JP4748341B2 - Phenol derivative having thioether structure or disulfide structure, and production method thereof - Google Patents

Description

〔式中、Ｒ_１は炭素数が２又は３のメチレン鎖、Ｒ_２は炭素数が１〜１０のメチレン鎖、Ｇは水素原子、メチル基、エチル基、ブチル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミン基、ノニル基、フェニレン基、ベンジル基又はハロゲン原子のいずれかを指す〕。
【００１１】
また、本発明は、式（２１）で表される（ジスルフィド構造をもつ）フェノール誘導体の製造法に関する。式（２１）のフェノール誘導体は、最初に、合成原料となる式（１１）で表される（チオエーテル構造をもつ）フェノール誘導体を製造する。
【化６】

〔式中、Ｒ_１、Ｒ_２、Ｇは、式（２１）中における意味と同じ。〕
【００１２】
式（１１）のフェノール誘導体の製造法においては、式（１）又は式（２）
【化７】

〔式中、Ｇは、式（２１）中における意味と同じ。〕で表されるフェノール化合物と、式（３）
【化８】
ＨＳ−Ｒ_２−ＳＨ （３）
〔式中、Ｒ_２は、式（２１）中における意味と同じ。〕で表されるジチオールとを、加熱・反応させる。
【００１３】
このようにして得られた式（１１）のフェノール誘導体を、溶媒中、過酸化水素を用いて酸化反応させることを特徴とする、前記式（２１）のフェノール誘導体の製造法である。
【００１４】
【発明の実施の形態】
以下、本発明を更に具体的に説明する。
本発明のジスルフィド構造をもつフェノール誘導体は、上で述べたように、式（２１）で表されるジスルフィド構造をもつフェノール誘導体である。
【００１５】
ここで、Ｒ_１が炭素数３のメチレン鎖の場合、上記フェノール誘導体は次の式（２２）で表される。
【化９】

〔式中、Ｒ_２は炭素数が１〜１０のメチレン鎖、Ｇは水素原子、メチル基、エチル基、ブチル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミン基、ノニル基、フェニレン基、ベンジル基又はハロゲン原子のいずれかを示す。〕
【００１６】
Ｇがメトキシ基の場合、上記フェノール誘導体は例えば次の式（２３）で表され、Ｇが水素原子の場合、上記フェノール誘導体は例えば次の式（２４）で表される。
【化１０】

〔式中、Ｒ_２は炭素数が１〜１０のメチレン鎖を示す。〕
【００１７】
チオエーテル構造をもつフェノール誘導体は、上で述べたように、式（１１）で表されるフェノール誘導体である。ここで、Ｒ_１が炭素数３のメチレン鎖の場合、上記フェノール誘導体は次の式（１２）で表される。
【化１１】

〔式中、Ｒ_２は炭素数が１〜１０のメチレン鎖、Ｇは水素原子、メチル基、エチル基、ブチル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミン基、ノニル基、フェニレン基、ベンジル基又はハロゲン原子のいずれかを示す。〕
【００１８】
Ｇがメトキシ基の場合、上記フェノール誘導体は例えば次の式（１３）で表され、Ｇが水素原子の場合、上記フェノール誘導体は例えば次の式（１４）で表される。
【化１２】

〔式中、Ｒ_２は炭素数が１〜１０のメチレン鎖を示す。〕
【００１９】
本発明の式（１１）のチオエーテル構造をもつフェノール誘導体の製造法について先ず、説明する。
式（１）のアリル基で置換されたフェノール又は式（２）のビニル基で置換されたフェノールの所定量を反応容器に秤量し、次いで、式（３）のジチオールの所定量を加える。ここで、式（１）のフェノール又は式（２）のフェノールの量と、式（３）のジチオールの量は等モル比を基本とする。一方が他方よりも過剰であれば、その過剰分は未反応のまま残るので好ましくない。
反応温度や反応時間等の反応条件は、反応（求核置換反応）が十分に進行する条件を選ぶ。概ね、反応温度は１００℃〜２００℃、反応時間は３０分〜７時間程度である。
【００２０】
さらに反応を具体的に説明する。反応は、反応容器中にて撹拌、還流させながら加熱する。雰囲気は窒素ガス等の不活性雰囲気中でもよいが、通常は、空気中で行う。所定の時間を保持すると、式（１１）のフェノール誘導体（フェノリックモノチオール）が得られる。得られたフェノール誘導体（フェノリックモノチオール）は、反応物混合系から単離・精製してもよいが、単離・精製することなくこれを原料として、式（２１）のフェノール誘導体の製造に供することができる。
【００２１】
次に、得られたフェノール誘導体（フェノリックモノチオール）を、溶媒中で、過酸化水素を用いて酸化反応させ、式（２１）のフェノール誘導体を得る。過酸化水素は、過酸化水素液（３０−３５％水溶液）として市販されているものを用いることができ、その使用量は基質であるフェノール誘導体（フェノリックモノチオール）と等モル又はほぼ等モルとする。
用いる溶媒としては、式（２１）のフェノール誘導体及び水（過酸化水素水中に存在するもの）の両方を溶かす溶媒、例えば、メタノール、エタノール等のアルコール類やアセトン等を用いることができ、好ましくはエタノールである。
反応温度や反応時間等の反応条件は、酸化反応が十分に進行する条件を選ぶ。概ね、反応温度５０℃〜７０℃、反応時間１時間〜３時間程度である。
【００２２】
さらに反応を具体的に説明する。フェノール誘導体（フェノリックモノチオール）の適量を反応容器に秤量し、これに過酸化水素液のエタノール希釈液（過酸化水素液と等重量のエタノールで薄めたもの）を徐々に滴下する。このとき滴下量は、過酸化水素基準でフェノール誘導体（フェノリックモノチオール）に対して等モル又はほぼ等モルとする。その後、攪拌しながら５０℃〜７０℃で加熱する。反応の進行をＧＰＣで確認する。反応終了後、アセトン及び蒸留水にて反応生成物を抽出し、さらにエバポレータにより濃縮し、式（２１）のフェノール誘導体（フェノリックジスルフィド）を得る。
【００２３】
なお、反応の進行過程を追ったＧＰＣは、溶離液にテトラヒドロフラン（ＴＨＦ）を用い、測定濃度は２．０ｇ／Ｌとした。測定機器は島津製作所製Ｃ−Ｒ４Ａ、カラムは東ソー社製ＴＳＫ ｇｅｌ Ｇ３０００ＨｘＬ＋ＴＳＫ ｇｅｌ Ｇ２０００ＨｘＬ、ＲＩモニタは日立製作所製Ｌ−３３００、ポンプには日立製作所製Ｌ−６０００を用いた。
【００２４】
【実施例】
以下、本発明を実施例により説明する。
実施例１ フェノリックモノチオール〔式（１４）のフェノール誘導体のうち、Ｒ_２が炭素数２のメチレン鎖である化合物〕の合成
２−アリルフェノール７４．０ｇ（０．５３６ｍｏｌ）をセパラブルフラスコに秤量し、これにエタンジチオール５０．５ｇ（０．５３６ｍｏｌ）を添加した。４つ口セパラブルフラスコの蓋（セパラブルカバー）側に還流管及び攪拌翼が付いた攪拌棒を取り付け、攪拌シールを介してその攪拌棒を攪拌用モータに繋いだ。この状態で、攪拌しながら、油浴上にて１５０℃で加熱を始めた。還流状態で、約４時間保持した。反応性生物のＧＰＣを図１に示した。２本のピークが存在し、初めに表れたピーク（左のピーク）は副生成物、２番目に表れたピーク（右のピーク）がモノチオール体である。
また、反応性生物の赤外吸収スペクトラムを図２に示した。２５５０ｃｍ^−１付近にチオール（ＳＨ）起因の吸収ピークが認められる。
【００２５】
実施例２ フェノリックジスルフィド〔式（２４）のフェノール誘導体のうち、Ｒ_２が炭素数２のメチレン鎖である化合物〕の合成
実施例１で得られたフェノリックモノチオール（含有率６５％）を３５ｇ（モノチオールのモル量が０．１ｍｏｌ）セパラブルフラスコに秤量し、エタノールで２倍にうすめた３０％過酸化水素水を徐々に滴下した（約３．４ｍｌ）。この後、攪拌しながら約７０℃で加熱した。ＧＰＣで反応の進行を追った。反応終了後、アセトン及び蒸留水にて反応生成物を抽出し、さらにエバポレータで濃縮した。濃縮物のＧＰＣを図３に示した。２本のピークがあり、初めに表れた大きなピーク（左のピーク）がフェノリックジスルフィド、２番目に表れたピーク（右のピーク）がモノチオール体のピークであった。これから、モノチオールがジスルフィドに反応していることが分かる。なお、ジスルフィドのピークは、図１の副生成物のピーク出現位置とわずかに異なっている。
濃縮物の赤外吸収スペクトラムを図４に示した。２５５０ｃｍ^−１付近のチオール（ＳＨ）起因の吸収ピークが消失していることから、チオールが反応してジスルフィドになったことが分かる。
【００２６】
＜応用例＞ 接着剤への応用
（ポリイミド樹脂の合成）
攪拌装置、窒素導入管、乾燥管を備えた１リットルの４つ口フラスコに、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパンを４１．０ｇ（０．１０モル）を入れ、窒素気流下、ＮＭＰ（Ｎ−メチルピロリドン）２５０ｇを加えて溶液とした。フラスコを水浴上に移し、激しく攪拌させながら１，２−（エチレン）ビス（トリメリテート二無水物）４１．０ｇ（０．１０モル）を少量ずつ加えた。酸二無水物がほぼ溶解したら、ゆっくりと攪拌しながら６時間反応させ、ポリアミド溶液を得た。
【００２７】
次に、前記のポリアミド溶液が入った４つ口フラスコに蒸留装置を装着し、キシレン２２０ｇを加えた。窒素気流下、１８０℃の油浴上で激しく攪拌しながら、イミド化により生成する縮合水をキシレン共に共沸留去した。その反応液を水中に注ぎ、沈殿したポリマーを濾別乾燥してポリイミド得た。
【００２８】
（ワニスの調合）
得られたポリイミド１００重量部に対してＤＭＡｃ（ジメチルアセトアミド）５００重量部とＴＣＧ−１（フィラー）２００重量部とを配合してポリイミドワニスを調合すると共に、この時点で、実施例２で得られたフェノリックジスルフィドを５重量部配合した。
【００２９】
（接着フィルムの作成）
ポリプロピレンフィルム基材上に上記ワニスを３０〜５０μｍの厚さに塗布し、８０℃で１０分、続いて１５０℃で３０分、加熱・乾燥し、室温で冷やしたのち、乾燥物を基材から剥がして接着フィルム（試験片Ａ）を得た。なお、上記フェノリックジスルフィド無添加で同様に作成した接着フィルム（試験片Ｂ）を比較（対照）として用いた。
【００３０】
（接着フィルムの評価）
上記方法で得られた接着フィルムについて、ピール接着力（引き剥がし強さ）を測定した。
接着フィルムを５ｍｍ×５ｍｍの大きさに切断し、これを５ｍｍ×５ｍｍのシリコンチップと銅リードフレームの間に挟み、１ｋｇの加重をかけて、１８０℃または２５０℃で圧着させた後、１８０℃で一時間加熱して接着フィルムを硬化させた。２４５℃または２７５℃、２０秒加熱時の引き剥がし強さをプッシュプルゲージで測定した。
【００３１】
（評価結果）
測定結果を表１に示した。
【表１】

【００３２】
フェノリックジスルフィドを配合していない接着フィルム（試験片Ｂ）のピール強度は、１８０℃圧着で０．３（２４５℃測定）、０．１（２７５℃測定）、２５０℃圧着で０．２（２４５℃測定）、０．１（２７５℃測定）であったのに対して、フェノリックジスルフィドを配合した接着フィルム（試験片Ａ）のピール強度は、１８０℃圧着で１．５（２４５℃測定）、１．７（２７５℃測定）、２５０℃圧着で１．９（２４５℃測定）、１．８（２７５℃測定）とピール強度が向上していた。
【００３３】
【発明の効果】
本発明の式（２１）のフェノール誘導体は新規な化合物である。
本発明の式（１１）のフェノール誘導体も新規な化合物であり、上記式（２１）のフェノール誘導体の合成中間体となる。
本発明に係る式（１１）のフェノール誘導体の製造法により、式（１１）のフェノール誘導体を容易に合成できる。
本発明に係る式（２１）のフェノール誘導体の製造法により、式（２１）のフェノール誘導体を容易に合成できる。
本発明で得られる式（２１）のフェノール誘導体は樹脂系接着剤に配合すれば、金属材料で被覆された表面層にも優れた接着力を示す。これらは、半導体実装技術に有用な添加剤となる。
【図面の簡単な説明】
【図１】実施例１における生成反応物（フェノリックモノチオール）のＧＰＣチャート
【図２】実施例１における生成反応物（フェノリックモノチオール）のＩＲ測定チャート
【図３】実施例２における生成反応物（フェノリックジスルフィド）のＧＰＣチャート
【図４】実施例２における生成反応物（フェノリックジスルフィド）のＩＲ測定チャート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel phenol derivative and a method for producing the same. The phenol derivative of the present invention is useful for improving the adhesive force of a polymer adhesive for liquid crystal display (LCD), semiconductor mounting and the like.
[0002]
[Prior art]
Phenolic resin is one of the widely used adhesives for liquid crystal displays (LCDs) for electrical and electronic parts and semiconductor packages, and specific phenol derivatives are used to enhance various properties of adhesives. is there.
[0003]
For example, in a conductive adhesive, in addition to an epoxy resin as a base resin, a polyallylphenol resin as a curing agent is blended to form an adhesive (Japanese Patent Laid-Open No. 6-322350).
[0004]
In the tape with adhesive for TAB, in addition to the polyimide resin that is a component of the adhesive, it contains a phenol derivative in which a sulfur atom or an oxygen atom is introduced between phenolic carbon and phenolic carbon, resulting in high adhesion and high insulation. A tape with an adhesive for TAB is obtained (Japanese Patent Laid-Open No. 11-260865).
[0005]
Moreover, in the adhesive for flexible printed circuit boards, a sulfur-containing phenol derivative having a specific structure is blended as an antioxidant for acrylonitrile butadiene rubber, which is a component other than the thermosetting resin (Japanese Patent Laid-Open No. 7-245478). ).
[0006]
On the other hand, with the further miniaturization and weight reduction of liquid crystal displays (LCD) and semiconductor packages, further advanced high-density packaging technology is required. In addition to copper, the surface layer of adherends targeted by adhesives such as recent anisotropic conductive films (ACF) and die bond films is also a comparison of silver, gold, gold / palladium, or silicon nitride. There is a relative increase in the number of metallic materials that are difficult to bond together.
[0007]
[Problems to be solved by the invention]
Surfaces coated with such materials as copper, silver, gold, gold / palladium, or silicon nitride are susceptible to contamination. In addition, conventional adhesives for these metal material surfaces may not always be satisfactory in terms of adhesion, stability, and the like.
[0008]
An object of the present invention is to provide a novel phenol derivative, and another object is to show excellent adhesion to a surface layer coated with a metal material such as copper, silver, gold, gold / palladium. It is to provide an adhesive.
[0009]
[Means for Solving the Problems]
The inventors of the present invention have studied various compounds or adhesives that exhibit excellent adhesion on metal surfaces coated with copper, silver, gold, gold / palladium, etc., and found that phenol derivatives having a thioether structure or a disulfide structure are bonded. The present inventors have found that it greatly contributes to improving the adhesive strength of the agent, and have completed the present invention.
[0010]
That is, the present invention is a phenol derivative (having a disulfide structure) represented by the formula (21).
[Chemical formula 5]

[Wherein R ₁ is a methylene chain having 2 or 3 carbon atoms, R ₂ is a methylene chain having 1 to 10 carbon atoms, G is a hydrogen atom, a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, It refers butoxy group, a hydroxyl group, a carboxyl group, a nitro group, an amine group, a nonyl group, a phenylene group, one of the benzyl group or a halogen atom].
[0011]
The present invention also relates to a method for producing a phenol derivative (having a disulfide structure) represented by formula (21). Phenol derivatives of the formula (21) is first (with thioether structure) represented by the formula (11) as a synthetic raw material for producing a phenol derivative.
[Chemical 6]

[Wherein R ₁ , R ₂ and G have the same meaning as in formula (21). ]
[0012]
Equation (11) In the production process of phenol induction of formula (1) or Formula (2)
[Chemical 7]

[Wherein G has the same meaning as in formula (21). A phenol compound represented by formula (3)
[Chemical 8]
_HS-R 2 -SH (3)
[Wherein, R ₂ has the same meaning as in formula (21). A dithiol represented by], Ru heated or reaction.
[0013]
The phenol derivatives of the so obtained this equation (11), in a solvent, characterized in that the oxidation reaction using hydrogen peroxide, is a method for producing a phenol derivative of the formula (21).
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described more specifically.
As described above, the phenol derivative having a disulfide structure of the present invention is a phenol derivative having a disulfide structure represented by the formula (21).
[0015]
Here, when R ₁ is a methylene chain having 3 carbon atoms, the phenol derivative is represented by the following formula (22).
[Chemical 9]

[Wherein R ₂ is a methylene chain having 1 to 10 carbon atoms, G is a hydrogen atom , methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy group, hydroxyl group, carboxyl group, nitro group, amine group , Nonyl group, phenylene group, benzyl group or halogen atom . ]
[0016]
When G is a methoxy group, the phenol derivative is represented, for example, by the following formula (23). When G is a hydrogen atom, the phenol derivative is represented, for example, by the following formula (24).
[Chemical Formula 10]

[Wherein R ₂ represents a methylene chain having 1 to 10 carbon atoms. ]
[0017]
Phenol derivatives with Chi thioether structure, as discussed above, a phenol derivative represented by the formula (11). Here, when R ₁ is a methylene chain having 3 carbon atoms, the phenol derivative is represented by the following formula (12).
Embedded image

[Wherein R ₂ is a methylene chain having 1 to 10 carbon atoms, G is a hydrogen atom , methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy group, hydroxyl group, carboxyl group, nitro group, amine group , Nonyl group, phenylene group, benzyl group or halogen atom . ]
[0018]
When G is a methoxy group, the phenol derivative is represented, for example, by the following formula (13). When G is a hydrogen atom, the phenol derivative is represented, for example, by the following formula (14).
Embedded image

[Wherein R ₂ represents a methylene chain having 1 to 10 carbon atoms. ]
[0019]
First, a method for producing a phenol derivative having a thioether structure of the formula (11) of the present invention will be described.
A predetermined amount of phenol substituted with an allyl group of formula (1) or phenol substituted with a vinyl group of formula (2) is weighed into a reaction vessel, and then a predetermined amount of dithiol of formula (3) is added. Here, the amount of phenol of formula (1) or phenol of formula (2) and the amount of dithiol of formula (3) are based on equimolar ratio. If one is more than the other, the excess remains unreacted, which is not preferable.
Reaction conditions such as reaction temperature and reaction time are selected so that the reaction (nucleophilic substitution reaction) proceeds sufficiently. In general, the reaction temperature is 100 ° C. to 200 ° C., and the reaction time is about 30 minutes to 7 hours.
[0020]
Further, the reaction will be specifically described. The reaction is heated while stirring and refluxing in a reaction vessel. The atmosphere may be an inert atmosphere such as nitrogen gas, but is usually performed in air. When the predetermined time is maintained, the phenol derivative (phenolic monothiol) of the formula (11) is obtained. The obtained phenol derivative (phenolic monothiol) may be isolated and purified from the reactant mixture system, but is used as a raw material for the production of the phenol derivative of formula (21) without isolation and purification. be able to.
[0021]
Next, the obtained phenol derivative (phenolic monothiol) is oxidized using hydrogen peroxide in a solvent to obtain a phenol derivative of the formula (21). As the hydrogen peroxide, a commercially available hydrogen peroxide solution (30-35% aqueous solution) can be used, and the amount used thereof is equimolar or nearly equimolar with the phenol derivative (phenolic monothiol) as the substrate. To do.
As the solvent to be used, a solvent that dissolves both the phenol derivative of the formula (21) and water (present in hydrogen peroxide water), for example, alcohols such as methanol and ethanol, acetone, and the like can be used. Ethanol.
Reaction conditions such as reaction temperature and reaction time are selected so that the oxidation reaction proceeds sufficiently. In general, the reaction temperature is 50 to 70 ° C., and the reaction time is about 1 to 3 hours.
[0022]
Further, the reaction will be specifically described. An appropriate amount of a phenol derivative (phenolic monothiol) is weighed in a reaction vessel, and an ethanol dilution of a hydrogen peroxide solution (thinned with an equal weight of ethanol to a hydrogen peroxide solution) is gradually added dropwise thereto. At this time, the dropping amount is equimolar or almost equimolar with respect to the phenol derivative (phenolic monothiol) based on hydrogen peroxide. Then, it heats at 50 to 70 degreeC, stirring. The progress of the reaction is confirmed by GPC. After completion of the reaction, the reaction product is extracted with acetone and distilled water, and further concentrated by an evaporator to obtain a phenol derivative (phenolic disulfide) of the formula (21).
[0023]
In addition, GPC which followed the progress process of reaction used tetrahydrofuran (THF) as an eluent, and measured concentration was 2.0 g / L. The measuring instrument was C-R4A manufactured by Shimadzu Corporation, the column was TSK gel G3000HxL + TSK gel G2000HxL manufactured by Tosoh Corporation, the RI monitor was L-3300 manufactured by Hitachi, and the pump L-6000 manufactured by Hitachi was used.
[0024]
【Example】
Hereinafter, the present invention will be described with reference to examples.
Example 1 Synthesis of phenolic monothiol [a compound in which R ₂ is a methylene chain having 2 carbon atoms among the phenol derivatives of formula (14)] Weigh 74.0 g (0.536 mol) of allylphenol into a separable flask. Then, 50.5 g (0.536 mol) of ethanedithiol was added thereto. A stirring rod with a reflux tube and a stirring blade was attached to the lid (separable cover) side of the four-necked separable flask, and the stirring rod was connected to a stirring motor via a stirring seal. In this state, heating was started at 150 ° C. on an oil bath while stirring. Hold at reflux for about 4 hours. The GPC of the reactive organism is shown in FIG. There are two peaks. The first peak (left peak) is a by-product, and the second peak (right peak) is a monothiol form.
Moreover, the infrared absorption spectrum of the reactive organism is shown in FIG. An absorption peak due to thiol (SH) is observed in the vicinity of 2550 cm ⁻¹ .
[0025]
Example 2 Synthesis of phenolic disulfide [a compound in which R ₂ is a methylene chain having 2 carbon atoms among the phenol derivatives of formula (24)] 35 g of phenolic monothiol (65% content) obtained in Example 1 30% hydrogen peroxide solution diluted with ethanol twice was gradually added dropwise (about 3.4 ml). This was followed by heating at about 70 ° C. with stirring. The progress of the reaction was followed by GPC. After completion of the reaction, the reaction product was extracted with acetone and distilled water, and further concentrated with an evaporator. The GPC of the concentrate is shown in FIG. There were two peaks. The first large peak (left peak) was phenolic disulfide, and the second peak (right peak) was a monothiol peak. This shows that monothiol is reacting with disulfide. The disulfide peak is slightly different from the peak appearance position of the by-product in FIG.
The infrared absorption spectrum of the concentrate is shown in FIG. Since the absorption peak due to thiol (SH) near 2550 cm ⁻¹ disappears, it can be seen that the thiol reacted to become disulfide.
[0026]
<Application examples> Application to adhesives (synthesis of polyimide resin)
Into a 1 liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a drying tube was placed 41.0 g (0.10 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane. In a nitrogen stream, 250 g of NMP (N-methylpyrrolidone) was added to prepare a solution. The flask was transferred to a water bath, and 41.0 g (0.10 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little with vigorous stirring. When the acid dianhydride was almost dissolved, the mixture was reacted for 6 hours with slow stirring to obtain a polyamide solution.
[0027]
Next, a distillation apparatus was attached to the four-necked flask containing the polyamide solution, and 220 g of xylene was added. Condensed water produced by imidization was distilled off azeotropically with xylene while stirring vigorously on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain a polyimide.
[0028]
(Varnish formulation)
A polyimide varnish was prepared by blending 500 parts by weight of DMAc (dimethylacetamide) and 200 parts by weight of TCG-1 (filler) with respect to 100 parts by weight of the obtained polyimide. 5 parts by weight of phenolic disulfide was added.
[0029]
(Creation of adhesive film)
The above varnish is applied on a polypropylene film substrate to a thickness of 30 to 50 μm, heated and dried at 80 ° C. for 10 minutes, then at 150 ° C. for 30 minutes, cooled at room temperature, and dried product is removed from the substrate. The adhesive film (test piece A) was obtained by peeling. In addition, the adhesive film (test piece B) produced similarly without adding the phenolic disulfide was used as a comparison (control).
[0030]
(Evaluation of adhesive film)
About the adhesive film obtained by the said method, the peel adhesive force (peeling strength) was measured.
The adhesive film is cut into a size of 5 mm × 5 mm, and is sandwiched between a 5 mm × 5 mm silicon chip and a copper lead frame, applied with a weight of 1 kg and pressed at 180 ° C. or 250 ° C., and then 180 ° C. The adhesive film was cured by heating for 1 hour. The peel strength when heated at 245 ° C. or 275 ° C. for 20 seconds was measured with a push-pull gauge.
[0031]
(Evaluation results)
The measurement results are shown in Table 1.
[Table 1]

[0032]
The peel strength of the adhesive film containing no phenolic disulfide (test piece B) is 0.3 (measured at 245 ° C.), 0.1 (measured at 275 ° C.), 0.1 (measured at 275 ° C.), and 0.2 (245) at 250 ° C. The peel strength of the adhesive film (test piece A) blended with phenolic disulfide is 1.5 (measured at 245 ° C.) at 180 ° C., whereas 0.1 (measured at 275 ° C.). The peel strength was improved by 1.7 (measured at 275 ° C.) and 1.9 (measured at 245 ° C.) and 1.8 (measured at 275 ° C.) when pressed at 250 ° C.
[0033]
【The invention's effect】
The phenol derivative of the formula (21) of the present invention is a novel compound.
The phenol derivative of the formula (11) of the present invention is also a novel compound and becomes a synthetic intermediate of the phenol derivative of the formula (21).
The phenol derivative of formula (11) can be easily synthesized by the method for producing a phenol derivative of formula (11) according to the present invention.
By the method for producing a phenol derivative of formula (21) according to the present invention, a phenol derivative of formula (21) can be easily synthesized.
When the phenol derivative of the formula (21) obtained in the present invention is blended with a resin-based adhesive, it exhibits excellent adhesive force even on a surface layer coated with a metal material. These are useful additives for semiconductor packaging technology.
[Brief description of the drawings]
1 is a GPC chart of a product reactant (phenolic monothiol) in Example 1. FIG. 2 is an IR measurement chart of a product reactant (phenolic monothiol) in Example 1. FIG. 3 is a product reactant in Example 2. GPC chart of (phenolic disulfide) FIG. 4 is an IR measurement chart of the product reaction product (phenolic disulfide) in Example 2.

Claims (2)

A phenol derivative represented by the formula (21).

[Wherein R ₁ is a methylene chain having 2 or 3 carbon atoms, R ₂ is a methylene chain having 1 to 10 carbon atoms , G is a hydrogen atom , a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, A butoxy group, a hydroxyl group, a carboxyl group, a nitro group, an amine group, a nonyl group, a phenylene group, a benzyl group, or a halogen atom is shown. ] Formula (1) or Formula (2)

[Wherein G is a hydrogen atom , methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy group, hydroxyl group, carboxyl group, nitro group, amine group, nonyl group, phenylene group, benzyl group or halogen atom. Indicates either . A phenol compound represented by formula (3)
[Chemical 3]
_HS-R 2 -SH (3)
[Wherein R ₂ represents a methylene chain having 1 to 10 carbon atoms. A dithiol represented by], heated to produce phenol derivatives reacted formula (11), a phenol derivative of formula (11), in a solvent, to the oxidation reaction with hydrogen peroxide, claim A process for producing a phenol derivative of formula (21) according to 1.

[Wherein R ₁ is a methylene chain having 2 or 3 carbon atoms , R ₂ is a methylene chain having 1 to 10 carbon atoms, G is a hydrogen atom, a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, A butoxy group, a hydroxyl group, a carboxyl group, a nitro group, an amine group, a nonyl group, a phenylene group, a benzyl group, a halogen atom, or a substituent is shown. ]

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