JP3555845B2 - Novel organosilicon compound, method for producing the same, surface treating agent and resin additive using the same - Google Patents
Novel organosilicon compound, method for producing the same, surface treating agent and resin additive using the same Download PDFInfo
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- JP3555845B2 JP3555845B2 JP10823799A JP10823799A JP3555845B2 JP 3555845 B2 JP3555845 B2 JP 3555845B2 JP 10823799 A JP10823799 A JP 10823799A JP 10823799 A JP10823799 A JP 10823799A JP 3555845 B2 JP3555845 B2 JP 3555845B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Description
【０００１】
【発明の属する技術分野】
本発明は、銅、鉄鋼、およびアルミニウム等の金属またはガラス繊維、シリカ、酸化アルミニウム、水酸化アルミニウム等の無機物質と樹脂との接着性の改善を行うための表面処理剤、または、エポキシ樹脂等の樹脂の機械的強度の改善を行うための樹脂添加剤およびさらに有用な有機ケイ素化合物に関する。
【０００２】
【従来の技術】
電子機器のボードは銅箔と紙−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を加熱、加圧して銅張積層板を作成した後、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作られる。
【０００３】
これらの過程では、銅箔と基材との接着、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、さまざまな性能が要求される。これらの要求を満たすために、銅箔は黄銅層形成処理（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（特公昭５８−７０７７号公報）、シランカップリング剤処理等が検討されている。また、樹脂は樹脂や硬化剤の種類およびその配合量を変えたり、添加剤等によって上記要求特性を満足させている。また、ガラス繊維はシランカップリング剤等の表面処理等が検討されている。しかしながら、最近、プリント回路が緻密化しているので、使用される電子機器用のボードに要求される特性はますます厳しくなっている。
【０００４】
これに伴うエッチング精度の向上に対応するため銅箔のプリプレグと接着される粗化面（Ｍ面）にはさらに低い表面粗さ（ロープロファイル）も求められている。しかし、Ｍ面の表面粗さは一方ではプリプレグとの接着にあたって、アンカー効果をもたらしているので、Ｍ面に対するこのロープロファイルの要求と接着力の向上とは二律背反の関係にあり、ロープロファイル化によるアンカー効果の低減分は別の手段による接着力の向上で補償することが必要である。
【０００５】
また、発電所などの高電圧・高容量の機器や半導体の封止等に使われている電気絶縁用注型材料はエポキシ樹脂のマトリックス中にシリカやアルミナ等の無機物質を充填した複合材料である。これらの材料には様々な電気的・機械的特性が要求されており、それらの特性を満足させるためには、無機物質と樹脂の接着性を向上させる必要がある。この対策としてシランカップリング剤を樹脂中に添加したり、無機物質をシランカップリング剤で表面処理することが提案されているが、さらなる樹脂／無機物質界面の改善が要求されている。
【０００６】
【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、すなわち銅、鉄鋼、およびアルミニウム等の金属またはガラス繊維、シリカ、酸化アルミニウム、水酸化アルミニウム等の無機物質と樹脂との接着性を向上させることができる新規な有機ケイ素化合物、その製造方法、並びにそれを用いた表面処理剤または樹脂添加剤を提供することを目的とするものである。
【０００７】
【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、前記一般式（１）に示す新規有機ケイ素化合物を金属または無機物質に表面処理した場合、樹脂との接着性を向上させることができ、また、エポキシ樹脂等の樹脂に添加しても硬化反応が促進され、かつ機械的強度が改善されることを見出した。
【０００８】
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）で表される新規有機ケイ素化合物、
【０００９】
【化３】
（ただし、式中、Ｒ１、Ｒ２、Ｒ３は水素、炭素数が１〜２０のアルキル基、ビニル基、フェニル基、又はベンジル基であり、Ｒ４、Ｒ５は炭素数１〜５のアルコキシル基で置換された又は無置換の炭素数１〜５のアルキル基であり、ｍは１〜１０、ｎは１〜３の整数である。ただし、Ｒ２、Ｒ３は結合してベンゼン環になっても良い。）
（２）下記一般式（２）で表されるイミダゾール化合物と下記一般式（３）で表されるイソシアネートシランを３０〜１００℃で反応させることを特徴とする前記（１）記載の有機ケイ素化合物の製造方法、
【００１１】
【化４】
（ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、ｍ、ｎは一般式（１）と同義）
（３）前記（１）に記載の有機ケイ素化合物を有効成分とする表面処理剤、
（４）前記（１）に記載の有機ケイ素化合物を有効成分とする樹脂添加剤、
にある。
【００１３】
上記一般式（１）におけるＲ１、Ｒ２、Ｒ３は、水素、炭素数１〜２０のアルキル基、ビニル基、フェニル基、又はベンジル基であれば本発明の効果を十分に発揮する。ただし、これらの置換基は使用する用途によって適したものを選定する必要がある。すなわち、フィラーや金属等に水溶液で表面処理したい場合は、水素または炭素数の少ないアルキル基が溶解性の点で好ましい。
【００１４】
また、樹脂に添加する場合は、対象樹脂との相溶性が高い置換基を選定する必要がある。上記一般式（１）におけるＲ４、Ｒ５は、炭素数１〜５のアルコキシル基で置換された又は無置換の炭素数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、縮合のし易さの点からメチル基またはエチル基が好適である。また、ｎは１〜３であるが、金属、無機物質や樹脂との反応性や架橋性の高い方が接着特性が向上するため、ｎは２または３が好適である。また、ｍは１〜１０である。
【００１５】
以下に本発明をさらに詳細に説明する。
【００１６】
本発明の上記新規有機ケイ素化合物（１）は下記反応式（４）で表される反応により合成される。すなわち、イミダゾール化合物とイソシアネートシランを混合し、３０〜１００℃に加熱することにより製造することができる。
【００１７】
【化５】
（反応式中、各記号は前記と同義）
上記反応式（４）のイミダゾール化合物とイソシアネートシランの反応モル比はイミダゾール化合物１モルに対して０．１〜１０モルのイソシアネートシランを反応させることにより製造できるが、イミダゾール化合物１モルに対してイソシアネートシランを１モルで反応させることが望ましい。
【００１９】
上記、新規有機ケイ素化合物を金属または無機物質の表面処理剤として用いる場合、その金属または無機物質には特に制限がない。例えば、金属では、銅、鉄、アルミニウム、亜鉛等またはそれらの合金、無機物質ではガラス繊維、シリカ、酸化アルミニウム、水酸化アルミニウム、酸化マグネシウム、炭酸バリウム、タルク等である。表面処理は、そのまま塗布しても良いが、水、メタノール、エタノール、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て噴霧するか、この液に金属または無機物質を浸漬させる方法で塗布することが簡便で好ましい。
【００２０】
なお、この新規有機ケイ素化合物は単独で用いても良いが、他のシランまたはチタネートカップリング剤、防錆剤と混合しても良い。
【００２１】
上記、本発明の新規有機ケイ素化合物は樹脂添加剤として用いる場合、その樹脂には特には制限がなく、熱可塑性樹脂でも熱硬化性樹脂でも良いが、特にはエポキシ樹脂に添加すると硬化剤または硬化促進剤として効果的に作用し、本発明の効果を十分に発揮することができる。本発明の新規有機ケイ素化合物は樹脂中のそのまま添加してもアルコール系、芳香族系、脂肪族系有機溶剤に溶解して添加しても良い。添加量は樹脂１００に対して０．００１〜５０添加すれば本発明の効果を十分発揮できる。なお、本発明の新規有機ケイ素化合物は、硬化剤、シランカップリング剤、可塑剤等の添加剤等と併用しても良い。
【００２２】
【発明の実施の形態】
実施例１
イミダゾール６．８ｇ（０．１モル）とイソシアネートプロピルトリエトキシシラン２４．９ｇ（０．１モル）を混合し、ジブチルスズラウレートを触媒として０．１ｇ添加し、５０℃で１時間反応させ、下記式（５）の有機ケイ素化合物を得た。反応の確認は液体クロマトグラフィーにより反応物の消失により行った。得られた化合物はＦＴ−ＩＲ、ＮＭＲにより同定した。本化合物の１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲスペクトルを図１〜３に示す。
【００２３】
【化６】
実施例２
表面処理剤としての適用
アルミ合金板（ＪＩＳ Ｈ４０００に規定するＡ２０２４Ｐ、日本テストパネル製、厚さ１．６ｍｍ、２５×１００ｍｍ）を上記実施例１で得られた有機ケイ素化合物の０．４％メタノール溶液に浸漬した後、熱風乾燥することにより表面処理した。この表面処理したアルミ合金板２枚をエポキシ樹脂組成物［エピコート８２８（エポキシ樹脂、油化シェルエポキシ製）：１００部、ジシアンジアミド（関東化学（株）製）：５部、２−エチル−４−メチルイミダゾール（四国化成製）：１部］により１００℃で１時間＋１５０℃で１時間の硬化条件で接着し、ＪＩＳ Ｋ６８５０に準じて引っ張り剪断接着試験を行った。また比較として未処理のアルミ合金板、および０．４％ ３−グリシドキシプロピルトリメトキシシランのメタノール溶液で処理したアルミ合金板についても同様に評価した。その結果を表１に示す。
【００２５】
【表１】
実施例３
樹脂への添加剤としての適用
未処理のアルミ合金板２枚をエポキシ樹脂組成物［エピコート８２８：１００部、ジシアンジアミド（関東化学（株）製）：５部、実施例１で得られた有機ケイ素化合物：１部］により１００℃で１時間＋１５０℃で１時間の硬化条件で接着し、ＪＩＳ Ｋ６８５０に準じて引っ張り剪断接着試験を行った。その結果を表２に示す。また、比較として新規有機ケイ素化合物の代わりに、２−エチル−４−メチルイミダゾール１部を用いて同様に評価した。その結果を表２に示す。
【００２７】
【表２】
【発明の効果】
以上説明したように、本発明の新規有機ケイ素化合物は表面処理剤、樹脂添加剤として金属と樹脂との接着性を改善することができる。
【図面の簡単な説明】
【図１】実施例１で得られた有機ケイ素化合物の１Ｈ−ＮＭＲチャート。
【図２】同上、１３Ｃ−ＮＭＲチャート。
【図３】同上、ＦＴ−ＩＲチャート。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a surface treatment agent for improving the adhesion between a resin such as copper, steel, aluminum or another metal or glass fiber, silica, aluminum oxide, or an inorganic material such as aluminum hydroxide, or an epoxy resin. And a more useful organosilicon compound for improving the mechanical strength of the resin.
[0002]
[Prior art]
The board of an electronic device is made by heating and pressing copper foil and paper-phenol resin impregnated base material or glass-epoxy resin impregnated base material to create a copper-clad laminate, and then etching to form a circuit network. It is made by mounting elements such as semiconductor devices.
[0003]
In these processes, various performances are required because bonding between the copper foil and the base material, heating, immersion in an acid or alkali solution, application of a resist ink, soldering, and the like are performed. In order to satisfy these requirements, the copper foil is subjected to a brass layer forming treatment (JP-B-51-35711 and JP-B-54-6701), a chromate treatment, and a zinc-chromium group comprising zinc or zinc oxide and chromium oxide. A mixture coating treatment (Japanese Patent Publication No. 58-7077), a silane coupling agent treatment, and the like have been studied. Further, the resin satisfies the above-mentioned required characteristics by changing the kind of the resin and the curing agent and the amount thereof, and by adding additives. Surface treatment of glass fibers with a silane coupling agent or the like is being studied. However, recently, as printed circuits are becoming more and more compact, characteristics required for boards for electronic devices to be used are becoming increasingly severe.
[0004]
In order to cope with the improvement in etching accuracy accompanying this, a further lower surface roughness (low profile) is required on a roughened surface (M surface) bonded to a prepreg of copper foil. However, on the other hand, the surface roughness of the M surface has an anchor effect in bonding with the prepreg, so that the requirement of the low profile for the M surface and the improvement of the adhesive force are in a trade-off relationship, and the low profile It is necessary to compensate for the reduction in the anchor effect by improving the adhesive force by another means.
[0005]
Also, the casting material for electrical insulation used for sealing high-voltage, high-capacity equipment such as power plants and semiconductors is a composite material in which an epoxy resin matrix is filled with an inorganic substance such as silica or alumina. is there. These materials are required to have various electrical and mechanical properties, and in order to satisfy those properties, it is necessary to improve the adhesion between the inorganic substance and the resin. As measures against this, it has been proposed to add a silane coupling agent to the resin or to perform a surface treatment of an inorganic substance with the silane coupling agent, but further improvement of the resin / inorganic substance interface is required.
[0006]
[Problems to be solved by the invention]
The present invention can meet such demands, that is, a novel metal or glass fiber such as copper, steel, and aluminum, or a novel material that can improve the adhesiveness between an inorganic substance such as silica, aluminum oxide and aluminum hydroxide and a resin. An object of the present invention is to provide an organosilicon compound, a method for producing the same, and a surface treating agent or a resin additive using the same.
[0007]
[Means for Solving the Problems]
As a result of intensive research, the present inventor has found that when the novel organosilicon compound represented by the general formula (1) is subjected to a surface treatment on a metal or an inorganic substance, the adhesion to a resin can be improved, It has been found that even when added to a resin such as a resin, the curing reaction is promoted and the mechanical strength is improved.
[0008]
The present invention has been made based on such findings, and the gist of the invention is as follows.
(1) a novel organosilicon compound represented by the following general formula (1),
[0009]
Embedded image
(Wherein, R 1 , R 2 , and R 3 are hydrogen, an alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group, or a benzyl group, and R 4 and R 5 have 1 to 5 carbon atoms. Is an alkyl group substituted or unsubstituted with an alkoxyl group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and n is an integer of 1 to 3. However, R 2 and R 3 are bonded to benzene (It may be a ring.)
(2) The organosilicon compound according to (1), wherein the imidazole compound represented by the following general formula (2) is reacted with an isocyanate silane represented by the following general formula (3) at 30 to 100 ° C. Manufacturing method,
[0011]
Embedded image
(However, R 1 , R 2 , R 3 , R 4 , R 5 , m, and n have the same meanings as in the general formula (1))
(3) a surface treatment agent comprising the organosilicon compound according to (1) as an active ingredient;
(4) a resin additive containing the organosilicon compound according to (1) as an active ingredient;
It is in.
[0013]
If R 1 , R 2 , and R 3 in the general formula (1) are hydrogen, an alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group, or a benzyl group, the effects of the present invention are sufficiently exhibited. However, it is necessary to select these substituents depending on the intended use. That is, when it is desired to perform a surface treatment on a filler, a metal, or the like with an aqueous solution, hydrogen or an alkyl group having a small number of carbon atoms is preferable in terms of solubility.
[0014]
When adding to a resin, it is necessary to select a substituent having high compatibility with the target resin. R 4 and R 5 in the general formula (1) are an alkyl group having 1 to 5 carbon atoms substituted or unsubstituted with an alkoxyl group having 1 to 5 carbon atoms. A methyl group or an ethyl group is preferred from the viewpoint of easy hydrolysis and condensation of the compound. In addition, n is 1 to 3. However, n is preferably 2 or 3, since the higher the reactivity or crosslinkability with a metal, an inorganic substance, or a resin improves the adhesive property. M is 1 to 10.
[0015]
Hereinafter, the present invention will be described in more detail.
[0016]
The novel organosilicon compound (1) of the present invention is synthesized by a reaction represented by the following reaction formula (4). That is, it can be produced by mixing an imidazole compound and an isocyanate silane and heating the mixture to 30 to 100 ° C.
[0017]
Embedded image
(In the reaction formula, each symbol is as defined above.)
The reaction molar ratio of the imidazole compound of the above reaction formula (4) to the isocyanate silane can be produced by reacting 0.1 to 10 mol of isocyanate silane with respect to 1 mol of the imidazole compound. It is desirable to react the silane in one mole.
[0019]
When the novel organosilicon compound is used as a surface treatment agent for a metal or inorganic substance, the metal or inorganic substance is not particularly limited. For example, metals include copper, iron, aluminum, zinc and the like or alloys thereof, and inorganic substances include glass fiber, silica, aluminum oxide, aluminum hydroxide, magnesium oxide, barium carbonate, talc and the like. The surface treatment may be applied as it is, but it may be diluted with a solvent such as water, methanol, ethanol, acetone, ethyl acetate, toluene, etc. to a concentration of 0.001 to 20% by weight, or sprayed with a metal. Alternatively, application by a method of immersing an inorganic substance is simple and preferable.
[0020]
The new organosilicon compound may be used alone, or may be mixed with another silane or titanate coupling agent or a rust inhibitor.
[0021]
When the novel organosilicon compound of the present invention is used as a resin additive, the resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. It effectively acts as an accelerator and can sufficiently exert the effects of the present invention. The novel organosilicon compound of the present invention may be added as it is in the resin or may be added by dissolving it in an alcohol, aromatic or aliphatic organic solvent. The effect of the present invention can be sufficiently exhibited by adding 0.001 to 50 to the
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
Example 1
6.8 g (0.1 mol) of imidazole and 24.9 g (0.1 mol) of isocyanatopropyltriethoxysilane are mixed, 0.1 g of dibutyltin laurate is added as a catalyst, and the mixture is reacted at 50 ° C. for 1 hour. An organosilicon compound of the formula (5) was obtained. Confirmation of the reaction was performed by disappearance of the reaction product by liquid chromatography. The obtained compound was identified by FT-IR and NMR. 1 H-NMR, 13 C-NMR and FT-IR spectra of the present compound are shown in FIGS.
[0023]
Embedded image
Example 2
Application as a surface treatment agent An aluminum alloy plate (A2024P defined by JIS H4000, manufactured by Nippon Test Panel, thickness 1.6 mm, 25 × 100 mm) was used as the organosilicon compound obtained in Example 1 above. After being immersed in a 0.4% methanol solution, the surface was treated by hot-air drying. Two pieces of the surface-treated aluminum alloy plate were used as an epoxy resin composition [Epicoat 828 (epoxy resin, manufactured by Yuka Shell Epoxy): 100 parts, dicyandiamide (Kanto Chemical Co., Ltd.): 5 parts, 2-ethyl-4- Methyl imidazole (manufactured by Shikoku Chemicals): 1 part] under a curing condition of 100 ° C. for 1 hour and 150 ° C. for 1 hour, and a tensile shear adhesion test was performed according to JIS K6850. For comparison, an untreated aluminum alloy plate and an aluminum alloy plate treated with a methanol solution of 0.4% 3-glycidoxypropyltrimethoxysilane were similarly evaluated. Table 1 shows the results.
[0025]
[Table 1]
Example 3
Application as an additive to resin Two untreated aluminum alloy plates were obtained in Example 1 with an epoxy resin composition [Epicoat 828: 100 parts, dicyandiamide (Kanto Chemical Co., Ltd.): 5 parts]. The obtained organosilicon compound: 1 part] was cured at 100 ° C. for 1 hour and at 150 ° C. for 1 hour under a curing condition, and a tensile shear adhesion test was performed according to JIS K6850. Table 2 shows the results. For comparison, the same evaluation was conducted using 1 part of 2-ethyl-4-methylimidazole instead of the novel organosilicon compound. Table 2 shows the results.
[0027]
[Table 2]
【The invention's effect】
As described above, the novel organosilicon compound of the present invention can improve the adhesion between a metal and a resin as a surface treatment agent and a resin additive.
[Brief description of the drawings]
FIG. 1 is a 1 H-NMR chart of an organosilicon compound obtained in Example 1.
FIG. 2 is a 13 C-NMR chart of
FIG. 3 is an FT-IR chart of
Claims (4)
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| JP10823799A JP3555845B2 (en) | 1999-04-15 | 1999-04-15 | Novel organosilicon compound, method for producing the same, surface treating agent and resin additive using the same |
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