1 LXWLHXNRALVRSL-UHFFFAOYSA-N 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002845 discoloration Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical group [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004262 preparative liquid chromatography Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- FTNCLFLVKLFJPL-UHFFFAOYSA-N triethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CC[Si](CC)(CC)CCCOCC1CO1 FTNCLFLVKLFJPL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属表面の防錆の改善
等を行うための表面処理剤、特にはプリント回路用銅張
積層板等に用いられる銅箔用表面処理剤として有用な新
規なベンゾトリアゾールシラン化合物及びその製造方
法、並びにその用途に関する。FIELD OF THE INVENTION The present invention relates to a novel surface treatment agent for improving rust prevention of a metal surface, and particularly useful as a surface treatment agent for copper foil used for copper clad laminates for printed circuits. Benzotriazole silane compound, its production method, and its use.
【０００２】[0002]
【従来の技術】プリント回路用の銅張積層板は銅箔を紙
−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。たとえ
ば、通常Ｍ面（粗化面、以下同様）と呼称されている基
材と接着される側には主として基材との接着性、耐薬品
性等が要求され、又Ｍ面の反対側の通常Ｓ面（光沢面、
以下同様）と呼称されている側には主として耐熱性、耐
湿性等が要求されている。又これらの両面には保管時に
銅箔の酸化変色の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、銅箔のＭ面には黄銅層形成処理
（特公昭５１−３５７１１号公報、同５４−６７０１号
公報）、Ｍ、Ｓ双方の面にはクロメート処理、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。A copper clad laminate for a printed circuit is formed by laminating a copper foil on a paper-phenol resin-impregnated base material or glass-epoxy resin-impregnated base material by heating and pressurizing it. A board for electronic equipment is made by forming a circuit network and mounting an element such as a semiconductor device on the circuit network.
In these processes, adhesion with a base material, heating, immersion in an acid or alkaline solution, application of resist ink, soldering, etc. are performed, so that various performances are required for the copper foil. For example, the side that is usually called the M surface (roughened surface, the same applies below) is mainly required to have adhesiveness with the base material, chemical resistance, etc. Usually S side (glossy surface,
The same shall apply hereinafter) is mainly required to have heat resistance and moisture resistance. It is also required that the copper foils on both sides of the copper foil do not undergo oxidative discoloration during storage. In order to satisfy these requirements, a brass layer forming treatment (Japanese Patent Publication No. 51-57711, 54-6701) on the M side of the copper foil, chromate treatment, zinc or oxidation on both sides of M and S. A coating treatment of a zinc-chromium group mixture consisting of zinc and chromium oxide (Japanese Patent Publication No. 58-7077) has been carried out.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記し
たように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。本発明は、こうした要請に対応でき
る、すなわち耐熱性に優れ、金属表面に対する防錆作用
が高い新規なシラン化合物、その製造方法、及びそれを
用いた新規な金属表面処理剤、特に銅箔用表面処理剤を
提供することを目的とするものである。However, since the printed circuit has been densified recently as described above, the characteristics required for the copper foil for the printed circuit used have become more and more severe. The present invention can meet such demands, that is, a novel silane compound having excellent heat resistance and a high rust preventive effect on a metal surface, a method for producing the same, and a novel metal surface treating agent using the same, particularly a surface for copper foil. The purpose is to provide a treating agent.
【０００４】[0004]
【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、特定のベンゾトリアゾール環を有するシラ
ン化合物が金属表面に対し優れた防錆作用を有すること
を見出した。As a result of intensive studies, the present inventor has found that a silane compound having a specific benzotriazole ring has an excellent rust preventive action on a metal surface.
【０００５】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）又は（２）で表される新規ベン
ゾトリアゾールシラン化合物。The present invention has been made based on such findings, and the gist thereof is (1) a novel benzotriazolesilane compound represented by the following general formula (1) or (2).
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】（ただし、一般式（１）又は（２）におい
て、Ｒ1は水素又は炭素数が１〜５のアルキル基、Ｒ2，
Ｒ3は炭素数が１〜３のアルキル基、ｎは一般式（１）
においては０〜３、一般式（２）においては１〜３） （２）前記一般式（１）及び（２）で表わされる新規ベ
ンゾトリアゾールシラン化合物からなる混合物、 （３）下記一般式（３）で表されるベンゾトリアゾール
化合物と下記一般式（４）で表される３−グリシドキシ
プロピルシラン化合物とを、８０〜２００℃で反応され
ることを特徴とする前記（１）記載のベンゾトリアゾー
ルシラン化合物の製造方法、(However, in the general formula (1) or (2), R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R 2 ,
R 3 is an alkyl group having 1 to 3 carbon atoms, and n is a general formula (1).
0 to 3, and 1 to 3 in the general formula (2) (2) A mixture of the novel benzotriazole silane compounds represented by the general formulas (1) and (2), (3) the following general formula (3) ) And a 3-glycidoxypropylsilane compound represented by the following general formula (4) are reacted at 80 to 200 ° C., the benzo described in (1) above. Method for producing triazole silane compound,
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】（ただし、一般式（３），（４）におい
て、Ｒ1は水素又は炭素数が１〜５のアルキル基、Ｒ2，
Ｒ3は炭素数が１〜３のアルキル基、ｎは０〜３） （４）前記（１）記載の一般式（１）又は（２）で表さ
れるベンゾトリアゾールシラン化合物の少なくとも１種
を有効成分とする金属表面処理剤、及び、 （５）前記（１）記載の一般式（１）又は（２）で表さ
れるベンゾトリアゾールシラン化合物の少なくとも１種
を有効成分とする銅箔用表面処理剤にある。(However, in the general formulas (3) and (4), R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R 2 ,
R 3 is an alkyl group having 1 to 3 carbon atoms, n is 0 to 3) (4) At least one benzotriazolesilane compound represented by the general formula (1) or (2) described in (1) above is used. A metal surface treating agent as an active ingredient, and (5) a surface for a copper foil containing as an active ingredient at least one benzotriazolesilane compound represented by the general formula (1) or (2) described in (1) above. It is in the treating agent.
【００１０】以下に本発明をさらに詳細に説明する。上
記一般式（１）又は（２）におけるＲ1は、水素又は炭
素数が１〜５のアルキル基であるが、特には合成の容易
性から水素、メチル基、エチル基等が好適である。Ｒ2
又はＲ3は炭素数が１〜３のアルキル基であるが、特に
は合成の容易性からメチル基、エチル基が好適である。
またｎは０〜３である。The present invention will be described in more detail below. R 1 in the general formula (1) or (2) is hydrogen or an alkyl group having 1 to 5 carbon atoms, and hydrogen, a methyl group, an ethyl group and the like are particularly preferable from the viewpoint of easy synthesis. R 2
Alternatively, R 3 is an alkyl group having 1 to 3 carbon atoms, and a methyl group and an ethyl group are particularly preferable because of easy synthesis.
Further, n is 0 to 3.
【００１１】本発明の上記ベンゾトリアゾールシラン化
合物（１）又は（２）は、一般式（３）で表されるベン
ゾトリアゾール化合物と一般式（４）で表される３−グ
リシドキシプロピルシラン化合物とを、８０〜２００℃
で反応させることにより製造することができる。その反
応を式で示すと次のようになる。The benzotriazole silane compound (1) or (2) of the present invention is a benzotriazole compound represented by the general formula (3) and a 3-glycidoxypropylsilane compound represented by the general formula (4). And 80 to 200 ° C
It can be produced by reacting with. The reaction is expressed by the following equation.
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】（上記式中、Ｒ1は水素又は炭素数が１〜
５のアルキル基、Ｒ2及びＲ3は炭素数１〜３のアルキル
基、ｎは一般式（１）及び（４）においては０〜３、一
般式（２）においては１〜３を表す） 上記一般式（３）で表されるベンゾトリアゾール化合物
は、ベンゾトリアゾール、５−アルキルベンゾトリアゾ
ールであるが、これらのうちとくに好ましいのは、ベン
ゾトリアゾール；５−アルキルベンゾトリアゾールとし
ては、５−メチルベンゾトリアゾール等を挙げることが
できる。又上記一般式（４）で表される３−グリシドキ
シプロピルシラン化合物は、３−グリシドキシプロピル
トリアルコキシシラン、３−グリシドキシプロピルジア
ルコキシアルキルシラン、３−グリシドキシプロピルア
ルコキシジアルキルシラン、３−グリシドキシトリアル
キルシランであり、これらのうちとくに好ましいものを
挙げれば、３−グリシドキシプロピルトリアルコキシシ
ランとしては、３−グリシドキシプロピルトリメトキシ
シラン、３−グリシドキシプロピルトリエトキシシラ
ン、また３−グリシドキシプロピルジアルコキシアルキ
ルシランとしては、３−グリシドキシプロピルジメトキ
シメチルシラン、３−グリシドキシプロピルアルコキシ
ジアルキルシランとしては、３−グリシドキシプロピル
エトキシジメチルシラン、３−グリシドキシプロピルト
リアルキルシランとしては、３−グリシドキシプロピル
トリエチルシラン等である。(In the above formula, R 1 is hydrogen or has 1 to 1 carbon atoms.
5 alkyl group, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, n is 0 to 3 in the general formulas (1) and (4), and 1 to 3 in the general formula (2)) The benzotriazole compound represented by the general formula (3) is benzotriazole or 5-alkylbenzotriazole, and among these, particularly preferred is benzotriazole; 5-alkylbenzotriazole is 5-methylbenzotriazole. Examples thereof include triazole. The 3-glycidoxypropylsilane compound represented by the general formula (4) includes 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, and 3-glycidoxypropylalkoxydialkyl. Silane and 3-glycidoxytrialkylsilane. Of these, particularly preferred are 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyl. Triethoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylalkoxydialkylsilane, 3-glycidoxypropylethoxydimethylsilane, Three The glycidoxypropyltrimethoxysilane alkyl silane, 3-glycidoxypropyl triethylsilane or the like.
【００１４】上記ベンゾトリアゾール化合物と３−グリ
シドキシプロピルシラン化合物との反応は、８０〜２０
０℃の温度に加熱したベンゾトリアゾール化合物に０．
１〜１０モル倍量の３−グリシドキシプロピルシラン化
合物を滴下させながら行うと良く、反応時間は５分〜２
時間程度で十分である。この反応は特には溶媒を必要と
はしないが、クロロホルム、ジオキサン、メタノール、
エタノール等の有機溶剤を反応溶媒として用いてもよ
い。尚、この反応は、水分を嫌うので、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。The reaction between the benzotriazole compound and the 3-glycidoxypropylsilane compound is 80 to 20.
The benzotriazole compound heated to a temperature of 0 ° C.
It is advisable to carry out the reaction while dropping a 1- to 10-fold molar amount of the 3-glycidoxypropylsilane compound, and the reaction time is 5 minutes to 2 minutes.
Time is enough. This reaction does not particularly require a solvent, but chloroform, dioxane, methanol,
An organic solvent such as ethanol may be used as a reaction solvent. Since this reaction does not like water, it is preferable to carry out the reaction in an atmosphere of a gas containing no water such as dry nitrogen or argon so as not to mix water.
【００１５】この反応において、上記一般式（１）又は
（２）で示したベンゾトリアゾールシラン化合物は混合
物の状態で得られるが、これらの化合物は、溶解度の差
を利用する方法、分取液体クロマトグラフィー等の既知
の手段により精製され、単離されうる。尚、金属表面処
理剤として用いる場合は、これらのベンゾトリアゾール
シラン化合物は必ずしも単離する必要はなく、混合物の
まま用いることが簡便で好ましい。In this reaction, the benzotriazole silane compound represented by the above general formula (1) or (2) is obtained in the form of a mixture, and these compounds are prepared by the method utilizing the difference in solubility, preparative liquid chromatography. It can be purified and isolated by known means such as chromatography. When used as a metal surface treatment agent, these benzotriazole silane compounds do not necessarily have to be isolated, and it is preferable to use the mixture as it is because it is simple.
【００１６】上記ベンゾトリアゾールシラン化合物を金
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。たとえば銅、亜鉛及びこれらの合金等の表
面処理剤として有用である。しかし、銅の表面処理剤と
して用いることが好適であり、特にはプリント回路用銅
張積層板等に用いられる銅箔の表面処理剤として用いる
と本発明の効果を十分に発揮することができる。この銅
箔には銅箔の表面を粗面化処理したもの、銅箔に黄銅層
形成処理したもの、クロメート処理したもの、亜鉛−ク
ロム基混合物被覆処理したもの等も包含される。When the above benzotriazole silane compound is used as a metal surface treating agent, the target metal is not particularly limited. For example, it is useful as a surface treatment agent for copper, zinc and alloys thereof. However, it is suitable to be used as a surface treatment agent for copper, and particularly when used as a surface treatment agent for a copper foil used for a copper clad laminate for printed circuits, the effects of the present invention can be sufficiently exhibited. The copper foil includes a copper foil whose surface has been roughened, a copper foil which has been subjected to a brass layer formation treatment, a chromate treatment, a zinc-chromium group mixture coating treatment, and the like.
【００１７】上記ベンゾトリアゾールシラン化合物は、
少なくともその一種をそのまま直接金属表面に塗布して
もよいが、メタノール、エタノール等のアルコール類、
又はそれらと水との混合溶液、更には、アセトン、酢酸
エチル、トルエン等の溶剤で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で塗
布することが簡便で好ましい。尚、このベンゾトリアゾ
ールシラン化合物は単独で用いてもよいが、他の防錆剤
等と混合して用いてもよい。The above benzotriazole silane compound is
At least one of them may be directly applied to the metal surface, but alcohols such as methanol and ethanol,
Alternatively, it is convenient to apply a method of diluting a mixed solution of them and water, and further diluting with a solvent such as acetone, ethyl acetate and toluene to 0.001 to 20% by weight, and immersing the metal in this solution. Is preferred. The benzotriazole silane compound may be used alone, or may be used as a mixture with another rust preventive agent or the like.
【００１８】[0018]
【実施例】ベンゾトリアゾールシラン化合物の合成 （ベンゾトリアゾール化合物と３−グリシドキシプロピ
ルトリメトキシシランとの反応） 実施例１ ベンゾトリアゾール１．１９ｇ（０．０１ｍｏｌ）を１
１０℃で融解し、アルゴン雰囲気下で撹拌しながら、３
−グリシドキシプロピルトリメトキシシラン２．３６ｇ
（０．０１ｍｏｌ）を１時間かけて滴下した。滴下終了
後、さらに１１０℃の温度で５分間反応させた。反応生
成物は透明な黄色の粘稠な液体（以下「混合成分１」と
いう）として得られた。Example Synthesis of benzotriazole silane compound (reaction of benzotriazole compound with 3-glycidoxypropyltrimethoxysilane) Example 1 1.19 g (0.01 mol) of benzotriazole
Melt at 10 ° C and stir under argon for 3
-Glycidoxypropyltrimethoxysilane 2.36 g
(0.01 mol) was added dropwise over 1 hour. After the dropping was completed, the reaction was further performed at a temperature of 110 ° C. for 5 minutes. The reaction product was obtained as a transparent yellow viscous liquid (hereinafter referred to as "mixed component 1").
【００１９】この生成物は透明な黄色の粘性液体で数週
間以上ゲル化せず安定であった。またアルコール、クロ
ロホルム、テトラヒドロフラン等に可溶であり、液体ク
ロマトグラフィーにより混合物であることを確認した。The product was a clear yellow viscous liquid and was stable without gelation for more than several weeks. It was also soluble in alcohol, chloroform, tetrahydrofuran, etc., and was confirmed to be a mixture by liquid chromatography.
【００２０】又、この一部を採取して、1Ｈ−ＮＭＲで
分析した結果、＞ＮＨピークは完全に消失しており、反
応は完全に進行していた。又ＩＲよりＯＨ基の伸縮振動
のピークも確認され、これからも上記した反応が進行し
たことがわかった（図１、２）。A part of this was taken and analyzed by 1 H-NMR. As a result, the> NH peak disappeared completely and the reaction proceeded completely. Further, from IR, a peak of stretching vibration of the OH group was also confirmed, and it was found that the above-mentioned reaction proceeded from this (FIGS. 1 and 2).
【００２１】上記反応生成物を少量のテトラヒドロフラ
ンで溶解し、次いでこれを多量のヘキサン中に注いだ。
可溶成分について、この操作を６回繰返した後、２成分
について分取ゲルパーミエーションクロマトグラフィー
により単離した（以下、化合物１，２）。The above reaction product was dissolved in a small amount of tetrahydrofuran and then poured into a large amount of hexane.
This operation was repeated 6 times for the soluble component, and then the two components were isolated by preparative gel permeation chromatography (hereinafter, compounds 1 and 2).
【００２２】化合物１について1Ｈ−ＮＭＲ、ＩＲスペ
クトル分析を行い、又、化合物２について1Ｈ−ＮＭＲ
スペクトル、ＩＲ、ＭＳスペクトル分析を行った。化合
物２のＭＳスペクトル分析結果を以下に示す。 化合物２；３２３（Ｍ+） 化合物１の1Ｈ−ＮＭＲスペクトルを図３に、同ＩＲス
ペクトルを図４に、又、化合物２の1Ｈ−ＮＭＲスペク
トルを図５に、同ＩＲスペクトルを図６に示す。Compound 1 was analyzed by 1 H-NMR and IR spectroscopy, and Compound 2 was analyzed by 1 H-NMR.
The spectrum, IR, and MS spectrum analysis was performed. The results of MS spectrum analysis of Compound 2 are shown below. Compound 2; 323 (M +) The 1 H-NMR spectrum of Compound 1 is shown in FIG. 3, the IR spectrum thereof is shown in FIG. 4, the 1 H-NMR spectrum of Compound 2 is shown in FIG. Shown in.
【００２３】これらの結果から、上記化合物１は上記一
般式（１）においてＲ1が水素、Ｒ2がメチル、ｎが３で
ある下記式（１−１）の構造を有し、又、化合物２は、
下記式（２−１）の構造を有していることがわかった。From these results, the compound 1 has a structure of the following formula (1-1) in which R 1 is hydrogen, R 2 is methyl and n is 3 in the general formula (1), and the compound is 2 is
It was found to have the structure of the following formula (2-1).
【００２４】[0024]
【化６】 [Chemical 6]
【００２５】実施例２ 実施例１のベンゾトリアゾールに代えて、５−メチルベ
ンゾトリアゾールを使用し、又、反応温度を１２０℃と
した以外は実施例１と同様に反応を行い、混合成分２を
得た。Example 2 In place of the benzotriazole of Example 1, 5-methylbenzotriazole was used, and the reaction was performed in the same manner as in Example 1 except that the reaction temperature was 120 ° C. Obtained.
【００２６】反応生成物は、透明な黄色の粘稠な液体と
して得られた。次に、以上生成したベンゾトリアゾール
シラン（混合成分１，２および化合物１，２）を銅箔の
表面処理剤として評価した。評価方法は以下の通りであ
る。The reaction product was obtained as a clear yellow viscous liquid. Next, the benzotriazole silane (mixing components 1 and 2 and compounds 1 and 2) generated above was evaluated as a surface treatment agent for copper foil. The evaluation method is as follows.
【００２７】耐熱性試験 電解銅箔（厚さ７５μｍ、４．５×４．５ｃｍ）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
の光沢面に、前記で得られた化合物１，２及び混合成分
１，２のベンゾトリアゾールシラン化合物をそれぞれ６
重量％の濃度になるようにメタノールに溶解し、この溶
液をスピンコーターで塗布し、０．３μｍのベンゾトリ
アゾールシラン化合物の薄膜を作成し、これを試験片と
した。 Heat resistance test Electrolytic copper foil (thickness 75 μm, 4.5 × 4.5 cm) was degreased with acetone and washed with a 3% sulfuric acid aqueous solution. On the shiny side of this copper foil, the benzotriazole silane compounds of the compounds 1 and 2 and the mixed components 1 and 2 obtained above were respectively added.
The solution was dissolved in methanol so that the concentration became wt%, and this solution was applied by a spin coater to prepare a 0.3 μm benzotriazolesilane compound thin film, which was used as a test piece.
【００２８】この試験片をそれぞれ、２００℃、２２０
℃、２４０℃の温度の恒温槽に３０分間入れて、加熱処
理した。比較のため、上記ベンゾトリアゾールシラン化
合物に代えて、シランカップリング剤として市販されて
いる３−グリシドキシプロピルトリメトキシシラン（以
下単に「エポキシシラン」と言う）及びベンゾトリアゾ
ールのメタノール溶液を同様に０．３μｍ塗布した銅箔
及び何も塗布しない銅箔（以下「ブランク」とする）に
ついて同様に加熱処理した。加熱後の変色の程度で耐熱
性を評価し、結果を表１に示した。The test pieces were tested at 200 ° C. and 220 ° C., respectively.
The sample was placed in a constant temperature bath at temperatures of 240 ° C. and 30 ° C. for 30 minutes for heat treatment. For comparison, instead of the benzotriazole silane compound, a commercially available silane coupling agent, 3-glycidoxypropyltrimethoxysilane (hereinafter simply referred to as “epoxysilane”) and a methanol solution of benzotriazole were similarly used. The copper foil with 0.3 μm applied and the copper foil with nothing applied (hereinafter referred to as “blank”) were similarly heat-treated. The heat resistance was evaluated by the degree of discoloration after heating, and the results are shown in Table 1.
【００２９】耐湿性試験 上記耐熱性試験と同様にしてベンゾトリアゾールシラ
ン、エポキシシラン、ベンゾトリアゾールを塗布した試
験片及びブランクを温度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。こ
の結果も表１に併せて示した。 Moisture resistance test In the same manner as in the above heat resistance test, test pieces and blanks coated with benzotriazolesilane, epoxysilane, and benzotriazole were placed in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 95% for 24 hours to cause discoloration. Moisture resistance was evaluated by the degree. The results are also shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】（注）耐熱性、耐湿性試験；５：変色な
し、４：わずかに変色、３：少し変色、２：橙色又は黄
色に変色、１：黒褐色に変色 以上の結果から本発明の化合物が、金属の表面処理剤と
して耐熱性、耐湿性（防錆作用）等に優れていることが
わかる。(Note) Heat resistance and humidity resistance test; 5: No discoloration, 4: Slightly discoloration, 3: Slightly discoloration, 2: Orange or yellow discoloration, 1: Black brown discoloration. However, it is found that the metal surface treatment agent is excellent in heat resistance, moisture resistance (corrosion preventive action) and the like.
【００３２】[0032]
【発明の効果】本発明の新規なベンゾトリアゾールシラ
ン化合物は金属表面処理剤、特に銅箔用表面処理剤とし
て有用なもので、耐熱性及び防錆作用に優れるという効
果を有するものである。INDUSTRIAL APPLICABILITY The novel benzotriazole silane compound of the present invention is useful as a metal surface treating agent, particularly as a surface treating agent for copper foil, and has the effects of excellent heat resistance and anticorrosive action.
【図１】混合成分１の1Ｈ−ＮＭＲスペクトルFIG. 1 1 H-NMR spectrum of mixed component 1
【図２】同ＩＲスペクトルFIG. 2 Same IR spectrum
【図３】化合物１（式（１−１））の1Ｈ−ＮＭＲスペ
クトルFIG. 3 1 H-NMR spectrum of compound 1 (formula (1-1))
【図４】同ＩＲスペクトルFIG. 4 IR spectrum
【図５】化合物２の1Ｈ−ＮＭＲスペクトルFIG. 5: 1 H-NMR spectrum of compound 2
【図６】同ＩＲスペクトルFIG. 6 is the same IR spectrum
───────────────────────────────────────────────────── フロントページの続き (72)発明者 荻野 幸男 埼玉県戸田市新曽南３丁目17番35号 株式 会社日鉱共石内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Ogino 3-17-35, Shinsōnan, Toda City, Saitama Prefecture Nikko Kyoishi Co., Ltd.
Claims (5)
新規ベンゾトリアゾールシラン化合物。 【化１】 （ただし、一般式（１）又は（２）において、Ｒ1は水
素又は炭素数が１〜５のアルキル基、Ｒ2，Ｒ3は炭素数
が１〜３のアルキル基、ｎは一般式（１）においては０
〜３、一般式（２）においては１〜３）1. A novel benzotriazole silane compound represented by the following general formula (1) or (2). [Chemical 1] (However, in the general formula (1) or (2), R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and n is a general formula ( 0 in 1)
~ 3, 1-3 in the general formula (2))
で表わされる新規ベンゾトリアゾールシラン化合物から
なる混合物。2. The general formulas (1) and (2) according to claim 1.
A mixture comprising a novel benzotriazole silane compound represented by:
アゾール化合物と下記一般式（４）で表される３−グリ
シドキシプロピルシラン化合物とを、８０〜２００℃で
反応させることを特徴とする請求項１記載のベンゾトリ
アゾールシラン化合物の製造方法。 【化２】 （ただし、一般式（３），（４）において、Ｒ1は水素
又は炭素数が１〜５のアルキル基、Ｒ2，Ｒ3は炭素数が
１〜３のアルキル基、ｎは０〜３）3. A benzotriazole compound represented by the following general formula (3) and a 3-glycidoxypropylsilane compound represented by the following general formula (4) are reacted at 80 to 200 ° C. The method for producing a benzotriazole silane compound according to claim 1. [Chemical 2] (However, in the general formulas (3) and (4), R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and n is 0 to 3 )
で表されるベンゾトリアゾールシラン化合物の少なくと
も１種を有効成分とする金属表面処理剤。4. The general formula (1) or (2) according to claim 1.
A metal surface treating agent containing at least one benzotriazole silane compound represented by
で表されるベンゾトリアゾールシラン化合物の少なくと
も１種を有効成分とする銅箔用表面処理剤。5. The general formula (1) or (2) according to claim 1.
A surface treatment agent for a copper foil containing at least one benzotriazole silane compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5070046A JPH06279463A (en) | 1993-03-29 | 1993-03-29 | Novel benzotriazole silanes, their production and surface treatment agent containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5070046A JPH06279463A (en) | 1993-03-29 | 1993-03-29 | Novel benzotriazole silanes, their production and surface treatment agent containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06279463A true JPH06279463A (en) | 1994-10-04 |
Family
ID=13420245
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5070046A Pending JPH06279463A (en) | 1993-03-29 | 1993-03-29 | Novel benzotriazole silanes, their production and surface treatment agent containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06279463A (en) |
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| JP2017190512A (en) * | 2016-04-15 | 2017-10-19 | 信越化学工業株式会社 | Metal surface treatment agent |
| KR20170118620A (en) | 2016-04-15 | 2017-10-25 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Metal surface treating agent |
| CN108250950A (en) * | 2018-01-17 | 2018-07-06 | 安徽工业大学 | A kind of hydrophilic high corrosion resistant type steel surface silanization treating agent and its synthetic method |
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