JPH06279464A - Novel azole silane, its production and surface treating agent containing the same - Google Patents
Novel azole silane, its production and surface treating agent containing the sameInfo
- Publication number
- JPH06279464A JPH06279464A JP5071737A JP7173793A JPH06279464A JP H06279464 A JPH06279464 A JP H06279464A JP 5071737 A JP5071737 A JP 5071737A JP 7173793 A JP7173793 A JP 7173793A JP H06279464 A JPH06279464 A JP H06279464A
- Authority
- JP
- Japan
- Prior art keywords
- azole
- general formula
- compound represented
- group
- copper foil
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- UGJPMSBRYUISGR-UHFFFAOYSA-N 1H-pyrrole silane Chemical compound [SiH4].N1C=CC=C1 UGJPMSBRYUISGR-UHFFFAOYSA-N 0.000 title description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- -1 azole silane compound Chemical class 0.000 claims description 35
- 229910000077 silane Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000012756 surface treatment agent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 9
- LXWLHXNRALVRSL-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propylsilane Chemical compound [SiH3]CCCOCC1CO1 LXWLHXNRALVRSL-UHFFFAOYSA-N 0.000 abstract description 3
- VNTPGSZQKARKHG-UHFFFAOYSA-N trimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group C[Si](C)(C)CCCOCC1CO1 VNTPGSZQKARKHG-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229950006098 orthocaine Drugs 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
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
Classifications
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
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
規なアゾール系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. Azole-based silane compound, a method for producing the same, and uses thereof.
【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、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 provides a novel silane compound capable of meeting such demands, that is, having a high anticorrosive action on a metal surface, a method for producing the same, and a novel metal surface treating agent using the same, particularly a surface treating agent for copper foil. The purpose is to do.
【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 azole 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)で表される新規アゾール系シラ
ン化合物、The present invention has been made based on such findings, and the gist thereof is (1) a novel azole silane compound represented by the following general formula (1),
【0006】[0006]
【化3】 [Chemical 3]
【0007】(ただし、一般式(1)において、R1,
R2は炭素数が1〜3のアルキル基、XはNH基又は硫
黄、Yは硫黄又はNH基、nは0〜3) (2)下記一般式(2)で表されるアゾール系化合物と
下記一般式(3)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
特徴とする前記(1)記載のアゾール系シラン化合物の
製造方法、(However, in the general formula (1), R 1 ,
R 2 is an alkyl group having 1 to 3 carbon atoms, X is an NH group or sulfur, Y is a sulfur or NH group, and n is 0 to 3) (2) An azole compound represented by the following general formula (2) A method for producing an azole-based silane compound according to (1) above, which comprises reacting a 3-glycidoxypropylsilane compound represented by the following general formula (3) at 80 to 200 ° C.
【0008】[0008]
【化4】 [Chemical 4]
【0009】(ただし、一般式(2),(3)におい
て、R1,R2は炭素数が1〜3のアルキル基、nは0〜
3、XはNH基又は硫黄、Yは硫黄又はNH基) (4)前記(1)記載の一般式(1)で表されるアゾー
ル系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)で表されるアゾー
ル系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 (2) and (3), R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms, and n is 0 to
3, X is an NH group or sulfur, and Y is a sulfur or NH group. (4) Metal surface treatment containing at least one azole silane compound represented by the general formula (1) described in (1) above as an active ingredient. And (5) a surface treatment agent for copper foil, which contains at least one azole-based silane compound represented by the general formula (1) described in (1) above as an active ingredient.
【0010】以下に本発明をさらに詳細に説明する。上
記一般式(1)におけるR1又はR2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。The present invention will be described in more detail below. R 1 or R 2 in the above general formula (1) is an alkyl group having 1 to 3 carbon atoms, and a methyl group and an ethyl group are particularly preferable from the viewpoint of easy synthesis.
【0011】本発明の上記アゾール系シラン化合物
(1)は、一般式(2)で表されるアゾール系化合物と
一般式(3)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 azole silane compound (1) of the present invention comprises the azole compound represented by the general formula (2) and the 3-glycidoxypropylsilane compound represented by the general formula (3), It can be produced by reacting at ˜200 ° C. The reaction is expressed by the following equation.
【0012】[0012]
【化5】 [Chemical 5]
【0013】(上記式中、R1及びR2は炭素数1〜3の
アルキル基、nは0〜3、XはNH基又は硫黄、Yは硫
黄又はNH基を表す) 上記一般式(2)で表されるアゾール系化合物として好
ましいのは、2−アミノベンゾチアゾール、2−メルカ
プトベンゾチアゾール、2−メルカプトベンズイミダゾ
ール等である。又上記一般式(3)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−グリシドキシプ
ロピル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。(Wherein R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms, n is 0 to 3, X is NH group or sulfur, and Y is sulfur or NH group). Preferred as the azole compound represented by) are 2-aminobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and the like. The 3-glycidoxypropylsilane compound represented by the above general formula (3) includes 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, and 3-glycidoxypropylalkoxydialkyl. Silane and 3-glycidoxypropyltrialkylsilane. Of these, particularly preferable ones are 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycid Xypropyltriethoxysilane, 3-glycidoxypropyldialkoxyalkylsilane is 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylalkoxydialkylsilane is 3-glycidoxypropylethoxydimethyl. Shi Down, as the 3-glycidoxypropyltrimethoxysilane alkyl silane, 3-glycidoxypropyl triethylsilane or the like.
【0014】上記アゾール系化合物と3−グリシドキシ
プロピルシラン化合物との反応は、80〜200℃の温
度に加熱したアゾール系化合物に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 azole compound and the 3-glycidoxypropylsilane compound is carried out by heating the azole compound at a temperature of 80 to 200 ° C. in an amount of 0.1 to 10 mole times the amount of 3-glycidoxypropylsilane. It is advisable to carry out the reaction while dropping the compound, and a reaction time of about 5 minutes to 2 hours is sufficient. This reaction does not require a solvent in particular, but an organic solvent such as chloroform, dioxane, methanol or 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】上記アゾール系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-mentioned azole type 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.
【0016】上記アゾール系シラン化合物は、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。At least one of the above-mentioned azole type silane compounds may be directly applied to the metal surface as it is, but alcohols such as methanol and ethanol, or a mixed solution thereof with water, and further acetone and ethyl acetate. It is convenient and preferable to dilute the solution with a solvent such as toluene to a concentration of 0.001 to 20% by weight and immerse the metal in this solution. The benzotriazole silane compound may be used alone, or may be used as a mixture with another rust preventive agent or the like.
【0017】[0017]
【実施例】アゾール系シラン化合物の合成 (2−メルカプトベンゾチアゾールと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 2−メルカプトベンゾチアゾール8.4g(0.05m
ol)を120℃で加温し、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
11.8g(0.05mol)を30分間かけて滴下し
た。滴下終了後、さらに120℃の温度で1時間反応さ
せた。Example Synthesis of azole silane compound ( reaction of 2-mercaptobenzothiazole with 3-glycidoxypropyltrimethoxysilane) Example 1 8.4 g of 2-mercaptobenzothiazole (0.05 m
ol) was heated at 120 ° C. and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring under an argon atmosphere. After the dropping was completed, the reaction was further performed at a temperature of 120 ° C. for 1 hour.
【0018】反応生成物は透明な黄色の粘稠な液体とし
て得られた(以下化合物1という)。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、ゲルパーミエーションクロマトグラ
フィーにより単一成分であることを確認した。The reaction product was obtained as a transparent yellow viscous liquid (hereinafter referred to as compound 1). 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 and the like, and was confirmed to be a single component by gel permeation chromatography.
【0019】又、この一部を採取して、1H−NMRで
分析した結果、−SH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)。また、MSスペクトルの分析
結果を以下に示す。Further, a part of this was taken and analyzed by 1 H-NMR. As a result, --SH was completely disappeared and the reaction was completely progressed. 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). The results of MS spectrum analysis are shown below.
【0020】MS;403(M+) 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がメチル、nが3である下記式(1−1)の
構造を有することがわかった。MS; 403 (M +) From these results, it is found that the above compound 1 has a structure of the following formula (1-1) in which R 1 is methyl and n is 3 in the above general formula (1). It was
【0021】[0021]
【化6】 [Chemical 6]
【0022】実施例2,3 実施例1の2−メルカプトベンゾチアゾールに代えて、
表1に示したアゾール系化合物を使用し、又、反応温度
を表1に示した反応温度とした以外は実施例1と同様に
反応を行い化合物2,3を合成した。Examples 2 and 3 Instead of the 2-mercaptobenzothiazole of Example 1,
Compounds 2 and 3 were synthesized by carrying out the reaction in the same manner as in Example 1 except that the azole compound shown in Table 1 was used and the reaction temperature was changed to the reaction temperature shown in Table 1.
【0023】[0023]
【表1】 [Table 1]
【0024】次に、以上生成したアゾール系シラン(化
合物1〜3)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。Next, the azole silanes (Compounds 1 to 3) thus produced were evaluated as a surface treatment agent for copper foil. The evaluation method is as follows.
【0025】耐湿性試験 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1〜3のアゾール系
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のアゾール系シラン化合物の薄膜を作成
し、これを試験片とした。 Moisture resistance test Electrolytic copper foil (thickness 75 μm, 4.5 × 4.5 cm) was degreased with acetone and washed with a 3% aqueous sulfuric acid solution. On the shiny side of this copper foil, the azole silane compounds of compounds 1 to 3 obtained above were dissolved in methanol to a concentration of 6% by weight, and this solution was applied with a spin coater to give a thickness of 0.3 μm. A thin film of the azole-based silane compound was prepared and used as a test piece.
【0026】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。比較のため、上記アゾール系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)及びアゾール系化合物の2−ア
ミノベンズチアゾール、2−メルカプトベンゾチアゾー
ル、2−メルカプトベンズイミダ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)について同様に評価し
た。結果を表2に示した。This test piece was placed in a thermo-hygrostat having a temperature of 80 ° C. and a humidity of 95% for 24 hours, and the humidity resistance was evaluated by the degree of discoloration. For comparison, 3-glycidoxypropyltrimethoxysilane (hereinafter simply referred to as “epoxysilane”) commercially available as a silane coupling agent and 2-aminobenz of the azole compound instead of the above-mentioned azole compound. Similarly, a copper foil coated with a methanol solution of thiazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole in a thickness of 0.3 μm and a copper foil on which nothing was coated (hereinafter referred to as “blank”) were evaluated in the same manner. The results are shown in Table 2.
【0027】[0027]
【表2】 [Table 2]
【0028】(注)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
して耐湿性(防錆作用)等に優れていることがわかる。(Note) Moisture resistance test; 5: No discoloration, 4: Slight discoloration, 3: Slight discoloration, 2: Orange or yellow discoloration,
1: Discoloration to blackish brown It can be seen from the above results that the compound of the present invention is excellent as a metal surface treating agent in moisture resistance (anticorrosion effect) and the like.
【0029】[0029]
【発明の効果】本発明の新規なアゾール系シラン化合物
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、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 azole-based silane compound of the present invention is useful as a metal surface treating agent, especially as a surface treating agent for copper foil, and has an effect of excellent rust prevention.
【図1】化合物1のIRスペクトルFIG. 1 IR spectrum of Compound 1
【図2】同1H−NMRスペクトルFIG. 2 Same 1 H-NMR 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 (4)
ル系シラン化合物。 【化1】 (ただし、一般式(1)において、R1,R2は炭素数が
1〜3のアルキル基、XはNH基又は硫黄、Yは硫黄又
はNH基、nは0〜3)1. A novel azole silane compound represented by the following general formula (1). [Chemical 1] (However, in the general formula (1), R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms, X is an NH group or sulfur, Y is a sulfur or NH group, and n is 0 to 3)
化合物と下記一般式(3)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記載のアゾール系シラン化
合物の製造方法。 【化2】 (ただし、一般式(2),(3)において、R1,R2は
炭素数が1〜3のアルキル基、nは0〜3、XはNH基
又は硫黄、Yは硫黄又はNH基)2. An azole compound represented by the following general formula (2) and a 3-glycidoxypropylsilane compound represented by the following general formula (3) are reacted at 80 to 200 ° C. The method for producing an azole-based silane compound according to claim 1. [Chemical 2] (However, in the general formulas (2) and (3), R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms, n is 0 to 3, X is NH group or sulfur, and Y is sulfur or NH group.)
アゾール系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。3. A metal surface treating agent comprising at least one azole-based silane compound represented by the general formula (1) as an active ingredient.
アゾール系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。4. A surface treatment agent for a copper foil, which contains at least one azole-based silane compound represented by the general formula (1) as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5071737A JPH06279464A (en) | 1993-03-30 | 1993-03-30 | Novel azole silane, its production and surface treating agent containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5071737A JPH06279464A (en) | 1993-03-30 | 1993-03-30 | Novel azole silane, its production and surface treating agent containing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06279464A true JPH06279464A (en) | 1994-10-04 |
Family
ID=13469142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5071737A Pending JPH06279464A (en) | 1993-03-30 | 1993-03-30 | Novel azole silane, its production and surface treating agent containing the same |
Country Status (1)
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JP (1) | JPH06279464A (en) |
Cited By (8)
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---|---|---|---|---|
JP2015143395A (en) * | 2013-12-25 | 2015-08-06 | 四国化成工業株式会社 | Surface treatment liquid of metal, surface treatment method and its application |
TWI570271B (en) * | 2009-09-11 | 2017-02-11 | Jx Nippon Mining & Metals Corp | Copper foil for lithium ion battery collectors |
JPWO2014156361A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
JPWO2014156362A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
CN108218911A (en) * | 2017-12-29 | 2018-06-29 | 烟台大学 | Silane of one kind structure containing benzothiazole and preparation method thereof |
CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
CN112368290A (en) * | 2018-06-18 | 2021-02-12 | 德国艾托特克公司 | Azole silane compound |
CN115820345A (en) * | 2021-09-16 | 2023-03-21 | 株式会社东芝 | Detergent and method for manufacturing semiconductor device |
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1993
- 1993-03-30 JP JP5071737A patent/JPH06279464A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI570271B (en) * | 2009-09-11 | 2017-02-11 | Jx Nippon Mining & Metals Corp | Copper foil for lithium ion battery collectors |
JPWO2014156361A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
JPWO2014156362A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
JP2015143395A (en) * | 2013-12-25 | 2015-08-06 | 四国化成工業株式会社 | Surface treatment liquid of metal, surface treatment method and its application |
CN108218911A (en) * | 2017-12-29 | 2018-06-29 | 烟台大学 | Silane of one kind structure containing benzothiazole and preparation method thereof |
CN112368290A (en) * | 2018-06-18 | 2021-02-12 | 德国艾托特克公司 | Azole silane compound |
CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
CN115820345A (en) * | 2021-09-16 | 2023-03-21 | 株式会社东芝 | Detergent and method for manufacturing semiconductor device |
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