JP4372461B2 - Novel imidazole silane compound, its production method and its use - Google Patents

Description

（但し、Ｒ^１は水素、ビニル基または炭素数が１〜５のアルキル基、Ｒ^２は水素または炭素数が１〜２０のアルキル基、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は炭素数が１〜３のアルキル基、ｎ、ｍはそれぞれ１〜３の整数、ｌまたはｋは１〜５の整数を表す）
【００１０】
（２）下記一般式（３）で表されるイミダゾール化合物と下記一般式（４）で表されるグリシドキシアルキルシランを６０〜２００℃で反応させた後、下記一般式（５）で表されるイソシアネートシランを−５〜１００℃で反応させて得られた反応混合物。
【化５】

（但し、Ｒ¹は水素、ビニル基または炭素数が１〜５のアルキル基、Ｒ²は水素または炭素数が１〜２０のアルキル基、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は炭素数が１〜３のアルキル基、ｎ、ｍはそれぞれ１〜３の整数、ｌまたはｋは１〜５の整数を表す）
【００１１】
（３）下記一般式（３）で表されるイミダゾール化合物と下記一般式（４）で表されるグリシドキシアルキルシランを６０〜２００℃で反応させたのち、下記一般式（５）で表されるイソシアネートシランを−５〜１００℃で反応させることを特徴とする前記（１）記載のイミダゾールシラン化合物の製造方法。
【化６】

（但し、Ｒ¹は水素、ビニル基または炭素数が１〜５のアルキル基、Ｒ²は水素または炭素数が１〜２０のアルキル基、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は炭素数が１〜３のアルキル基、ｎ、ｍはそれぞれ１〜３の整数、ｌまたはｋは１〜５の整数を表す）
【００１２】
（４）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を有効成分とする表面処理剤
（５）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を有効成分とする樹脂添加剤
（６）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有する樹脂組成物
（７）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有するペースト
（８）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有するワニス
（９）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有するレジスト
【００１３】
（１０）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有するプリプレグ
（１１）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有するプライマー
（１２）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有する塗料
（１３）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有する接着剤
（１４）上記一般式(１)および／または（２）で表されるイミダゾールシラン化合物を含有する封止材料
である。
【００１４】
以下、本発明の構成について説明する。
本発明のイミダゾールシランのＲ^１〜Ｒ^６は各規定された通りの意義を有するが、特に合成の容易性からＲ^１は水素、メチル、ビニルが好ましく、Ｒ^２は水素、メチル、エチル、ウンデシル、ヘプタデシルが好ましく、また、Ｒ^３またはＲ^５はメチル、エチルが好ましい。Ｒ^４またはＲ^６はメチル基が好ましい。また、ｍまたはｎは無機化合物との反応性の点から３が好ましい。
【００１５】
本発明のイミダゾールシランの合成方法に関して、前段階の反応であるイミダゾール化合物とグリシドキシアルキルシランの反応は特開平０５―１８６４７９号公報に開示されている。後段階の反応である前記前段階の反応混合物とイソシアネートシランの反応は、−５〜１００℃で反応させることにより目的生成物をえることができる。しかし、反応を穏やかに進行させるために室温下で反応混合物中にイソシアネートシランを滴下する方法が好ましい。反応混合物／イソシアネートシランの反応モル比は、０．８〜１．２であれば本発明の効果を十分発揮するが、特に好ましくは０．９〜１．１である。
【００１６】
前段階の反応であるイミダゾール化合物とグリシドキシアルキルシランの反応により、以下の（Ａ）〜（Ｄ）成分が生成する。
【００１７】
【化７】

【００１８】
後段階の反応では、上記（Ａ）、（Ｃ）、（Ｄ）中の水酸基とイソシアネートシラン中のイソシアネート基が反応して以下の（Ａ）’、（Ｃ）’、（Ｄ）’が生成する。なお、（Ａ）〜（Ｄ）及び（Ａ）’、（Ｃ）’、（Ｄ）’における各記号は前記と同義である。
【００１９】
【化８】

すなわち、イミダゾール化合物、グリシドキシアルキルシラン、イソシアネートシランのモル比が１：１：１の場合、得られる生成物は、（Ａ）’、（Ｂ）、（Ｃ）’、（Ｄ）’の混合物である。
これらの生成物の比は、反応条件（反応温度、時間、滴下速度等）や、ｍ、Ｒ^３、Ｒ^４の数や種類によって大きく変化する。それぞれの化合物は、カラムクロマトグラフィー等を使用することによって単離することもできるが、表面処理剤や樹脂添加剤として使用するには、（１）または（２）式の化合物を単離せず、反応混合物をそのまま使用しても本発明の効果を十分に発揮する。
【００２０】
本発明のイミダゾールシランを表面処理剤として使用する際、直接塗布してもよいが、水、メタノール、エタノール等のアルコール類、さらにはアセトン、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、この液に無機材料または金属材料を浸漬させたり、スプレーにより噴霧させることが取り扱う上で簡便で好ましい。また、本イミダゾールシランは単独で用いてもよいが、他の防錆剤、あるいはカップリング剤等と混合して用いても良い。また表面処理する材料は特に制限がないが、シリカ、アルミナ、水酸化アルミニウム、タルク等のフィラーやガラス繊維、炭素繊維、アラミド繊維等の繊維、または鉄鋼、亜鉛めっき鋼板、銅箔、アルミ、マグネシウム等の金属材料等が挙げられる。
【００２１】
本発明のイミダゾールシランは、樹脂に添加してその樹脂の他の基材に対する密着性を向上することができる。特に本発明のイミダゾールシランは溶剤への溶解性がよいので、ペースト状樹脂、プリプレグ用含浸樹脂、レジスト、ワニス、プライマー、塗料等の溶剤系樹脂組成物への添加剤としても有用である。これらへの樹脂添加剤として使用する際、その樹脂の種類には特に制限がないが、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アクリル樹脂、およびこれらの樹脂が含有されている組成物に添加することが好ましい。この中でも電子材料分野で一般的に使用されているエポキシ樹脂組成物が特に適している。
【００２２】
このようなエポキシ樹脂としては、たとえばビスフェノールＡ、ビスフェノールＦなどのビスフェノール類のジグリシジルエーテル化物（ビスフェノール型エポキシ樹脂）、ポリエチレンオキシド、ポリプロピレンオキシドなどのポリアルキレンオキシドのジグリシジルエーテル（脂肪族エポキシ樹脂）や側鎖、または主鎖にゴム、ウレタン、ポリエーテル、ポリエステル等の可撓性樹脂で変性されたもの、フェノールノボラック、クレゾールノボラックなどのグリシジルエーテル化物（ノボラック型エポキシ樹脂）、あるいはポリブタジエンなどの共役ジエンポリマーのエポキシ化物などが挙げられる。
【００２３】
本発明のエポキシ樹脂組成物は、前記の特定のイミダゾールシランを密着性向上剤として使用するが、この場合エポキシ樹脂の硬化剤として、また、他の硬化剤と共に使用する場合には硬化促進剤としても機能する。その他エポキシ樹脂用硬化剤として知られている他の硬化剤、硬化促進剤を併用することができる。
このような硬化剤あるいは硬化促進剤としては、たとえば、エポキシ樹脂の硬化剤としてはジシアンジアミドなどのグアニジン系硬化剤、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジド、ドデカン酸ジヒドラジドなどのジヒドラジド系硬化剤、フェノールノボラック等のフェノール系硬化剤、メチルテトラヒドロ無水フタル酸等の酸無水物系硬化剤、ジアミノジフェニルメタン等のアミン系硬化剤、２−エチル−４−メチルイミダゾール等のイミダゾール系硬化剤を用いることができる。また、硬化促進剤として２−エチル−４−メチルイミダゾール等のイミダゾール類、ベンジルジメチルアミン等の３級アミン類、トリフェニルフォスフィン等の芳香族フォスフィン類、三フッ化ホウ素モノエチルアミン等のルイス酸が挙げられる。
【００２４】
上記の本発明のイミダゾールシランなどの硬化剤およびその他の硬化剤の使用量は、特に制限はないが、エポキシ樹脂１００重量部に対して通常１〜２５重量部、好ましくは４〜１０重量部であり、また硬化促進剤については同様に０．１〜５重量部、好ましくは０．１〜２．０重量部で使用される。
硬化剤が１重量部未満では硬化性が低下し、２５重量部を超えると硬化物自体の脆性が増し、何れも充分な接着強度が得られないので好ましくない。一方、硬化促進剤が０．１重量部未満では充分な接着強度が得られず、５重量部を超えると剪断強度が低下する。
【００２５】
また、本発明のエポキシ樹脂組成物には必要に応じて接着向上剤として、シランカップリング剤を添加することができる。シランカップリング剤を添加することにより、特に金属に対する接着強度を向上させることができる。このようなシランカップリング剤としては、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン・塩酸塩などを挙げることができる。
【００２６】
本発明のエポキシ樹脂組成物は前述のエポキシ樹脂、イミダゾールシランを必須成分として、必要に応じて他の硬化剤、硬化促進剤、シランカップリング剤を含むが、さらに必要に応じて、他のエポキシ樹脂、モノエポキシ化合物からなる反応性希釈剤、難燃剤、着色剤、低応力化剤、充填剤等を配合することができる。
【００２７】
なお、本発明のイミダゾールシランは硬化剤としても機能するが、硬化剤として作用する他に、硬化促進剤、接着向上剤としての作用も同時に果たしている。本発明のエポキシ樹脂組成物は、一般の硬化性エポキシ樹脂が利用できる分野において同様に利用することができるが、接着剤、とくに金属用接着剤に好適である。
【００２８】
【実施例】
次に本発明を実施例によって説明するが、本発明はこれらの実施例によって限定されるものではない。
新規イミダゾールシランの合成
イミダゾール６８ｇ（１ｍｏｌ）を１００℃で溶融し、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２３６ｇ（１ｍｏｌ）を３０分かけて滴下した。滴下終了後、さらに１００℃の温度で１時間反応させた。
反応式を以下に示す。反応生成物の液体クロマトグラフィーの面積比は、（Ａ）：（Ｂ）：（Ｃ）：（Ｄ）＝４５：２０：２９：６であることが確認された。
【００２９】
反応は以下の式で示すことができる。
【化９】

【００３０】
１時間反応後、反応混合物を室温に冷却し、３−イソシアネートプロピルトリエトキシシラン２４７ｇ（１ｍｏｌ）を１時間かけて滴下した。得られた生成物は透明な褐色粘性液体であった。図１にこの生成物のＦＴ−ＩＲ、および図２に¹³Ｃ−ＮＭＲのチャートを示す。
【００３１】
このＦＴ−ＩＲ（図１）より原料のイソシアネートシランのイソシアネート基による２３００ｃｍ^-1付近のバンドおよび水酸基による３４００ｃｍ^-1付近のバンドがほとんど観察されていないこと、および１７２０ｃｍ^-1付近にウレタン結合のバンドが生成していることにより定量的に反応が進行していることを確認した。また、図２に示す¹³Ｃ−ＮＭＲチャートにそれぞれの化合物の帰属を記載した。下記式中炭素原子上の丸数字は、図２の¹³Ｃ−ＮＭＲチャートにおける丸数字に対応する。以上ＦＴ−ＩＲと¹³Ｃ−ＮＭＲの結果より、下記式で表される（Ａ）’、（Ｂ）、（Ｃ）’、（Ｄ）’の混合物であることを確認した。その液体クロマトグラフィーの面積比は、（Ａ）’：（Ｂ）：（Ｃ）’：（Ｄ）’＝３７：６：３２：２５であった。
【００３２】
【化１０】

【００３３】
溶解性テスト
前記新規イミダゾールシラン（反応混合物）を各種溶剤へ約５％の濃度となるよう添加し、溶液の性状を目視により観察した。その結果を表１に示す。
また比較として従来のイミダゾールシラン（イミダゾールと３−グリシドキシプロピルトリメトキシシランの反応生成物の意、以下同様）も表１に示す。表１の結果から新規イミダゾールシランは従来のイミダゾールシランに比べて溶解性が向上し、ペースト、プリプレグ用含浸樹脂、ワニス、レジスト、塗料、接着剤等への溶剤系の添加剤として、または表面処理剤として使用可能であることが確認された。
【００３４】
【表１】

○ ：溶解
△ ：一部溶解
× ：不溶
【００３５】
貯蔵安定性テスト
エポキシ樹脂（エピコート８２８、ジャパンエポキシレジン製）１００部に対して新規イミダゾールシラン（反応混合物）および前記従来のイミダゾールシランをそれぞれ１部添加し、十分混合した後、室温に放置した。それぞれのサンプルを経時的に粘度測定し、その粘度上昇の比較により、貯蔵安定性を評価した。その結果を図３に示す。
図３の結果から新規イミダゾールシランは従来のイミダゾールシランに比べて粘度上昇が少なく、貯蔵安定性が改善されていることが確認された。
【００３６】
接着性データ
以下の組成、手順により封止材を作成し、各種金属に対する接着強度を評価した。その結果を表２に示す。また比較としてイミダゾールシラン未添加についても評価した。
【００３７】

【００３８】
封止材作製手順
・（ア）原料配合：フィラー、エポキシ樹脂、フェノール樹脂、ＴＰＰ、カル ナバワックス、カーボンブラック、シランカップリング剤の順で自動乳鉢に添 加。
・（イ）ドライブレンド：自動乳鉢を使用し、約１０分ブレンド。
・熱混練：熱ロール機を硬化剤の軟化点＋１０〜１５℃（９０℃）に温めて混 練。原料が黒色に変色してから約４分間熱混練を継続。
・（ウ）粉砕：スタンプミルを使用し、約３０分間粉砕。
【００３９】
せん断強度評価用金属
銅材：約０．１μｍ銅ストライクめっきした銅合金（Ｃ７０２５）、サイズ：５０×２５×０．１５ｍｍ
銀材：約５μｍ銀めっきした銅合金（Ｃ７０２５）、サイズ：５０×２５×０．１５ｍｍ
ＰＰＦ材：銅合金（Ｃ７０２５）、サイズ：５０×２５×０．１５ｍｍに以下のめっきを行った。
約０．５μｍのＮｉめっき
→約０．０５μｍのＰｄめっき
→約０．００５μｍのＡｕめっき
【００４０】
評価方法
せん断強度：２枚の金属板を封止材で張り合わせてサンプルを作成し、引張り試験機により剪断強度を測定。接着面積：２５×１２．５ｍｍ。硬化時間：１７５℃、６時間。
【００４１】
【表２】

【００４２】
【発明の効果】
以上の実施例および比較例から本発明の新規イミダゾールシランは溶剤への溶解性や貯蔵安定性が従来品に比べて改善され、金属に対して優れた密着性を示すことが確認された。
【図面の簡単な説明】
【図１】実施例の合成例で得られた本発明の新規イミダゾールシラン反応混合物のＦＴ−ＩＲチャート。
【図２】同上^１３Ｃ−ＮＭＲチャート。
【図３】実施例の貯蔵安定性テストの結果を示すグラフ。[0001]
[Technical field to which the invention belongs]
The present invention relates to a novel silane coupling agent that improves adhesion to metals, inorganic materials, or organic materials and fluidity and storage stability of the resin composition, a method for producing the same, and a surface treatment agent containing the same as an active ingredient, The present invention relates to a resin additive and a resin composition containing the same, and can be used in the fields of electronic materials, paints, primers, adhesives, and the like. In particular, the present invention is suitable for a field where adhesion with an inorganic material and storage stability are required in an encapsulant or an adhesive additive used in an electronic material.
[0002]
[Prior art]
In recent years, in the field of electronic materials, there has been a trend toward light, thin, and miniaturization as well as halogen, antimony-free, lead-free soldering, etc., and further improvements in properties are required for sealing materials and the like.
For example, an epoxy resin composition in which a novolac epoxy resin is cured with a phenol novolac resin has been used as a sealing resin for semiconductors. However, due to the high integration of semiconductors, package size has become smaller and thinner, and environmental problems have led to the flow of lead-free solder, and the demand for sealing resin has been increasing year by year due to the development of lead frame PPF (pre-plated frame). It has become tough, and it has become difficult to ensure reliability with conventional epoxy resin compositions. Specific required characteristics include adhesion to the chip and lead frame, in particular, no cracking or peeling of the interface even if the substrate is immersed in solder after absorbing moisture.
[0003]
Moreover, the glass substrate epoxy laminated board is most often used as the insulating material of the printed wiring board. As a laminated board epoxy resin, a resin using dicyandiamide as a curing agent has been generally used, but a method using a phenol novolac resin as a curing agent has been attracting attention because of heat resistance requirements such as lead-free solder. It was. However, when a phenol novolac resin is used as a curing agent, there is a drawback that adhesion to a copper foil, particularly adhesion to an inner layer copper foil in a multilayer board, is significantly inferior to that of a dicyandiamide type.
[0004]
As a means for improving the adhesion between such a metal or inorganic substance and the resin, a surface treatment of a silane coupling agent or a method of adding to the resin is generally used.
Epoxy, amino, and mercapto silane coupling agents are effective for the above sealing materials, and they have been used for many years. There is an increasing number of people who are not fully satisfied.
[0005]
The present inventors have developed a silane coupling agent having an imidazole group (for example, Patent Document 1, Japanese Patent Laid-Open No. 05-186479). Compared to commercially available silane coupling agents, this silane coupling agent greatly improves the adhesion between metals and inorganic substances and resins, and is used in various fields as additives for resin compositions and inorganic substances such as metals and fillers. I confirmed that I can do it. However, this type of imidazole silane is fast to hydrolyze and easily gelled, so that it is difficult to handle. For example, when added to an epoxy resin composition, it has shortcomings of storage stability and poor solubility in a solvent. Therefore, it is unsuitable as an additive to a solvent-based resin composition such as an impregnating resin for prepreg, resist, varnish, paint, and the like.
[0006]
[Patent Document 1]
JP-A-5-186479 [0007]
[Problems to be solved by the invention]
Under such circumstances, the present invention improves the adhesion between inorganic materials and organic materials when used as a surface treatment agent or resin additive, and is a novel imidazole having good storage stability and solubility in solvents. The object is to provide a silane compound.
[0008]
[Means for Solving the Problems]
The present inventors consider that the solubility and storage stability of the imidazolesilane in a solvent are due to the hydroxyl group contained in the molecule, and the solution to the above problem can be achieved by adding another functional group to the hydroxyl group. Tried. As a result, they found that the reaction with a specific isocyanate compound was effective, and reached the present invention.
[0009]
That is, the present invention
(1) A novel imidazolesilane compound represented by the following general formula (1).
[Formula 4]

(Wherein, ^{R 1} is hydrogen, a vinyl group or an alkyl group having a carbon number of 1-5, an alkyl group of ^{R 2} is hydrogen or a carbon number ^{1~20, R 3, R 4,} R 5, R 6 are carbon atoms Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5)
[0010]
(2) After reacting an imidazole compound represented by the following general formula (3) and a glycidoxyalkylsilane represented by the following general formula (4) at 60 to 200 ° C., the following formula (5) Reaction mixture obtained by reacting the isocyanate silane to be reacted at -5 to 100 ° C.
[Chemical formula 5]

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ are carbon numbers. Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5)
[0011]
(3) After reacting the imidazole compound represented by the following general formula (3) with the glycidoxyalkylsilane represented by the following general formula (4) at 60 to 200 ° C., the following formula (5) The method for producing an imidazole silane compound according to (1), wherein the isocyanate silane is reacted at -5 to 100 ° C.
[Chemical 6]

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ are carbon numbers. Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5)
[0012]
(4) Surface treatment agent comprising an imidazolesilane compound represented by the above general formula (1) and / or (2) as an active ingredient (5) Imidazole represented by the above general formula (1) and / or (2) Resin additive containing silane compound as active ingredient (6) Resin composition containing imidazole silane compound represented by general formula (1) and / or (2) (7) General formula (1) and / or (8) Paste containing imidazole silane compound represented by (2) Varnish containing imidazole silane compound represented by general formula (1) and / or (2) (9) General formula (1) and / Or a resist containing an imidazolesilane compound represented by (2)
(10) Prepreg containing the imidazole silane compound represented by the general formula (1) and / or (2) (11) Containing the imidazole silane compound represented by the general formula (1) and / or (2) Primer (12) Paint containing imidazolesilane compound represented by general formula (1) and / or (2) (13) Imidazolesilane compound represented by general formula (1) and / or (2) (14) A sealing material containing an imidazolesilane compound represented by the general formula (1) and / or (2).
[0014]
The configuration of the present invention will be described below.
R ^{1 to} R ⁶ of the imidazole silane of the present invention have the meanings as defined, but R ¹ is preferably hydrogen, methyl, or vinyl, and R ² is hydrogen, methyl, ethyl, undecyl or the like because of the ease of synthesis. Heptadecyl is preferred, and R ³ or R ⁵ is preferably methyl or ethyl. R ⁴ or R ⁶ is preferably a methyl group. M or n is preferably 3 from the viewpoint of reactivity with an inorganic compound.
[0015]
Regarding the method for synthesizing imidazole silane of the present invention, the reaction of imidazole compound and glycidoxyalkylsilane, which is the previous reaction, is disclosed in JP-A No. 05-186479. The target product can be obtained by reacting the reaction mixture of the preceding stage and the isocyanate silane, which is a subsequent stage reaction, at −5 to 100 ° C. However, a method in which isocyanate silane is dropped into the reaction mixture at room temperature in order to allow the reaction to proceed gently is preferred. If the reaction mixture / isocyanate silane reaction molar ratio is 0.8 to 1.2, the effect of the present invention can be sufficiently exerted, but it is particularly preferably 0.9 to 1.1.
[0016]
The following components (A) to (D) are generated by the reaction of the imidazole compound and glycidoxyalkylsilane, which is the previous reaction.
[0017]
[Chemical 7]

[0018]
In the subsequent reaction, the hydroxyl groups in the above (A), (C), and (D) react with the isocyanate groups in the isocyanate silane to produce the following (A) ′, (C) ′, and (D) ′. To do. In addition, each symbol in (A) to (D) and (A) ′, (C) ′, (D) ′ has the same meaning as described above.
[0019]
[Chemical 8]

That is, when the molar ratio of imidazole compound, glycidoxyalkyl silane, and isocyanate silane is 1: 1: 1, the resulting product is (A) ′, (B), (C) ′, (D) ′. It is a mixture.
The ratio of these products varies greatly depending on the reaction conditions (reaction temperature, time, dropping speed, etc.) and the number and type of m, R ³ and R ⁴ . Each compound can be isolated by using column chromatography or the like, but in order to use it as a surface treatment agent or a resin additive, the compound of the formula (1) or (2) is not isolated, Even if the reaction mixture is used as it is, the effect of the present invention is sufficiently exhibited.
[0020]
When using the imidazole silane of the present invention as a surface treatment agent, it may be applied directly, but it is 0.001 to 20 wt.% With alcohols such as water, methanol and ethanol, and further with a solvent such as acetone, ethyl acetate and toluene. In view of handling, it is preferable that the inorganic material or the metal material is immersed in the solution or sprayed by spraying. Moreover, although this imidazole silane may be used independently, you may mix and use with another antirust agent or a coupling agent. The surface treatment material is not particularly limited, but fillers such as silica, alumina, aluminum hydroxide and talc, fibers such as glass fiber, carbon fiber and aramid fiber, or steel, galvanized steel sheet, copper foil, aluminum, magnesium Examples thereof include metal materials.
[0021]
The imidazole silane of this invention can be added to resin and can improve the adhesiveness with respect to the other base material of the resin. In particular, since the imidazole silane of the present invention has good solubility in a solvent, it is useful as an additive to solvent-based resin compositions such as paste resins, prepreg impregnating resins, resists, varnishes, primers, and paints. When used as a resin additive to these, there are no particular restrictions on the type of resin, but it should be added to epoxy resins, urethane resins, polyester resins, acrylic resins, and compositions containing these resins. Is preferred. Among these, epoxy resin compositions generally used in the field of electronic materials are particularly suitable.
[0022]
Examples of such epoxy resins include diglycidyl ethers of bisphenols such as bisphenol A and bisphenol F (bisphenol type epoxy resins), and diglycidyl ethers of polyalkylene oxides such as polyethylene oxide and polypropylene oxide (aliphatic epoxy resins). Or modified with flexible resin such as rubber, urethane, polyether, polyester in the main chain, glycidyl etherified product (novolac type epoxy resin) such as phenol novolak and cresol novolak, or conjugate such as polybutadiene Examples include epoxidized diene polymers.
[0023]
The epoxy resin composition of the present invention uses the specific imidazole silane as an adhesion improver. In this case, as an epoxy resin curing agent, or as a curing accelerator when used with other curing agents. Also works. In addition, other curing agents and curing accelerators known as epoxy resin curing agents can be used in combination.
Examples of such a curing agent or curing accelerator include epoxy resin curing agents such as guanidine curing agents such as dicyandiamide, dihydrazide curing agents such as adipic acid dihydrazide, isophthalic acid dihydrazide, dodecanoic acid dihydrazide, and phenol novolac. Phenolic curing agents, acid anhydride curing agents such as methyltetrahydrophthalic anhydride, amine curing agents such as diaminodiphenylmethane, and imidazole curing agents such as 2-ethyl-4-methylimidazole can be used. Further, imidazoles such as 2-ethyl-4-methylimidazole, tertiary amines such as benzyldimethylamine, aromatic phosphines such as triphenylphosphine, Lewis acids such as boron trifluoride monoethylamine as curing accelerators. Is mentioned.
[0024]
The amount of the curing agent such as imidazolesilane of the present invention and other curing agents is not particularly limited, but is usually 1 to 25 parts by weight, preferably 4 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. In addition, the curing accelerator is similarly used in an amount of 0.1 to 5 parts by weight, preferably 0.1 to 2.0 parts by weight.
If the curing agent is less than 1 part by weight, the curability is lowered, and if it exceeds 25 parts by weight, the brittleness of the cured product itself is increased, and any of them is not preferable because sufficient adhesive strength cannot be obtained. On the other hand, if the curing accelerator is less than 0.1 parts by weight, sufficient adhesive strength cannot be obtained, and if it exceeds 5 parts by weight, the shear strength is lowered.
[0025]
Moreover, a silane coupling agent can be added to the epoxy resin composition of the present invention as an adhesion improver, if necessary. By adding a silane coupling agent, it is possible to particularly improve the adhesion strength to metal. Examples of such silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β. (Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hydrochloric acid A salt etc. can be mentioned.
[0026]
The epoxy resin composition of the present invention contains the above-mentioned epoxy resin and imidazole silane as essential components, and includes other curing agents, curing accelerators, and silane coupling agents as necessary. A reactive diluent made of a resin, a monoepoxy compound, a flame retardant, a colorant, a stress reducing agent, a filler, and the like can be blended.
[0027]
In addition, although the imidazole silane of this invention functions also as a hardening | curing agent, besides acting as a hardening | curing agent, the effect | action as a hardening accelerator and an adhesive improvement agent is also fulfill | performed simultaneously. The epoxy resin composition of the present invention can be similarly used in fields where general curable epoxy resins can be used, but is suitable for adhesives, particularly metal adhesives.
[0028]
【Example】
EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited by these Examples.
Synthesis of novel imidazole silane 68 g (1 mol) of imidazole was melted at 100 ° C., and 236 g (1 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring. After completion of the dropping, the reaction was further carried out at 100 ° C. for 1 hour.
The reaction formula is shown below. It was confirmed that the area ratio of the reaction product by liquid chromatography was (A) :( B) :( C) :( D) = 45: 20: 29: 6.
[0029]
The reaction can be represented by the following formula:
[Chemical 9]

[0030]
After reacting for 1 hour, the reaction mixture was cooled to room temperature, and 247 g (1 mol) of 3-isocyanatopropyltriethoxysilane was added dropwise over 1 hour. The resulting product was a clear brown viscous liquid. FIG. 1 shows a FT-IR chart of this product, and FIG. 2 shows a ¹³ C-NMR chart.
[0031]
The FT-IR (Fig. 1) than the material band near 3400 cm ^-1 due to the band and hydroxyl near 2300 cm ^-1 due to the isocyanate groups of the isocyanate silane is hardly observed, and 1720cm band urethane bond in the vicinity of ^-1 It was confirmed that the reaction progressed quantitatively due to the formation of. Moreover, attribution of each compound was described on the ¹³ C-NMR chart shown in FIG. The circled number on the carbon atom in the following formula corresponds to the circled number in the ¹³ C-NMR chart of FIG. As described above, from the results of FT-IR and ¹³ C-NMR, it was confirmed that the mixture was a mixture of (A) ′, (B), (C) ′, and (D) ′ represented by the following formula. The area ratio of the liquid chromatography was (A) ′ :( B) :( C) ′ :( D) ′ = 37: 6: 32: 25.
[0032]
[Chemical Formula 10]

[0033]
Solubility test The novel imidazole silane (reaction mixture) was added to various solvents to a concentration of about 5%, and the properties of the solution were visually observed. The results are shown in Table 1.
For comparison, conventional imidazole silane (meaning reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane, hereinafter the same) is also shown in Table 1. From the results in Table 1, the new imidazole silane has improved solubility compared to conventional imidazole silanes, and as a solvent-based additive to pastes, impregnating resins for prepregs, varnishes, resists, paints, adhesives, etc., or surface treatment It was confirmed that it can be used as an agent.
[0034]
[Table 1]

○: dissolved △: partially dissolved ×: insoluble [0035]
1 part each of new imidazole silane (reaction mixture) and the conventional imidazole silane was added to 100 parts of storage stability test epoxy resin (Epicoat 828, Japan Epoxy Resin), and the mixture was allowed to stand at room temperature. The viscosity of each sample was measured over time, and the storage stability was evaluated by comparing the increase in viscosity. The result is shown in FIG.
From the results shown in FIG. 3, it was confirmed that the novel imidazole silane had less viscosity increase than the conventional imidazole silane, and the storage stability was improved.
[0036]
Adhesive data A sealing material was prepared by the following composition and procedure, and the adhesive strength to various metals was evaluated. The results are shown in Table 2. For comparison, imidazole silane not added was also evaluated.
[0037]

[0038]
Sealing material preparation procedure (a) Raw material formulation: Filler, epoxy resin, phenolic resin, TPP, carnauba wax, carbon black, silane coupling agent are added to the automatic mortar in this order.
・ (I) Dry blend: Using an automatic mortar, blend for about 10 minutes.
Heat kneading: Kneading by heating a hot roll machine to the softening point of the curing agent +10 to 15 ° C (90 ° C) Heat kneading is continued for about 4 minutes after the raw material turns black.
(C) Grinding: Using a stamp mill, grind for about 30 minutes.
[0039]
Metallic copper material for shear strength evaluation: Copper alloy plated with about 0.1 μm copper strike (C7025), Size: 50 × 25 × 0.15 mm
Silver material: Copper alloy (C7025) plated with about 5 μm silver, Size: 50 × 25 × 0.15 mm
PPF material: Copper alloy (C7025), Size: 50 × 25 × 0.15 mm was plated as follows.
About 0.5 μm Ni plating → about 0.05 μm Pd plating → about 0.005 μm Au plating
Evaluation method Shear strength: A sample is prepared by bonding two metal plates with a sealing material, and the shear strength is measured by a tensile tester. Adhesive area: 25 × 12.5 mm. Curing time: 175 ° C., 6 hours.
[0041]
[Table 2]

[0042]
【The invention's effect】
From the above Examples and Comparative Examples, it was confirmed that the novel imidazole silane of the present invention has improved solubility in solvents and storage stability compared to conventional products, and exhibits excellent adhesion to metals.
[Brief description of the drawings]
FIG. 1 is an FT-IR chart of the novel imidazolesilane reaction mixture of the present invention obtained in the synthesis example of the example.
FIG. 2 is a ¹³ C-NMR chart as above.
FIG. 3 is a graph showing the results of a storage stability test of an example.

Claims (14)

A novel imidazolesilane compound represented by the following general formula (1) or (2).

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ are carbon numbers. Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5) After reacting the imidazole compound represented by the following general formula (3) and the glycidoxyalkylsilane represented by the following general formula (4) at 60 to 200 ° C., an isocyanate represented by the following general formula (5) A reaction mixture obtained by reacting silane at −5 to 100 ° C.

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ are carbon numbers. Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5) An isocyanate represented by the following general formula (5) after reacting an imidazole compound represented by the following general formula (3) and a glycidoxyalkylsilane represented by the following general formula (4) at 60 to 200 ° C. The method for producing an imidazole silane compound according to claim 1, wherein silane is reacted at -5 to 100 ° C.

(However, R ¹ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ are carbon numbers. Is an alkyl group of 1 to 3, n and m are each an integer of 1 to 3, l or k represents an integer of 1 to 5) A surface treatment agent comprising an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 as an active ingredient. The resin additive which uses the imidazole silane compound represented by General formula (1) and / or (2) of Claim 1 as an active ingredient. The resin composition containing the imidazole silane compound represented by General formula (1) and / or (2) of Claim 1 . A paste containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . A varnish containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . A resist containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . A prepreg containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . A primer containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . The coating material containing the imidazole silane compound represented by General formula (1) and / or (2) of Claim 1 . An adhesive containing an imidazolesilane compound represented by the general formula (1) and / or (2) according to claim 1 . The sealing material containing the imidazole silane compound represented by General formula (1) and / or (2) of Claim 1 .

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